CN106220575A - A kind of hydrazone compounds containing methoxyl group benzopyrazines structure and preparation method and application - Google Patents
A kind of hydrazone compounds containing methoxyl group benzopyrazines structure and preparation method and application Download PDFInfo
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- CN106220575A CN106220575A CN201610615196.4A CN201610615196A CN106220575A CN 106220575 A CN106220575 A CN 106220575A CN 201610615196 A CN201610615196 A CN 201610615196A CN 106220575 A CN106220575 A CN 106220575A
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- methoxyl group
- compound
- hydrazone compounds
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- compounds containing
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- -1 hydrazone compounds Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 claims description 4
- MFYLRNKOXORIPK-UHFFFAOYSA-N (3-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 MFYLRNKOXORIPK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 claims description 4
- ZBBQSGVRBQKLLE-UHFFFAOYSA-N 3-phenyl-1H-quinoxalin-2-one Chemical compound OC1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 ZBBQSGVRBQKLLE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical group ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- 230000002363 herbicidal effect Effects 0.000 claims description 3
- 239000004009 herbicide Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000009333 weeding Methods 0.000 abstract description 13
- 239000000575 pesticide Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 229940126214 compound 3 Drugs 0.000 abstract description 3
- 238000012827 research and development Methods 0.000 abstract description 2
- 229940125904 compound 1 Drugs 0.000 abstract 2
- 229940125782 compound 2 Drugs 0.000 abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 55
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 15
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 240000007241 Agrostis stolonifera Species 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- MQIVNMHALJNFMG-ILYHAJGMSA-N Benquinox Chemical compound O/N=C(\C=C1)/C=C/C\1=N\NC(C1=CC=CC=C1)=O MQIVNMHALJNFMG-ILYHAJGMSA-N 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- 240000003211 Corylus maxima Species 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000233639 Pythium Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QYCSNMDOZNUZIT-UHFFFAOYSA-N benzhydrylidenehydrazine Chemical class C=1C=CC=CC=1C(=NN)C1=CC=CC=C1 QYCSNMDOZNUZIT-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XFDJMIHUAHSGKG-UHFFFAOYSA-N chlorethoxyfos Chemical compound CCOP(=S)(OCC)OC(Cl)C(Cl)(Cl)Cl XFDJMIHUAHSGKG-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of hydrazone compounds containing methoxyl group benzopyrazines structure and its preparation method and application.It prepares compound 1 with 7 methoxyl group ortho-nitranilines and hydrazine hydrate；Compound 1 prepares compound 2 with BMF effect；Compound 2 and phosphorus oxychloride reaction prepare compound 3；Compound 3 and hydrazine hydrate react and prepare compound 4；Compound 4 reacts prepared compound (I) with replacing aldehyde compound.Its raw material is simple and easy to get, and preparation method is simple, convenient post-treatment, and product yield is high, and this compound is to have certain activity of weeding, provides the foundation for novel pesticide research and development.
Description
Technical field
The invention belongs to hydrazone compounds preparing technical field, be specifically related to a kind of hydrazone containing methoxyl group benzopyrazines structure
Compounds and preparation method and application.
Background technology
Heterocycle structure is synthetic drug, the important key factor of the materials such as pesticide, and this is efficient due to heterocycle, low toxicity and
Can carry out what diversified substituted feature was determined.It has become as medicine, a study hotspot in the field of pesticide.Hydrazone class
Compound has the biological activity widely such as good weeding, parasite killing, sterilization, simultaneously because tying containing C=N Asia in its molecular structure
Structure so that it is have stronger coordination ability and various coordination mode, can synthesize a lot of highly active new compound, and hydrazone
Compounds and coordination compound thereof also have good antitumor and antioxidative activity, therefore lead at pesticide, medicine, detection and material
All there is application in territory.The extensive concern of the person that receives pesticide research especially, studies more and more deep in terms of New pesticides discovery.Previous generation
Recording the kind of the existing commercialization fifties, E.I.Du Pont Company reported Benzophenonehydrazones analog derivative when 1973 to be had and well kills
Worm activity, especially has high-efficiency activated to lepidoptera pest；The benquinox that Beyer Co., Ltd develops is preventing and treating pythium spp and soil fungi
The seed and the sprout term disease that cause have better effects；Schiff bases and fatty acyl hydrazone compounds are by obvious activity of weeding, and it is right
Broad leaved weed and barnyard grass have excellent activity.
The present invention based on before research on the basis of provide a kind of have activity of weeding containing methoxyl group benzopyrazines tie
The preparation method of the hydrazone compounds of structure and application technology.
Summary of the invention
It is an object of the present invention to provide a kind of hydrazone compounds containing methoxyl group benzopyrazines structure with activity of weeding and
Its preparation method and application.
Described a kind of hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that its structural formula such as (I) institute
Show:
Wherein: R1It is 2,4-Dichlorobenzene base, 4-trifluoromethyl, 2-hydroxy phenyl, 2-nitrobenzophenone, 2-fluorophenyl,
4-bromophenyl, 3-chlorphenyl, 2-methoxyphenyl, 3-nitrobenzophenone, 3,4-Dimethoxyphenyls, 4-aminomethyl phenyl.
The preparation method of the described hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that include walking as follows
Rapid:
1) in organic solvent, under the effect of Raney Ni, 5-methoxyl group ortho-nitraniline and hydrazine hydrate reaction obtain such as formula
Compound 4-methoxyl group o-phenylenediamine shown in 1；
2) in organic solvent, by step 1) the 4-methoxyl group o-phenylenediamine that obtains reacts with MBF under ethanol effect
To compound 7-methoxyl group 2-hydroxyl-3-phenyl quinoxaline as shown in Equation 2；
3) by step 2) the 7-methoxyl group 2-hydroxyl-3-phenyl quinoxaline that obtains generates such as formula with phosphorus oxychloride action-reaction
Compound 7-methoxyl group-2-chloro-3-phenyl quinoxaline shown in 3；
4) by step 3) the 7-methoxyl group-2-chloro-3-phenyl quinoxaline that obtains generates such as formula 4 institute with hydrazine hydrate action-reaction
Compound (7-methoxyl group-3-phenyl quinoxaline-2-base) hydrazine shown；
5) under ethanol effect, by step 4) (7-methoxyl group-3-phenyl quinoxaline-2-base) hydrazine of obtaining with replace aldehydes
Compound reaction generates the target hydrazone compounds as shown in formula (I), and the substituent group replaced in aldehyde compound is 2,4-dichloro
Phenyl, 4-trifluoromethyl, 2-hydroxy phenyl, 2-nitrobenzophenone, 2-fluorophenyl, 4-bromophenyl, 3-chlorphenyl, 2-methoxyl group
Phenyl, 3-nitrobenzophenone, 3,4-Dimethoxyphenyls or 4-aminomethyl phenyl.；
Preparation process is as follows:
The preparation method of the described hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that step 1) in 5-
The amount of the material of methoxyl group ortho-nitraniline and the mass ratio of Raney Ni are 1:2.5～4.5；Consumption of organic solvent is with 5-first
The amount of the material of epoxide ortho-nitraniline is calculated as 0.3～0.5ml/mmol, and the consumption of the hydrazine hydrate of 85% is with 5-methoxyl group neighbour's nitre
The amount of the material of base aniline is calculated as 0.7～0.8ml/mmol.
The preparation method of the described hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that step 2) in 4-
Methoxyl group o-phenylenediamine is 1:1.5～3.5 with the ratio of the amount of the material of MBF, and consumption of organic solvent is with 4-methoxyl group o-phenylenediamine
The amount of material be calculated as 0.9～1.1ml/mmol.
The preparation method of the described hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that step 3) in three
Chlorethoxyfos volumetric usage is calculated as 0.3～0.5ml/mmol with the amount of the material of 7-methoxyl group-2-hydroxyl-3-phenyl quinoxaline.
The preparation method of the described hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that step 4) in 7-
Methoxyl group-2-chloro-3-phenyl quinoxaline is 1:1.5～4.5 with the ratio of the amount of the material of hydrazine hydrate.
The preparation method of the described hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that step 5) in
(7-methoxyl group-3-phenyl quinoxaline-2-base) hydrazine is 1:0.9～1.1 with the ratio of the amount of the material replacing aldehyde compound.
The preparation method of the described hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that step 5) in have
Machine solvent load is calculated as 7.0～8.0ml/mmol with the amount replacing the material of aldehyde compound.
The described hydrazone compounds containing methoxyl group benzopyrazines structure is as the application of herbicide.
Compared with prior art, the beneficial effects are mainly as follows: the invention provides a kind of containing methoxybenzene
And the preparation method of the hydrazone compounds of pyrazine structure and application, its raw material is simple and easy to get, and preparation method is simple, post processing side
Just, product yield is high, and this compound, for having activity of weeding, particularly has good preventing and treating when preventing and treating the weeds such as creeping bentgrass
Effect, the research and development for novel pesticide provide the foundation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This:
The hydrazone compounds containing methoxyl group benzopyrazines structure (I) of the present invention can synthesize in the following manner:
In 250mL single port flask, it is sequentially added into 0.1mol 7-methoxyl group ortho-nitraniline, 40mL methanol, 75mL hydration
Hydrazine (85%), 0.25～0.45Raney Ni (weight in wet base), be heated to reflux, and follows the trail of with TCL and disappears to raw material, and reaction cools down after terminating
To room temperature, being filtered to remove Raney Ni, decompression is distilled off solvent and obtains filbert crystal, i.e. obtains chemical combination as shown in Equation 1
Thing 1 o-phenylenediamine.In 250mL single port flask, add 0.1mol o-phenylenediamine, dissolved with 100mL ethanol, more slowly drip
Add MBF, have yellow solid to occur, according to substituent R during dropping1Change, the response time is different, reacts at normal temperatures
Time period is 30-120min, after reaction completely, is filtered to remove solvent, with alcohol flushing three times, obtains chemical combination as shown in Equation 2
Thing 7-methoxyl group-2-hydroxyl-3-phenyl quinoxaline.40mLPOCl is added in compound 23Make solvent, under heated reflux condition
Carrying out chlorination, follow the trail of with TLC and disappear to raw material, reaction is cooled to room temperature after terminating, and is poured slowly in 500g frozen water, separates out immediately
A large amount of yellow solids, sucking filtration, washing are dried, and obtain compound 3 as shown in Equation 3.In 250mL there-necked flask, add chemical combination
Thing 3 also makees solvent with 60mL ethanol, is slowly added dropwise the hydrazine hydrate of 18g (0.3mol) 85%, is warming up to backflow, instead after dropping
Answering 4-5h, reaction is cooled to room temperature after terminating, and pours in 300g frozen water, separates out a large amount of white solid immediately, through sucking filtration, washing and
It is dried, prepares thick product, obtain compound 4 as shown in Equation 4 by recrystallization.0.377g is added in 50mL round-bottomed flask
(0.002mol) hydrazine, addition 15mL ethanol does and is slowly added dropwise 0.002mol replacement aldehyde compound, raw material under solvent, stirring condition
Dissolve rapidly, then have solid to separate out, be stirred overnight under room temperature, some plate monitoring, after raw material reaction is complete, sucking filtration, use petroleum ether
Wash three times with the mixed liquor of ethanol, obtain reddish yellow pressed powder, i.e. as shown in formula (I) containing methoxyl group benzopyrazines structure
Hydrazone compounds.
Embodiment 1～11, the structural formula of particular compound is as shown in table 2, and other synthesis condition does not changes.
Embodiment 1
(E)-3-(2-(2-fluorophenyl) hydrazine)-6-methoxyl group-phenyl quinoxaline, reddish yellow solid, productivity 51.6%,
m.p.86-88℃；1H NMR (400MHz, CDCl3/TMS), δ 3.99 (s, 3H, OCH3), 7.06 (q, J=8.8Hz, 1H, Ph-
H), 7.23 (q, J=7.1Hz, 1H, Ph-H), 7.47 (m, 2H, Ph-H), 7.55-7.58 (m, 5H, Ph-H), 7.87 (m, 3H,
Ph-H), 7.97 (d, J=10.0Hz, 1H, Ph-H), 8.15 (m, 2H, 1NH, 1=CH) .HRMS (ESI) m/z:Calculated,
373.1459,Found,373.1464[M+H]+
Embodiment 2
(E)-2-((2-(7-methoxyl group-3-phenyl quinoxaline-2-base) hydrazine) methyl) phenol, reddish yellow solid, productivity
63.0%, m.p.101-104 DEG C；1H NMR (400MHz, CDCl3/TMS), δ 4.00 (s, 3H, OCH3), 7.32 (t, J=
6.0Hz, 1H, Ph-H), 7.46-7.62 (m, 7H, Ph-H), 7.80-7.88 (m, 3H, Ph-H), 7.97 (d, J=6.0Hz, 1H,
Ph-H).HRMS(ESI)m/z:Calculated,371.1503,Found,371.1514[M+H]+
Embodiment 3
(E)-3-(2-(2,4-Dichlorobenzene base) hydrazine)-6-methoxyl group-2-phenyl quinoxaline, reddish yellow solid, productivity
73.4%, m.p.80-84 DEG C；1H NMR (400MHz, CDCl3/TMS), δ 4.00 (s, 3H, OCH3), 7.32 (d, J=8.0Hz,
1H, Ph-H), 7.40 (d, J=9.2Hz, 1H, Ph-H), 7.47 (m, 2H, Ph-H), 7.56 (m, 3H, Ph-H), 7.86 (m, 2H,
Ph-H), 7.97 (d, J=10.0Hz, 1H, Ph-H), 8.12 (d, J=10.0Hz, 1H, NH), 8.19 (m, 1H ,=CH) .HRMS
(ESI)m/z:Calculated,423.0774,Found,423.0776[M+H]+
Embodiment 4
(E)-3-(2-(3-chlorphenyl) hydrazine)-6-methoxyl group-2-phenyl quinoxaline, reddish yellow solid, productivity 64.9%,
m.p.74-77℃；1H NMR(400MHz,CDCl3/TMS),δ4.02(s,3H,OCH3),7.33(m,1H,Ph-H),7.43(m,
1H, Ph-H), 7.50-7.56 (m, 7H, Ph-H), 7.63 (m, 3H, Ph-H), 8.02 (s, 1H, NH), 8.10 (d, J=8.2Hz,
1H ,=CH) .HRMS (ESI) m/z:Calculated, 389.1164, Found, 389.1163 [M+H]+
Embodiment 5
(E)-6-methoxyl group-2-phenyl-3-(2-(4-(trifluoromethyl) benzal) hydrazine) quinoxaline, reddish yellow solid, produces
Rate 22.0%, m.p.162-165 DEG C；1H NMR(400MHz,CDCl3/TMS),δ4.00(s,3H,OCH3),7.47(m,2H,
Ph-H), 7.56 (m, 5H, Ph-H), 7.74 (d, J=5.6Hz 1H, Ph-H), 7.88 (m, 3H, Ph-H), 7.97 (d, J=
6.0Hz,1H,Ph-H).HRMS(ESI)m/z:Calculated,423.1427,Found,423.1436[M+H]+
Embodiment 6
(E)-6-methoxyl group-3-(2-(2-nitrobenzophenone) hydrazine)-2-phenyl quinoxaline, reddish yellow solid, productivity 98.0%,
m.p.149-151℃；1H NMR(400MHz,CDCl3/TMS),δ4.00(s,3H,OCH3),7.46(s,1H,Ph-H),7.56
(m, 3H, Ph-H), 7.61 (m, 3H, Ph-H), 7.70 (t, J=6.4Hz, 2H, Ph-H), 7.87 (m, 2H, Ph-H), 7.97 (d, J
=6.0Hz, 1H, Ph-H), 8.04 (d, J=5.6Hz, 1H, NH), 8.33 (m, 1H ,=CH) .HRMS (ESI) m/z:
Calculated,400.1404,Found,400.1411[M+H]+
Embodiment 7
(E)-6-methoxyl group-3-(2-(3-nitrobenzophenone) hydrazine)-2-phenyl quinoxaline, reddish yellow solid, productivity 72.0%,
m.p.147-150℃；1H NMR(400MHz,CDCl3/TMS),δ4.00(s,3H,OCH3),7.40(s,1H,Ph-H),7.46
(s, 1H, Ph-H), 7.55 (m, 3H, Ph-H), 7.60 (t, J=7.8Hz, 1H, Ph-H), 7.61 (m, 1H, Ph-H), 7.87 (m,
2H, Ph-H), 7.97 (d, J=8.0Hz, 1H, Ph-H), 8.10 (m, 1H, NH), 8.26 (m, 1H ,=CH) .HRMS (ESI) m/z:
Calculated,400.1404,Found,400.1413[M+H]+
Embodiment 8
(E)-3-(2-(3,4-Dimethoxyphenyl) hydrazine)-6-methoxyl group-2-phenyl quinoxaline, reddish yellow solid, productivity
69.9%, m.p.130-134 DEG C；1H NMR(400MHz,CDCl3/TMS),δ3.95(s,3H,OCH3),3.99(s,3H,
OCH3),4.02(s,3H,OCH3),7.46(s,1H,Ph-H),7.55-7.63(m,7H,Ph-H),7.87(m,2H,Ph-H),
7.97 (d, J=6.4Hz, 1H, Ph-H) .HRMS (ESI) m/z:Calculated, 415.1765, Found, 415.1772 [M+H]
+ embodiment 9
(E)-6-methoxyl group-3-(2-(2-methoxyphenyl) hydrazine)-2-phenyl quinoxaline, reddish yellow solid, productivity
49.0%, m.p.116-120 DEG C；1H NMR(400MHz,CDCl3/TMS),δ4.00(s,6H,OCH3),7.36(m,1H,Ph-
H), 7.46 (s, 1H, Ph-H), 7.54-7.64 (m, 7H, Ph-H), 7.87 (m, 2H, Ph-H), 7.97 (d, J=8.0Hz, 1H,
Ph-H), 8.18 (m, 1H, NH), 8.89 (m, 1H ,=CH) .HRMS (ESI) m/z:Calculated, 385.1659, Found,
385.1669[M+H]+
Embodiment 10
(E)-3-(2-(4-bromophenyl) hydrazine)-6-methoxyl group-2-phenyl quinoxaline, reddish yellow solid, productivity 63.9%,
m.p.123-127℃；1H NMR(400MHz,CDCl3/TMS),δ4.00(s,3H,OCH3),7.46(s,1H,Ph-H),7.55-
7.57 (m, 5H, Ph-H), 7.66 (m, 3H, Ph-H), 7.87 (m, 2H, Ph-H), 7.97 (d, J=5.6Hz, 1H, Ph-H) .HRMS
(ESI)m/z:Calculated,433.0659,Found,433.0500[M+H]+
Embodiment 11
(E)-6-methoxyl group-3-(2-(4-aminomethyl phenyl) hydrazine)-2-phenyl quinoxaline, reddish yellow solid, productivity 52.2%,
m.p.140-144℃；1H NMR(400MHz,CDCl3/TMS),δ2.40(s,3H,CH3),4.00(s,3H,OCH3),7.47(m,
1H, Ph-H), 7.55-7.63 (m, 6H, Ph-H), 7.77 (m, 2H, Ph-H), 7.88 (m, 2H, Ph-H), 7.97 (d, J=
6.0Hz,1H,Ph-H).HRMS(ESI)m/z:Calculated,369.1710,Found,369.1720[M+H]+
Embodiment 12 activity of weeding is tested
Subjects: creeping bentgrass, Caulis et Folium Lactucae Sativae.
Test method: complete the filter paper of a diameter 5.6cm in the culture dish of diameter 6cm, add 2 milliliters certain density
Test compounds solution, the sowing seed soaking Semen Brassicae campestris 10 of 6 hours.At 28 ± 1 DEG C, dark culturing measures radicle after 7 days long
Degree.By compound under dark condition, the growth inhibited of crop radicle is come the activity of weeding of detection compound.Test concentrations:
1mM.Each process is in triplicate.Activity graded index: 5 grades: >=80%；4 grades: 60～80%；3 grades: 40～59%；2 grades: 20
～39%；1 grade: 1～20%；0 grade: 0%.
Activity of weeding test result is as shown in table 1
The Herbicide activity data of table 1 compound C1-C11
Showing from table 1 activity of weeding, the selected 2 kinds of plants of test are had necessarily under test sets concentration by this compounds
Activity of weeding.Compound C5 is to creeping bentgrass, and Caulis et Folium Lactucae Sativae all has certain activity of weeding, and compound C6, C8 are respectively to Caulis et Folium Lactucae Sativae, Jian's stock
Grain husk has certain activity of weeding.Particular compound structure is as shown in table 2
The concrete structure of table 2 compound C1-C11
Claims (9)
1. the hydrazone compounds containing methoxyl group benzopyrazines structure, it is characterised in that its structural formula is as shown in (I):
Wherein: R1It is 2,4-Dichlorobenzene base, 4-trifluoromethyl, 2-hydroxy phenyl, 2-nitrobenzophenone, 2-fluorophenyl, 4-bromobenzene
Base, 3-chlorphenyl, 2-methoxyphenyl, 3-nitrobenzophenone, 3,4-Dimethoxyphenyls, 4-aminomethyl phenyl.
2. a preparation method for the hydrazone compounds containing methoxyl group benzopyrazines structure as claimed in claim 1, its feature
It is to comprise the steps:
1) in organic solvent, under the effect of Raney Ni, 5-methoxyl group ortho-nitraniline and hydrazine hydrate reaction obtain such as formula 1 institute
The compound 4-methoxyl group o-phenylenediamine shown；
2) in organic solvent, by step 1) the 4-methoxyl group o-phenylenediamine that obtains react with MBF under ethanol effect obtain as
Compound 7-methoxyl group 2-hydroxyl-3-phenyl quinoxaline shown in formula 2；
3) by step 2) the 7-methoxyl group 2-hydroxyl-3-phenyl quinoxaline that obtains generates such as formula 3 institute with phosphorus oxychloride action-reaction
The compound 7-methoxyl group-2-chloro-3-phenyl quinoxaline shown；
4) by step 3) the 7-methoxyl group-2-chloro-3-phenyl quinoxaline that obtains generates as shown in Equation 4 with hydrazine hydrate action-reaction
Compound (7-methoxyl group-3-phenyl quinoxaline-2-base) hydrazine；
5) under ethanol effect, by step 4) (7-methoxyl group-3-phenyl quinoxaline-2-base) hydrazine of obtaining with replace aldehydes chemical combination
Thing reaction generates the target hydrazone compounds as shown in formula (I), and the substituent group replaced in aldehyde compound is 2,4-Dichlorobenzene base,
4-trifluoromethyl, 2-hydroxy phenyl, 2-nitrobenzophenone, 2-fluorophenyl, 4-bromophenyl, 3-chlorphenyl, 2-methoxyphenyl,
3-nitrobenzophenone, 3,4-Dimethoxyphenyls or 4-aminomethyl phenyl.；
Preparation process is as follows:
The preparation method of the hydrazone compounds containing methoxyl group benzopyrazines structure the most according to claim 2, its feature exists
In step 1) in the amount of material of 5-methoxyl group ortho-nitraniline and the mass ratio of Raney Ni be 1:2.5～4.5；Organic molten
Agent consumption is calculated as 0.3～0.5ml/mmol with the amount of the material of 5-methoxyl group ortho-nitraniline, the consumption of the hydrazine hydrate of 85% with
The amount of the material of 5-methoxyl group ortho-nitraniline is calculated as 0.7～0.8ml/mmol.
The preparation method of the hydrazone compounds containing methoxyl group benzopyrazines structure the most according to claim 2, its feature exists
In step 2) in the ratio of 4-methoxyl group o-phenylenediamine and the amount of the material of MBF be 1:1.5～3.5, consumption of organic solvent is with 4-first
The amount of the material of epoxide o-phenylenediamine is calculated as 0.9～1.1ml/mmol.
The preparation method of the hydrazone compounds containing methoxyl group benzopyrazines structure the most according to claim 2, its feature exists
In step 3) in phosphorus oxychloride volumetric usage with the amount of the material of 7-methoxyl group-2-hydroxyl-3-phenyl quinoxaline be calculated as 0.3～
0.5ml/mmol。
The preparation method of the hydrazone compounds containing methoxyl group benzopyrazines structure the most according to claim 2, its feature exists
In step 4) in the ratio of 7-methoxyl group-2-chloro-3-phenyl quinoxaline and the amount of the material of hydrazine hydrate be 1:1.5～4.5.
The preparation method of the hydrazone compounds containing methoxyl group benzopyrazines structure the most according to claim 2, its feature exists
In step 5) in the ratio of amount of (7-methoxyl group-3-phenyl quinoxaline-2-base) hydrazine and the material replacing aldehyde compound be 1:0.9
～1.1.
The preparation method of the hydrazone compounds containing methoxyl group benzopyrazines structure the most according to claim 2, its feature exists
In step 5) in consumption of organic solvent be calculated as 7.0～8.0ml/mmol with the amount of material replacing aldehyde compound.
9. the hydrazone compounds application as herbicide containing methoxyl group benzopyrazines structure as claimed in claim 1.
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|---|---|---|---|---|
| CN86106281A (en) * | 1985-08-20 | 1987-03-04 | 山道士有限公司 | Semicarbazone class and thiosemicarbazone class |
| CN103509408B (en) * | 2012-06-15 | 2015-03-25 | 佳能株式会社 | Ink, ink cartridge and ink jet recording method |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106281A (en) * | 1985-08-20 | 1987-03-04 | 山道士有限公司 | Semicarbazone class and thiosemicarbazone class |
| CN103509408B (en) * | 2012-06-15 | 2015-03-25 | 佳能株式会社 | Ink, ink cartridge and ink jet recording method |
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