CN106220575B - A kind of hydrazone compounds and the preparation method and application thereof of the structure of benzopyrazines containing methoxyl group - Google Patents
A kind of hydrazone compounds and the preparation method and application thereof of the structure of benzopyrazines containing methoxyl group Download PDFInfo
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- CN106220575B CN106220575B CN201610615196.4A CN201610615196A CN106220575B CN 106220575 B CN106220575 B CN 106220575B CN 201610615196 A CN201610615196 A CN 201610615196A CN 106220575 B CN106220575 B CN 106220575B
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- methoxyl group
- compound
- hydrazone compounds
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- -1 hydrazone compounds Chemical class 0.000 title claims abstract description 76
- 150000003252 quinoxalines Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 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 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000036571 hydration Effects 0.000 claims abstract description 4
- 238000006703 hydration reaction Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- KPGPIQKEKAEAHM-UHFFFAOYSA-N 2-chloro-3-phenylquinoxaline Chemical compound ClC1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 KPGPIQKEKAEAHM-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 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 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 240000007241 Agrostis stolonifera Species 0.000 claims description 4
- 244000106835 Bindesalat Species 0.000 claims description 4
- 235000000318 Bindesalat Nutrition 0.000 claims description 4
- 230000002363 herbicidal effect Effects 0.000 claims description 4
- 239000004009 herbicide Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- OHTYZZYAMUVKQS-UHFFFAOYSA-N phenyl-[4-(trifluoromethyl)phenyl]methanone Chemical group C1=CC(C(F)(F)F)=CC=C1C(=O)C1=CC=CC=C1 OHTYZZYAMUVKQS-UHFFFAOYSA-N 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 16
- 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 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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
- 150000007857 hydrazones Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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 description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- 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
- 239000005457 ice water Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZTPAUBJZUBGGEY-UHFFFAOYSA-N (2,4-dichlorophenyl)hydrazine Chemical compound NNC1=CC=C(Cl)C=C1Cl ZTPAUBJZUBGGEY-UHFFFAOYSA-N 0.000 description 1
- PENWGQNPFRRVQI-UHFFFAOYSA-N (2-fluorophenyl)hydrazine Chemical compound NNC1=CC=CC=C1F PENWGQNPFRRVQI-UHFFFAOYSA-N 0.000 description 1
- SMLQYLWIEBFFKG-UHFFFAOYSA-N (3,4-dimethoxyphenyl)hydrazine Chemical compound COC1=CC=C(NN)C=C1OC SMLQYLWIEBFFKG-UHFFFAOYSA-N 0.000 description 1
- GFPJLZASIVURDY-UHFFFAOYSA-N (3-chlorophenyl)hydrazine Chemical compound NNC1=CC=CC(Cl)=C1 GFPJLZASIVURDY-UHFFFAOYSA-N 0.000 description 1
- NRESDXFFSNBDGP-UHFFFAOYSA-N (4-bromophenyl)hydrazine Chemical compound NNC1=CC=C(Br)C=C1 NRESDXFFSNBDGP-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 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
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 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
- 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
- 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
- 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
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 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
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005292 vacuum distillation 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of hydrazone compounds and its preparation method and application of structure of benzopyrazines containing methoxyl group.Compound 1 is made with 7- methoxyl group ortho-nitraniline and hydrazine hydrate in it；Compound 1 and BMF, which are acted on, is made compound 2；Compound 3 is made in compound 2 and phosphorus oxychloride reaction；Compound 4 is made in compound 3 and hydration hydrazine reaction；Compound 4 reacts obtained compound (I) with aldehyde compound is replaced.Its raw material is simple and easy to get, and preparation method is simple, convenient post-treatment, and product yield is high, and the compound is to provide the foundation with certain activity of weeding for novel pesticide research and development.
Description
Technical field
The invention belongs to hydrazone compounds preparation technical fields, and in particular to a kind of hydrazone of the structure of benzopyrazines containing methoxyl group
Class compound and the preparation method and application thereof.
Background technique
Heterocycle structure is synthetic drug, the important key factor of the substances such as pesticide, this is because heterocycle is efficient, low toxicity and
It can carry out what the characteristics of diversification replaces 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 tying because containing the Asia C=N in its molecular structure
Structure makes it have the coordination mode of stronger coordination ability and multiplicity, can synthesize the new compound of many high activities, and hydrazone
There are also good antitumor and oxidation resistant activity for class compound and its complex, therefore lead 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
It records and has the kind of commercialization the fifties, E.I.Du Pont Company, which reported Benzophenonehydrazones analog derivative at 1973 and has, well to kill
Worm activity, especially has lepidoptera pest high-efficiency activated；The benquinox that Beyer Co., Ltd develops is in prevention and treatment 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
Broadleaf weeds and barnyard grass have excellent activity.
The present invention is based on provide a kind of knot of benzopyrazines containing methoxyl group with activity of weeding on the basis of studying before
The preparation method and application technology of the hydrazone compounds of structure.
Summary of the invention
The hydrazone compounds for the structure of benzopyrazines containing methoxyl group with activity of weeding that it is an object of the present invention to provide a kind of and
Preparation method and application.
The hydrazone compounds of a kind of structure of benzopyrazines containing methoxyl group, it is characterised in that its structural formula such as (I) institute
Show:
Wherein: R1For 2,4- dichlorophenyl, 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 hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that including walking as follows
It is rapid:
1) in organic solvent, 5- methoxyl group ortho-nitraniline and hydration hydrazine reaction are obtained such as formula under the action of Raney Ni
1 compound represented 4- methoxyl group o-phenylenediamine；
2) in organic solvent, the 4- methoxyl group o-phenylenediamine that step 1) obtains is reacted under ethyl alcohol effect with MBF
To compound 7- methoxyl group 2- hydroxyl -3- phenyl quinoxaline as shown in Equation 2；
3) the 7- methoxyl group 2- hydroxyl -3- phenyl quinoxaline for obtaining step 2) and phosphorus oxychloride action-reaction are generated such as formula
The 3 chloro- 3- phenyl quinoxalines of compound represented 7- methoxyl group -2-；
4) the chloro- 3- phenyl quinoxaline of 7- methoxyl group -2- for obtaining step 3) and hydrazine hydrate action-reaction are generated such as 4 institute of formula
Compound (7- methoxyl group -3- phenyl quinoxaline -2- base) hydrazine shown；
5) under ethyl alcohol effect, (7- methoxyl group -3- phenyl quinoxaline -2- base) hydrazine and substitution aldehydes that step 4) is obtained
Compound reaction generates the target hydrazone compounds as shown in formula (I), and replacing the substituent group 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 hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that 5- in step 1)
The amount of the substance 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 substance of oxygroup ortho-nitraniline is calculated as 0.3~0.5ml/mmol, and the dosage of 85% hydrazine hydrate is with 5- methoxyl group neighbour's nitre
The amount of the substance of base aniline is calculated as 0.7~0.8ml/mmol.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that 4- in step 2)
The ratio between amount of substance of methoxyl group o-phenylenediamine and MBF is 1:1.5~3.5, and consumption of organic solvent is with 4- methoxyl group o-phenylenediamine
The amount of substance be calculated as 0.9~1.1ml/mmol.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that three in step 3)
Chlorethoxyfos volumetric usage is calculated as 0.3~0.5ml/mmol with the amount of the substance of 7- methoxyl group -2- hydroxyl -3- phenyl quinoxaline.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that 7- in step 4)
The ratio between amount of substance of the chloro- 3- phenyl quinoxaline of methoxyl group -2- and hydrazine hydrate is 1:1.5~4.5.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that in step 5)
The ratio between (7- methoxyl group -3- phenyl quinoxaline -2- base) hydrazine and the amount of substance for replacing aldehyde compound are 1:0.9~1.1.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that have in step 5)
Solvent 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 methoxyl group as herbicide.
Compared with prior art, the beneficial effects are mainly reflected as follows: the present invention provides one kind contain methoxybenzene
And the preparation method and application of the hydrazone compounds of pyrazine structure, raw material is simple and easy to get, and preparation method is simple, post-processing side
Just, product yield is high, which is especially to have good prevention and treatment when preventing and treating the weeds such as creeping bentgrass with activity of weeding
Effect provides the foundation for the research and development of novel pesticide.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
The hydrazone compounds (I) of the structure of benzopyrazines containing methoxyl group of the invention can synthesize in the following manner:
In 250mL single-necked flask, 0.1mol 7- methoxyl group ortho-nitraniline, 40mL methanol, 75mL hydration are sequentially added
Hydrazine (85%), 0.25~0.45Raney Ni (weight in wet base), are heated to reflux, and are tracked with TCL to raw material and are disappeared, cooled down after reaction
To room temperature, it is filtered to remove Raney Ni, vacuum distillation removes solvent and obtains filbert crystal to get chemical combination as shown in Equation 1 is arrived
1 o-phenylenediamine of object.In 250mL single-necked flask, 0.1mol o-phenylenediamine is added, is dissolved with 100mL ethyl alcohol, then slowly drop
Add MBF, has yellow solid appearance during dropwise addition, according to substituent R1Variation, the reaction time is different, reacts at normal temperature
Period is 30-120min, after fully reacting, is filtered to remove solvent, is flushed three times with ethyl alcohol, obtains chemical combination as shown in Equation 2
Object 7- methoxyl group -2- hydroxyl -3- phenyl quinoxaline.40mLPOCl is added in compound 23Solvent is made, under heated reflux condition
Chlorination is carried out, is tracked with TLC to raw material and is disappeared, be cooled to room temperature after reaction, be poured slowly into 500g ice water, be precipitated immediately
A large amount of yellow solids filter, washing drying, obtain compound 3 as shown in Equation 3.In 250mL three-necked flask, chemical combination is added
Object 3 simultaneously makees solvent with 60mL ethyl alcohol, and the hydrazine hydrate of 18g (0.3mol) 85% is slowly added dropwise, reflux is warming up to after being added dropwise, instead
Answer 4-5h, be cooled to room temperature after reaction, pour into 300g ice water, a large amount of white solids are precipitated immediately, through suction filtration, washing and
It is dry, crude product is made, by recrystallizing to obtain compound 4 as shown in Equation 4.0.377g is added in 50mL round-bottomed flask
(0.002mol) hydrazine is added 15mL ethyl alcohol and makees solvent, and 0.002mol is slowly added dropwise under stirring condition and replaces aldehyde compound, raw material
Dissolution rapidly, then has solid precipitation, is stirred overnight at room temperature, and contact plate monitoring after raw material fully reacting, filters, uses petroleum ether
Mixed liquor washing with ethyl alcohol obtains reddish yellow solid powder, i.e., the structure of benzopyrazines containing methoxyl group as shown in formula (I) three times
Hydrazone compounds.
The structural formula of embodiment 1~11, particular compound is as shown in table 2, and other synthesis conditions do not change.
Embodiment 1
(E) -3- (2- (2- fluorophenyl) hydrazine) -6- methoxyl group-phenyl quinoxaline, reddish yellow solid, yield 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, yield
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- dichlorophenyl) hydrazine) -6- methoxyl group -2- phenyl quinoxaline, reddish yellow solid, yield
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, yield 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 produce
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, yield 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, yield 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, yield
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, yield
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, yield 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, yield 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]+
The test of 12 activity of weeding of embodiment
Subjects: creeping bentgrass, romaine lettuce.
Test method: completing the filter paper of a diameter 5.6cm in the culture dish of diameter 6cm, 2 milliliters of addition is certain density
Test compounds solution, rape seed 10 of sowing seed soaking 6 hours.It is long that radicle is measured at 28 ± 1 DEG C, after dark culturing 7 days
Degree.By compound under dark condition to the growth inhibition of crop radicle come the activity of weeding of detection compound.Test concentrations:
1mM.Each processing is in triplicate.Active 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 1 compound C1-C11 of table
It is certain to show that such compound has the selected 2 kinds of plants of test in the case where test sets concentration from 1 activity of weeding of table
Activity of weeding.Compound C5 is to creeping bentgrass, and romaine lettuce has certain activity of weeding, and compound C6, C8 are respectively to romaine lettuce, Jian's stock
Grain husk has certain activity of weeding.Particular compound structure is as shown in table 2
The specific structure of 2 compound C1-C11 of table
Claims (10)
1. a kind of hydrazone compounds of the structure of benzopyrazines containing methoxyl group, it is characterised in that its structural formula is such as shown in (I):
(I)
Wherein: R1For 4- trifluoromethyl, 2- nitrobenzophenone, 3,4- Dimethoxyphenyls.
2. a kind of preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group as described in claim 1, feature
It is to include the following steps:
1) in organic solvent, 5- methoxyl group ortho-nitraniline and hydration hydrazine reaction are obtained such as 1 institute of formula under the action of Raney Ni
The compound 4- methoxyl group o-phenylenediamine shown；
2) in organic solvent, 4- methoxyl group o-phenylenediamine that step 1) obtains is reacted obtain with MBF under ethyl alcohol effect as
2 compound represented 7- methoxyl group 2- hydroxyl -3- phenyl quinoxaline of formula；
3) the 7- methoxyl group 2- hydroxyl -3- phenyl quinoxaline for obtaining step 2 and phosphorus oxychloride action-reaction are generated such as 3 institute of formula
The chloro- 3- phenyl quinoxaline of compound 7- methoxyl group -2- shown；
4) the chloro- 3- phenyl quinoxaline of 7- methoxyl group -2- for obtaining step 3) and hydrazine hydrate action-reaction generate as shown in Equation 4
Compound (7- methoxyl group -3- phenyl quinoxaline -2- base) hydrazine；
5) under ethyl alcohol effect, (7- methoxyl group -3- phenyl quinoxaline -2- base) hydrazine and substitution aldehydes chemical combination that step 4) is obtained
Object reaction generates target hydrazone compounds as shown in the formula (I), and replacing the substituent group in aldehyde compound is 4- trifluoromethylbenzene
Base, 2- nitrobenzophenone, 3,4- Dimethoxyphenyls；
Preparation process is as follows:
。
3. the preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group according to claim 2, feature exist
The amount of the substance of 5- methoxyl group ortho-nitraniline and the mass ratio of Raney Ni are 1:2.5 ~ 4.5 in step 1)；It is organic molten
Agent dosage is calculated as 0.3 ~ 0.5ml/mmol with the amount of the substance of 5- methoxyl group ortho-nitraniline, the hydrazine hydrate that hydrazine hydrate is 85%,
The dosage of 85% hydrazine hydrate is calculated as 0.7 ~ 0.8ml/mmol with the amount of the substance of 5- methoxyl group ortho-nitraniline.
4. the preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group according to claim 2, feature exist
The ratio between amount of substance of 4- methoxyl group o-phenylenediamine and MBF is 1:1.5 ~ 3.5 in step 2, and consumption of organic solvent is with 4- methoxy
The amount of the substance of base o-phenylenediamine is calculated as 0.9 ~ 1.1ml/mmol.
5. the preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group according to claim 2, feature exist
In step 3) phosphorus oxychloride volumetric usage be calculated as 0.3 with the amount of the substance of 7- methoxyl group -2- hydroxyl -3- phenyl quinoxaline ~
0.5ml/mmol。
6. the preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group according to claim 2, feature exist
The ratio between amount of substance of the chloro- 3- phenyl quinoxaline of 7- methoxyl group -2- and hydrazine hydrate is 1:1.5 ~ 4.5 in step 4).
7. the preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group according to claim 2, feature exist
The ratio between (7- methoxyl group -3- phenyl quinoxaline -2- base) hydrazine and the amount of substance for replacing aldehyde compound are 1:0.9 in step 5)
~1.1。
8. the preparation method of the hydrazone compounds of the structure of benzopyrazines containing methoxyl group according to claim 2, feature exist
Consumption of organic solvent is in step 5) to replace the amount of the substance of aldehyde compound to be calculated as 7.0 ~ 8.0ml/mmol.
9. a kind of hydrazone compounds answering as romaine lettuce herbicide of the structure of benzopyrazines containing methoxyl group as described in claim 1
With wherein R1For 4- trifluoromethyl or 2- nitrobenzophenone.
10. a kind of hydrazone compounds of the structure of benzopyrazines containing methoxyl group as described in claim 1 are as creeping bentgrass herbicide
Application, wherein R1For 4- trifluoromethyl or 3,4- Dimethoxyphenyl.
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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
- 2016-07-28 CN CN201610615196.4A patent/CN106220575B/en active Active
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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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| Biological activity of drug like small molecules based on quinoxaline containing amino substitution at C-2;K. Raghavendra Rao,等;《Der Pharma Chemica》;20150331;第7卷(第2期);第77-85页，尤其是第78页方案1 * |
| Studies on Compounds Related to Pyrazine. 11. The Reaction of 3-Substituted-2-hydrazinoquinoxalines with Carbonyl Compounds;DEN-ITSUS HIH,等;《Journal of the American Chemical Society》;19600805;第82卷;第4044-4054页， * |
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