CN106432108A - Hydrazone compound containing methyl quinoxaline structure, preparation method and application thereof - Google Patents
Hydrazone compound containing methyl quinoxaline structure, preparation method and application thereof Download PDFInfo
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- CN106432108A CN106432108A CN201610613074.1A CN201610613074A CN106432108A CN 106432108 A CN106432108 A CN 106432108A CN 201610613074 A CN201610613074 A CN 201610613074A CN 106432108 A CN106432108 A CN 106432108A
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention discloses a hydrazone compound containing a methyl quinoxaline structure, a preparation method and an application thereof. 5-Methyl-o-nitroaniline and hydrazine hydrate are used to prepare a compound 1; the compound 1 reacts with BMF to prepare a compound 2; the compound 2 reacts with phosphorus oxychloride to prepare a compound 3; and the compound 3 reacts with hydrazine hydrate to prepare a compound 4; and the compound 4 reacts with a substituted aldehyde compound to prepare the compound (I). The raw material is simple and easy to obtain, the preparation method is simple, the post-treatment is convenient, the product yield is high, and the compound has herbicidal activity, has a certain weeding effect especially on Agrostis stolonifera and provides a foundation for research and development of new pesticides.
Description
Technical field
The invention belongs to hydrazone compounds preparing technical field is and in particular to a kind of hydrazone class of benzopyrazines containing methyl structure
Compound and preparation method and application.
Background technology
Heterocycle structure is synthetic drug, the important key factor of the material such as pesticide, and this is efficient due to heterocycle, low toxicity and
Can carry out what the diversified feature replacing was determined.It has become as medicine, a study hotspot in the field of pesticide.Hydrazone class
Compound has the widely biological activity such as good weeding, parasite killing, sterilization, simultaneously because containing the sub- knot of C=N in its molecular structure
Structure, so as to have stronger coordination ability and various coordination mode, can synthesize much highly active new compounds, and hydrazone
Class compound and its coordination compound also have good antitumor and antioxidative activity, therefore lead in pesticide, medicine, detection and material
All there is application in domain.The extensive concern of the person that even more receives pesticide research, in terms of New pesticides discovery, research is more and more deep.Previous generation
Record the kind of the existing commercialization fifties, E.I.Du Pont Company reported Benzophenonehydrazones analog derivative when 1973 and has and well kills
Worm activity, especially has high-efficiency activated to lepidoptera pest；The benquinox that Beyer Co., Ltd develops is in preventing and treating pythium spp and soil fungi
The seed causing and sprout term disease have better effects；, by obvious activity of weeding, it is right for schiff bases and fatty acylhydrazone
Broad leaved weed and barnyard grass have excellent activity.
The present invention provides a kind of structure of benzopyrazines containing methyl with activity of weeding based on the basis of studying before
The preparation method of hydrazone compounds and application technology.
Content of the invention
It is an object of the present invention to provide a kind of hydrazone compounds of the structure of benzopyrazines containing methyl with activity of weeding and its
Preparation method and application.
A kind of hydrazone compounds of described structure of benzopyrazines containing methyl are it is characterised in that its structural formula is as shown in (I)：
Wherein:R1For 3,4,5- trimethoxyphenyls, 2,4- Dichlorobenzene base, 3- nitrobenzophenone, 2- bromophenyl, 2- hydroxy benzeness
Base, 2- nitrobenzophenone, 2- fluorophenyl, 4- bromophenyl, 4- isopropyl phenyl, 2- methoxyphenyl, 4- fluorophenyl, 3,4- dimethoxies
Base phenyl, 4- aminomethyl phenyl, 2- furan phenyl, methyl.
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that include following walking
Suddenly：
1) in organic solvent, in the presence of Raney Ni, 5- methyl ortho-nitraniline and hydration hydrazine reaction obtain as formula 1
Shown compound 5- methyl ortho-nitraniline；
2) in organic solvent, by step 1) the 5- methyl ortho-nitraniline that obtains reacted with MBF under ethanol effect
To compound 7- methyl -2- hydroxyl -3- phenyl quinoxaline as shown in Equation 2；
3) by step 2) the 7- methyl -2- hydroxyl -3- phenyl quinoxaline that obtains generated as formula 3 with phosphorus oxychloride action-reaction
The shown chloro- 3- phenyl quinoxaline of compound 7- methyl -2-；
4) by step 3) the 7- methyl -2- chloro- 3- phenyl quinoxaline that obtains generated as shown in Equation 4 with hydrazine hydrate action-reaction
Compound (7- methyl -3- phenyl quinoxaline -2- base) hydrazine；
5) in organic solvent, by step 4) (7- methyl -3- phenyl quinoxaline -2- base) hydrazine of obtaining with replace aldehydes
Compound reaction generates the target hydrazone compounds as shown in formula (I)；
Preparation process is as follows：
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that step 1) in 5- first
The mass ratio of the amount of the material of base ortho-nitraniline and Raney Ni is 1:2.5～4.5, organic solvent is methanol, its volume
Consumption is calculated as 0.3～0.5ml/mmol with the amount of the material of 5- methyl ortho-nitraniline, and the consumption of 85% hydrazine hydrate is with 5- first
The amount of the material of base ortho-nitraniline is calculated as 0.7～0.8ml/mmol.
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that step 2) in 4- first
Base o-phenylenediamine is 1 with the ratio of the amount of the material of MBF:1.5～3.5.
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that step 2) in organic
Solvent is methanol, ethanol or DMF, and its volumetric usage is calculated as 0.9～1.1ml/mmol with the amount of the material of 4- methyl-o-phenylenediamine.
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that step 3) in trichlorine
Oxygen phosphorus volumetric usage is calculated as 0.3～0.5ml/mmol with the amount of the material of 7- methyl -2- hydroxyl -3- phenyl quinoxaline.
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that step 4) in 7- first
Base -2- chloro- 3- phenyl quinoxaline is 1 with the ratio of the amount of the material of hydrazine hydrate:1.5～4.5.
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that step 5) in (7-
Methyl -3- phenyl quinoxaline -2- base) hydrazine with replace aldehyde compound material amount ratio be 1:0.9～1.1.
The preparation method of the described hydrazone compounds of the structure of benzopyrazines containing methyl is it is characterised in that step 5) in organic
Solvent is methanol, ethanol or DMF, and its consumption is calculated as 7.0～8.0ml/mmol with the amount replacing the material of aldehyde compound.
The hydrazone compounds of the described structure of benzopyrazines containing methyl are as the application of herbicide.
Compared with prior art, the beneficial effects are mainly as follows：The invention provides a kind of benzo containing methyl
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 is to have activity of weeding, particularly has good preventive and therapeutic effect in preventing and treating creeping bentgrass, is
The research and development of novel pesticide provide the foundation.
Specific embodiment
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 of benzopyrazines containing methyl of the present invention can synthesize in the following manner：
In 250mL single-necked flask, sequentially add 0.1mol 5- methyl ortho-nitraniline, 40mL methanol, 75mL hydrazine hydrate
(85%), 0.25～0.45Raney Ni (weight in wet base), is heated to reflux, and is followed the trail of with TCL and disappears to raw material, and reaction is cooled to after terminating
Room temperature, is filtered to remove Raney Ni, and vacuum distillation removes solvent and obtains filbert crystal, that is, obtain compound as shown in Equation 1
14- methyl-o-phenylenediamine.In 250mL single-necked flask, add 0.1mol substituted o-phenylenediamine, dissolved with 100mL ethanol,
It is slowly added dropwise MBF again, have yellow solid to occur, according to substituent R during Deca1Change, the response time is different, normal
Warm section of lower response time is 30-120min, after reaction completely, is filtered to remove solvent, with alcohol flushing three times, obtains as formula 2 institute
The compound 7- methyl -2- hydroxyl -3- phenyl quinoxaline showing.40mLPOCl is added in compound 23Make solvent, be heated to reflux
Under the conditions of carry out chlorination, with TLC follow the trail of to raw material disappear, reaction terminate after be cooled to room temperature, be poured slowly in 500g frozen water, stand
Separate out a large amount of yellow solids, sucking filtration, washing drying, obtain compound 3 as shown in Equation 3.In 250mL there-necked flask, plus
Enter compound 3 and make solvent with 60mL ethanol, be slowly added dropwise the hydrazine hydrate of 18g (0.3mol) 85%, be warming up to after completion of dropping
Backflow, reacts 4-5h, and reaction is cooled to room temperature after terminating, pours in 300g frozen water, separate out a large amount of white solids immediately, through taking out
Filter, washing and dry, prepared crude product, obtain compound 4 as shown in Equation 4 by recrystallization.50mL round-bottomed flask adds
0.377g (0.002mol) hydrazine, adds 15mL ethanol to do and is slowly added dropwise 0.002mol replacement aldehydes chemical combination under solvent, stirring condition
Thing, raw material dissolves rapidly, then has solid to separate out, is stirred overnight under room temperature, point plate monitoring, after raw material reaction is complete, sucking filtration, use
The mixed liquor of petroleum ether and ethanol washs three times, obtains reddish yellow pressed powder, i.e. the knot of benzopyrazines containing methyl as shown in formula (I)
The hydrazone compounds of structure.
Embodiment 1～15, as shown in table 2, other synthesis conditions do not change the structural formula of particular compound.
Embodiment 1
(E)-(2- (2- (7- methyl -3- phenyl quinoxaline -2- base) hydrazine) methyl) phenol, reddish yellow solid, yield
87.5%, m.p.113-116 DEG C；1H NMR(400MHz,CDCl3/TMS),δ2.50(S,3H,CH3),6.95(m,1H,Ph-H),
7.13(m,1H,Ph-H),7.32-7.88(m,9H,Ph-H),8.10(s,1H,Ph-H),8.29(s,1H,NH),8.70(m,1H,
=CH), 11.65 (m, 1H, OH) .HRMS (ESI) m/z:Calculated,355.1553,Found,355.1572[M+H]+.
Embodiment 2
(E) -3- (2- (2- bromophenyl) hydrazine) -6- methyl -2- phenyl quinoxaline, reddish yellow solid, yield 68.3%,
m.p.80-83℃；1H NMR(400MHz,CDCl3/TMS),δ2.52(S,3H,CH3), 7.26 (q, J=6.0Hz, 1H, Ph-H),
7.38 (t, J=6.0Hz, 2H, Ph-H), 7.57-7.77 (m, 8H, Ph-H), 8.17 (m, 1H, Ph-H) .FTIR υ (cm-1):
687.47,1088.49,1462.76,1610.96,2929.38,2958.79,3063.75.HRMS(ESI)m/z:
Calculated,417.0709,Found,417.0729[M+H]+.
Embodiment 3
(E) -6- methyl -3- (2- (3- nitrobenzophenone) hydrazine) -2- phenyl quinoxaline, reddish yellow solid, yield 71.9%,
m.p.172-175℃；1H NMR(400MHz,CDCl3/TMS),δ2.55(S,3H,CH3), 7.23 (d, J=6.8Hz, 1H, Ph-
), H 7.37 (d, J=6.8Hz, 1H, Ph-H), 7.63 (m, 3H, Ph-H), 7.74 (m, 3H, Ph-H), 7.87 (m, 2H, Ph-H),
8.16 (q, J=6.8Hz, 2H, Ph-H), 8.59 (m, 1H, NH), 8.89 (m, 1H ,=CH) .HRMS (ESI) m/z:
Calculated,384.1455,Found,384.1478[M+H]+.
Embodiment 4
(E) -3- (2- (3,4- Dimethoxyphenyl) hydrazine) -6- methyl -2- phenyl quinoxaline, reddish yellow solid, yield
81.8%, m.p.105-108 DEG C；1H NMR(400MHz,CDCl3/TMS),δ2.53(S,3H,CH3),4.02(S,3H,OCH3),
4.05(S,3H,OCH3), 7.13 (t, J=5.0Hz, 1H, Ph-H), 7.23 (d, J=2.0Hz, 1H, Ph-H), 7.34 (m, 1H,
Ph-H), 7.51-7.56 (m, 5H, Ph-H), 7.63 (m, 1H, Ph-H), 8.02 (s, 1H, Ph-H), 8.09 (d, J=6.4Hz,
1H, Ph-H), 8.87 (m, 2H, 1NH, 1=CH) .HRMS (ESI) m/z:Calculated,399.1816,Found,399.1842
[M+H]+.
Embodiment 5
(E) -3- (2- (2- fluorophenyl) hydrazine) -6- methyl -2- phenyl quinoxaline, reddish yellow solid, yield 78.7%,
m.p.139-141℃；1H NMR(400MHz,CDCl3/TMS),δ2.53(S,3H,CH3),7.20(m,1H,Ph-H),7.37(q,
J=8.6Hz, 2H, Ph-H), 7.43 (d, J=8.2Hz, 1H, Ph-H), 7.47 (q, J=7.0Hz, 1H, Ph-H), 7.54-7.59
(m, 2H, Ph-H), 7.72-7.76 (m, 2H, Ph-H), 7.79 (t, J=7.2Hz, 1H, Ph-H), 8.87 (m, 2H, 1NH, 1=
CH).HRMS(ESI)m/z:Calculated,357.1510,Found,357.1513[M+H]+.
Embodiment 6
(E) -3- (2- (2,4- Dichlorobenzene base) hydrazine) -6- methyl -2- phenyl quinoxaline, reddish yellow solid, yield 60.8%,
m.p.141-143℃；1H NMR(400MHz,CDCl3/TMS),δ2.53(S,3H,CH3),7.08-7.46(m,2H,Ph-H),
7.60 (m, 4H, Ph-H), 7.70 (m, 2H, Ph-H), 8.04-8.06 (m, 2H, Ph-H), 8.89 (m, 1H ,=CH) .HRMS
(ESI)m/z:Calculated,407.0825,Found,407.0829[M+H]+.
Embodiment 7
(E) -6- methyl -2- phenyl -3- (2- (2,3,4- trimethoxy) hydrazine) quinoxaline, reddish yellow solid, yield
74.5%, m.p.82-85 DEG C；1H NMR(400MHz,CDCl3/TMS),δ2.54(S,3H,CH3),3.96(s,9H,OCH3),
7.06 (s, 2H, Ph-H), 7.56-8.60 (m, 8H, 7Ph-H, 1=CH) .HRMS (ESI) m/z:Calculated,429.1921,
Found,429.1926[M+H]+.
Embodiment 8
(E) -6- methyl -3- (2- (2- nitrobenzophenone) hydrazine) -2- phenyl quinoxaline, reddish yellow solid, yield 46.0%,
m.p.119-121℃；1H NMR(400MHz,CDCl3/TMS),δ2.54(S,3H,CH3),7.46-7.54(m,5H,Ph-H),
7.68 (t, J=7.5Hz, 1H, Ph-H), 7.71-7.89 (m, 3H, Ph-H), 8.00 (d, J=8.6Hz, 2H, Ph-H), 8.27
(m, 1H, Ph-H), 8.73 (m, 1H, 1=CH) .HRMS (ESI) m/z:Calculated,384.1455,Found,384.1456
[M+H]+.
Embodiment 9
(E) -3- (2- (4- bromophenyl) hydrazine) -6- methyl -2- phenyl quinoxaline, reddish yellow solid, yield 95.8%,
m.p.139-142℃；1H NMR(400MHz,CDCl3/TMS),δ2.50(S, 3H,CH3), 7.45 (d, J=8.6Hz, 2H, Ph-
H),7.55(m,5H,Ph-H),7.63-7.66(m,3H,Ph-H),7.81(m,1H,Ph-H),8.01(s,1H,Ph-H),8.10
(d, J=8.2Hz, 1H, Ph-H), 8.86 (m, 1H ,=CH) .HRMS (ESI) m/z:Calculated,417.0709,Found,
417.0697[M+H]+.
Embodiment 10
(E) -3- (2- (3- chlorphenyl) hydrazine) -6- methyl -2- phenyl quinoxaline, reddish yellow solid, yield 50.0%,
m.p.127-130℃；1H NMR(400MHz,CDCl3/TMS),δ2.52(S,3H,CH3),7.36(m,2H,Ph-H),7.43(d,
J=8.6Hz, 1H, Ph-H), 7.55 (m, 2H, Ph-H), 7.60-7.65 (m, 4H, Ph-H), 7.86 (t, J=10.0Hz, 2H,
), Ph-H 8.03 (s, 1H, Ph-H), 8.10 (d, J=8.2Hz, 1H, Ph-H), 8.86 (m, 1H ,=CH) .HRMS (ESI) m/z:
Calculated,373.1215,Found,373.1211[M+H]+.
Embodiment 11
(E) -3- (2- (2- methoxyphenyl) hydrazine) -6 methyl -2- phenyl quinoxaline, reddish yellow solid, yield 86.0%,
m.p.105-108℃；1H NMR(400MHz,CDCl3/TMS),δ2.50(S,3H,CH3),3.68(s,3H,OCH3),7.12(m,
1H, Ph-H), 7.17-7.26 (m, 2H, Ph-H), 7.34 (d, J=8.6Hz, 1H, Ph-H), 7.62 (m, 3H, Ph-H), 7.89
(m, 2H, Ph-H), 8.06 (d, J=8.2Hz, 1H, Ph-H), 8.88 (m, 2H, 1NH, 1=CH) .HRMS (ESI) m/z:
Calculated,369.1710,Found,369.1711[M+H]+.
Embodiment 12
(E) -6- methyl -3- (2- (4- aminomethyl phenyl) hydrazine) -2- phenyl quinoxaline, reddish yellow solid, yield 80.7%,
m.p.240-243℃；1H NMR(400MHz,CDCl3/TMS),δ2.52(S,3H,CH3),2.56(s,3H,CH3),7.46(m,
4H, Ph-H), 7.61 (m, 2H, Ph-H), 7.63 (m, 2H, Ph-H), 8.00 (s, 1H, Ph-H), 8.07 (d, J=6.8Hz, 1H,
), Ph-H 8.88 (m, 3H, 1Ph-H, 1NH, 1=CH) .HRMS (ESI) m/z:Calculated,353.1761,Found,
353.1764[M+H]+.
Embodiment 13
(E) -3- (2- (2- (furan -3- base) benzal) hydrazine) -6- methyl -2- phenyl quinoxaline, reddish yellow solid, yield
78.9%, m.p.123-126 DEG C；1H NMR(400MHz,CDCl3/TMS),δ2.55(S,3H,CH3),6.78(m,1H,furan-
), H 7.17 (d, J=3.2Hz, 1H, furan-H), 7.34 (m, 1H, Ph-H), 7.48 (m, 1H, Ph-H), 7.62 (m, 3H, Ph-
), H 7.82 (m, 1H, furan-H), 8.02 (s, 1H, Ph-H), 8.10 (d, J=8.2Hz, 1H, Ph-H), 8.85 (m, 3H, 1Ph-
H, 1NH, 1=CH) .HRMS (ESI) m/z:Calculated,329.1397,Found,329.1407[M+H]+.
Embodiment 14 activity of weeding is tested
Subjects：Creeping bentgrass, Caulis et Folium Lactucae Sativae etc..
Test method：The filter paper of a diameter 5.6cm is completed, 2 milliliters of addition is certain density in the culture dish of diameter 6cm
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 to the growth inhibited of crop radicle come the activity of weeding of detection compound.Test concentrations：
1mM.Each is processed 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 table 1 compound B-11-B13
Particular compound structure is as shown in table 2
The concrete structure of table 2 compound B-11-B14
Show from table 1 activity of weeding, compound B7, B8, B10, B12, B13 have certain activity of weeding to creeping bentgrass.
Compound B-11 2 has certain activity of weeding to Caulis et Folium Lactucae Sativae.
Claims (10)
1. a kind of hydrazone compounds of the structure of benzopyrazines containing methyl are it is characterised in that its structural formula is as shown in (I)：
Wherein:R1For 3,4,5- trimethoxyphenyls, 2,4- Dichlorobenzene base, 3- nitrobenzophenone, 2- bromophenyl, 2- hydroxy phenyl, 2-
Nitrobenzophenone, 2- fluorophenyl, 4- bromophenyl, 4- isopropyl phenyl, 2- methoxyphenyl, 4- fluorophenyl, 3,4- dimethoxy benzenes
Base, 4- aminomethyl phenyl, 2- furan phenyl, methyl.
2. a kind of preparation method of the hydrazone compounds of the structure of benzopyrazines containing methyl as claimed in claim 1, its feature exists
In comprising the steps：
1) in organic solvent, in the presence of Raney Ni, 5- methyl ortho-nitraniline and hydration hydrazine reaction obtain as shown in Equation 1
Compound 5- methyl ortho-nitraniline；
2) in organic solvent, by step 1) the 5- methyl ortho-nitraniline that obtains react with MBF under ethanol effect obtain as
Compound 7- methyl -2- hydroxyl -3- phenyl quinoxaline shown in formula 2；
3) by step 2) the 7- methyl -2- hydroxyl -3- phenyl quinoxaline that obtains generated as shown in Equation 3 with phosphorus oxychloride action-reaction
The chloro- 3- phenyl quinoxaline of compound 7- methyl -2-；
4) by step 3) the 7- methyl -2- chloro- 3- phenyl quinoxaline that obtains generates change as shown in Equation 4 with hydrazine hydrate action-reaction
Compound (7- methyl -3- phenyl quinoxaline -2- base) hydrazine；
5) in organic solvent, by step 4) (7- methyl -3- phenyl quinoxaline -2- base) hydrazine of obtaining with replace aldehyde compound
Reaction generates the target hydrazone compounds as shown in formula (I)；
Preparation process is as follows：
3. the hydrazone compounds of the structure of benzopyrazines containing methyl according to claim 2 preparation method it is characterised in that
Step 1) in the mass ratio of the amount of material of 5- methyl ortho-nitraniline and RaneyNi be 1:2.5～4.5, organic solvent is
Methanol, its volumetric usage is calculated as 0.3～0.5ml/mmol with the amount of the material of 5- methyl ortho-nitraniline, 85% hydrazine hydrate
Consumption is calculated as 0.7～0.8ml/mmol with the amount of the material of 5- methyl ortho-nitraniline.
4. the hydrazone compounds of the structure of benzopyrazines containing methyl according to claim 2 preparation method it is characterised in that
Step 2) in the ratio of 4- methyl-o-phenylenediamine and the amount of the material of MBF be 1:1.5～3.5.
5. the hydrazone compounds of the structure of benzopyrazines containing methyl according to claim 2 preparation method it is characterised in that
Step 2) in organic solvent be methanol, ethanol or DMF, its volumetric usage is calculated as 0.9 with the amount of the material of 4- methyl-o-phenylenediamine
～1.1ml/mmol.
6. the hydrazone compounds of the structure of benzopyrazines containing methyl according to claim 2 preparation method it is characterised in that
Step 3) in phosphorus oxychloride volumetric usage 0.3～0.5ml/ is calculated as with the amount of the material of 7- methyl -2- hydroxyl -3- phenyl quinoxaline
mmol.
7. the hydrazone compounds of the structure of benzopyrazines containing methyl according to claim 2 preparation method it is characterised in that
Step 4) in the ratio of 7- methyl -2- chloro- 3- phenyl quinoxaline and the amount of the material of hydrazine hydrate be 1:1.5～4.5.
8. the hydrazone compounds of the structure of benzopyrazines containing methyl according to claim 2 preparation method it is characterised in that
Step 5) in (7- methyl -3- phenyl quinoxaline -2- base) hydrazine with replace aldehyde compound material amount ratio be 1:0.9～
1.1.
9. the hydrazone compounds of the structure of benzopyrazines containing methyl according to claim 2 preparation method it is characterised in that
Step 5) in organic solvent be methanol, ethanol or DMF, its consumption is calculated as 7.0 with the amount replacing the material of aldehyde compound～
8.0ml/mmol.
10. a kind of hydrazone compounds of the structure of benzopyrazines containing methyl as claimed in claim 1 are as the application of herbicide.
Priority Applications (1)
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Citations (2)
| 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 |
| CN104387367A (en) * | 2014-11-02 | 2015-03-04 | 湖南华腾制药有限公司 | Method for preparing disubstituted benzimidazole derivative |
-
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Patent Citations (2)
| 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 |
| CN104387367A (en) * | 2014-11-02 | 2015-03-04 | 湖南华腾制药有限公司 | Method for preparing disubstituted benzimidazole derivative |
Non-Patent Citations (3)
| Title |
|---|
| DEN-ITSUS HIH,等: "Studies on Compounds Related to Pyrazine. 11. The Reaction of 3-Substituted-2-hydrazinoquinoxalines with Carbonyl Compounds", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| K. RAGHAVENDRA RAO,等: "Biological activity of drug like small molecules based on quinoxaline containing amino substitution at C-2", 《DER PHARMA CHEMICA》 * |
| 张矛: "喹喔啉苯腙衍生物和肉桂酰胺衍生物的合成及生物活性研究", 《中国优秀硕士学位论文全文数据库 农业科技辑》 * |
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Application publication date: 20170222 Assignee: Hangzhou Guangyoujiu Enterprise Management Partnership (L.P.) Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033595 Denomination of invention: A hydrazone compound containing a methyl benzopyrazine structure and its preparation method and application Granted publication date: 20190222 License type: Common License Record date: 20230316 Application publication date: 20170222 Assignee: Hangzhou baibeiyou Biotechnology Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033594 Denomination of invention: A hydrazone compound containing a methyl benzopyrazine structure and its preparation method and application Granted publication date: 20190222 License type: Common License Record date: 20230315 Application publication date: 20170222 Assignee: Hangzhou Zhiguo Enterprise Service Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033596 Denomination of invention: A hydrazone compound containing a methyl benzopyrazine structure and its preparation method and application Granted publication date: 20190222 License type: Common License Record date: 20230316 |