CN106243110B - A kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group and its preparation method and application - Google Patents
A kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of 1,2,4 triazole derivatives of the structure of benzopyrazines containing methoxyl group and its preparation method and application.It generates compound (II) with 4 methoxyl group, 2 nitroaniline and hydrazine hydrate.It is reacted again with MBF, obtains product (III).Compound (III) is used into POCl3Chlorination obtains product (IV).Compound object (IV) obtains intermediate product (V) with hydration hydrazine reaction.Compound (V) is with POCl3Make solvent, with substitution acid compounds react the structure of benzopyrazines containing methoxyl group shown in formula (I) 1,2,4 triazole derivatives；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 with activity of weeding, has good herbicidal effect especially for creeping bentgrass, is provided the foundation for novel pesticide research and development.
Description
Technical field
The invention belongs to 1,2,4- triazole class compounds preparing technical fields, and in particular to a kind of benzopyrazines containing methoxyl group
1,2,4- triazole derivatives of structure and its preparation method and application.
Background technology
The synthesis of quinoxaline, triazole compound is chemistry of pesticide, iatrochemistry, polymer chemistry, Coordinative Chemistry
Important directions.Quinoxaline compound has significant bioactivity, is widely used in the fields such as pesticide, medicine, dyestuff.Three
Nitrogen azole compounds are again because its good sterilization, weeding, desinsection and plant growth regulating activity are applied in pesticide field.Some reports
Road shows that fused heterocyclic compound usually has the mixed attributes of single heterocycle.In order to find high-efficiency activated noval chemical compound, in 4 class benzene
And splice upper triazole structure in pyrazine structure, synthesis has new the 1 of activity of weeding, 2,4- triazole derivatives.
The present invention provides a kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group with activity of weeding
Preparation method and application technology.
The content of the invention
1,2,4- triazole derivatives and its preparation side it is an object of the present invention to provide a kind of structure of benzopyrazines containing methoxyl group
Method and application.
1,2,4- triazole derivatives of a kind of structure of benzopyrazines containing methoxyl group, it is characterised in that its structural formula is such as
(I) shown in：
Wherein：R1For phenyl, undecyl, 3- fluorophenyls, 4- amyl phenyl, 4- nitrobenzophenones, 3- nitrobenzophenones, 4- first
Phenyl, 4- isopropyl phenyls, 2- chloropyridines, 4- n-propyl phenyl, 2- furans, 2,4- dichlorophenyls, 3- chlorphenyls, 4- fluorine
Phenyl, 3- aminomethyl phenyls.
The preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that including
Following steps：
1) it is solvent in methanol, Raney Ni are under catalysts conditions, and 4- methoxyl group -2- nitroanilines are heated with hydrazine hydrate
Reflux is made such as formula (II) compound represented (II)；
2) chemical combination of compound (II) and methyl benzoylformate the reaction synthesis obtained step 1) as shown in formula (III)
Object (III) crude product；
3) compound (III) crude product obtained step 2) washs after purification through ethyl alcohol, uses POCl3Solvent is made, is heated back
Chlorination reaction is carried out under the conditions of stream, is terminated through TLC monitoring reactions, it is post-treated to obtain such as formula (IV) compound represented (IV),
And carry out the next step；
4) using ethyl alcohol as solvent, compound (IV) and hydration hydrazine reaction that step 3) is obtained are obtained shown in formula (V)
(7- methoxyl group -3- phenyl quinoxaline -2- bases) hydrazine crude product (V)；
5) compound (V) crude product obtained step 4) is after recrystallization purifying, with POCl3Solvent is made, with substitution acid
Class compound react the structure of benzopyrazines containing methoxyl group shown in formula (I) 1,2,4- triazole derivatives；
Preparation process is as follows：
The preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that step
1) in, each substance inventory of addition is：0.1mol 4- methoxyl groups ortho-nitranilines, 30-50mL methanol, 70-80mL85%
Hydrazine hydrate, 0.25~0.45g Raney Ni are preferably 0.1mol 4- methoxyl groups ortho-nitraniline, 40mL methanol, 75mL85%
Hydrazine hydrate, 0.25~0.45g Raney Ni, Raney Ni be weight in wet base.
The preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that step
2) reaction temperature in is room temperature, reaction time 30-90min.
The preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that step
3) post-processing approach is in：It is poured slowly into after completion of the reaction in ice water, a large amount of yellow solids is precipitated immediately, filter, washing drying,
Obtain compound (IV).
The preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that step
4) in, the molar ratio of compound (IV) and 85% hydrazine hydrate is 1：2.5-3.5 it is preferably 1：3.
The preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that chemical combination
The ratio between the amount of substance of object (V) with substituting acid compounds is 1:1：1.2, the time is heated to reflux as 3.5-4.54h, preferably object
The ratio between amount of matter is 1:1：1.2, the time is heated to reflux as 4h.
The preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that step
3) in, TLC is extracted reaction solution when monitoring, and is added in ice water and is cracked POCl3, then product is extracted with ethyl acetate, organic layer is taken, with
Ethyl acetate：Petroleum ether=1:3 mixed liquors are solvent, monitor the carry out degree of reaction.
Application of the 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group as herbicide.
The 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group are as herbicide in prevention creeping bentgrass, life
The application of dish weeds.
Compared with prior art, the beneficial effects are mainly as follows：The present invention provides one kind to contain methoxybenzene
And the 1 of pyrazine structure, the preparation method of 2,4- triazole derivatives and its preparation method and application, raw material is simple and easy to get, prepares
Method is simple, convenient post-treatment, and product yield is high, and the compound is with activity of weeding, especially for prevention Jian's stock
It is clever, romaine lettuce weeds etc. that there is good effect, it provides the foundation for the research and development of novel pesticide.
Compared with prior art, the beneficial effects are mainly as follows：The present invention provides one kind to contain methoxybenzene
And the 1 of pyrazine structure, the preparation method of 2,4- triazole derivatives and its preparation method and application, raw material is simple and easy to get, prepares
Method is simple, convenient post-treatment, and product yield is high, and the compound is with activity of weeding, especially for prevention Jian's stock
It is clever, romaine lettuce weeds etc. that there is good effect, it provides the foundation for the research and development of novel pesticide.
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 1,2,4- triazole derivatives (I) of the structure of benzopyrazines containing methoxyl group of the present invention can synthesize in the following manner：
In 250mL single-necked flasks, 0.1mol 4- methoxyl group -2- nitroanilines, 40mL methanol, 75mL water are sequentially added
Hydrazine (85%), 0.25~0.45g Raney Ni (weight in wet base) are closed, is heated to reflux, is tracked to raw material and disappeared with TLC, after reaction
It is cooled to room temperature, is filtered to remove Raney Ni, vacuum distillation removes solvent and obtains filbert crystal, obtains the 4- shown in formula (II) and take
For o-phenylenediamine.0.1mol 4- methoxyl groups o-phenylenediamines (II) are dissolved with 100mL ethyl alcohol, then MBF are slowly added dropwise, normal
Warm section of lower reaction time is 30-90min, after the reaction was complete, is filtered to remove solvent, and product (III) is obtained three times with alcohol flushing.It will
Compound (III) is added in 100mL single-necked flasks, and with 40mL POCl3Solvent is made, chlorination is carried out under heated reflux condition,
It is cooled to room temperature, is poured slowly into 500g ice water after reaction, a large amount of yellow solids are precipitated immediately, filter, washing drying, obtain
To product (IV).Solvent is made with 60mL ethyl alcohol, the hydrazine hydrate of 18g (0.3mol) 85% is slowly added dropwise in product (IV), is added dropwise
After be warming up to reflux, react 4-5h, be cooled to room temperature, poured into 300g ice water after reaction, be precipitated immediately a large amount of white
Through filtering, washing and dry, crude product is made, by recrystallizing to obtain intermediate product (V) in color solid.By compound (V) with
POCl3Make solvent, with substitution acid compounds react the structure of benzopyrazines containing methoxyl group shown in formula (I) 1,2,4- triazoles
Derivative.
Embodiment 1~15, the acids different from substituent group synthesis compound 1~15 is as follows, other synthesis conditions
Do not change.
Embodiment 1
8- methoxyl groups-Isosorbide-5-Nitrae-diphenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 40.0%, fusing point 168-171
℃；1H NMR(400MHz,CDCl3/TMS),δ4.00(s,3H,OCH3),7.45-7.48(m,3H,Ph-H),7.56(m,3H,
Ph-H),7.63-7.71(m,3H,Ph-H),7.77(m,1H,Ph-H),7.88(m,2H,Ph-H),7.97(m,1H,Ph-H)
.HRMS(ESI)m/z:Calculated,353.1397,Found,353.1391[M+H]+.
Embodiment 2
8- methoxyl group -4- phenyl -1- undecyls-[1,2,4] triazole [4,3-a] quinoxaline, yield 76.2%, fusing point
125-130℃；1H NMR (400MHZ, CDCl3/TMS), δ 0.90 (t, J=5.6Hz, 3H, CH3), 1.28 (m, 16H, CH2),
1.66 (m, J=6.0Hz, 2H, CH2), 2.37 (t, J=6.0Hz, 2H, CH2), 4.00 (s, 3H, OCH3), 7.46 (m, 2H, Ph-
H),7.56(m,3H,Ph-H),7.88(m,2H,Ph-H),7.97(m,1H,Ph-H).HRMS(ESI)m/z:Calculated,
431.2805,Found,431.2809[M+H]+.
Embodiment 3
1- (3- fluorophenyls) -8- methoxyl group -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 60.1%, fusing point
164-168℃；1H NMR(400MHZ,CDCl3/TMS),δ4.00(s,3H,OCH3),7.45-7.48(m,3H,Ph-H),
7.54-7.58(m,4H,Ph-H),7.63-7.70(m,2H,Ph-H),7.68(m,2H,Ph-H),7.97(m,1H,Ph-H)
.HRMS(ESI)m/z:Calculated,371.1303,Found,371.1307[M+H]+.
Embodiment 4
8- methoxyl groups -1- (4- n-pentyls phenyl) -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 64.3%,
90-94 DEG C of fusing point；1H NMR (400MHZ, CDCl3/TMS), δ 4.00 (s, 3H, OCH3), 0.92 (t, J=5.2Hz, 3H,
), CH3 1.35 (m, 4H, CH2), 1.66 (m, J=6.0Hz, 2H, CH2), 2.70 (t, J=6.0Hz, 2H, CH2), 7.30 (d, J
=6.8Hz, 2H, Ph-H), 7.48 (s, 1H, Ph-H), 7.55 (m, 3H, Ph-H), 7.88 (m, 2H, Ph-H), 7.97 (d, J=
7.2Hz, 1H, Ph-H), 8.04 (d, J=6.4Hz, 2H, Ph-H) .HRMS (ESI) m/z:Calculated,423.2179,
Found,423.2188[M+H]+.
Embodiment 5
8- methoxyl groups -1- (4- nitrobenzophenones) -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 70.0% melt
153-157 DEG C of point；1H NMR(400MHZ,CDCl3/TMS),δ4.00(s,3H,OCH3),7.47(m,2H,Ph-H),7.56(m,
3H,Ph-H),7.64(m,2H,Ph-H),7.87(m,2H,Ph-H),7.97(m,1H,Ph-H),8.06(m,1H,Ph-H),8.18
(m,1H,Ph-H).HRMS(ESI)m/z:Calculated,398.1248,Found,398.1263[M+H]+.
Embodiment 6
8- methoxyl groups -1- (3- nitrobenzophenones) -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 63.0% melt
144-149 DEG C of point；1H NMR(400MHZ,CDCl3/TMS),δ4.00(s,3H,OCH3),7.47(m,2H,Ph-H),7.56(m,
2H, Ph-H), 7.63 (m, 2H, Ph-H), 7.87 (m, 2H, Ph-H), 7.92 (t, J=6.4Hz, 1H, Ph-H), 7.97 (m, 1H,
Ph-H),8.19(m,2H,Ph-H).HRMS(ESI)m/z:Calculated,398.1263,Found,398.1248[M+H]+.
Embodiment 7
8- methoxyl groups -1- (4- methoxyphenyls) -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 59.4%,
150-154 DEG C of fusing point；1H NMR(400MHZ,CDCl3/TMS),δ3.91(s,3H,OCH3),4.00(s,3H,OCH3),7.47
(m, 2H, Ph-H), 7.55-7.62 (m, 3H, Ph-H), 7.72 (d, J=7.2Hz, 1H, Ph-H), 7.87 (m, 2H, Ph-H),
7.97(m,1H,Ph-H),8.09(m,3H,Ph-H).HRMS(ESI)m/z:Calculated,383.1503,Found,
383.1519[M+H]+.
Embodiment 8
1- (4- isopropyl phenyls) -8- methoxyl group -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 66.0%,
154-159 DEG C of fusing point；1H NMR (400MHZ, CDCl3/TMS), δ 1.30 (d, J=5.6Hz, 6H, CH3), 3.01 (m, J=
5.6Hz, 1H, CH), 4.00 (s, 3H, OCH3), 7.34 (d, J=6.4Hz, 1H, Ph-H), 7.46-7.59 (m, 7H, Ph-H),
7.17 (m, 2H, Ph-H), 7.97 (d, J=8.0Hz, 1H, Ph-H), 8.04 (m, 1H, Ph-H) .HRMS (ESI) m/z:
Calculated,395.1866,Found,395.1876[M+H]+.
Embodiment 9
1- (2- chloropyridine -4- bases) -8- methoxyl group -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield
40.0%, 127-131 DEG C of fusing point；1H NMR(400MHZ,CDCl3/TMS),δ4.00(s,3H,OCH3),7.46(m,1H,Ph-
H),7.55(m,3H,Ph-H),7.60-7.65(m,3H,Ph-H),7.87(m,2H,Ph-H),7.97(m,1H,Ph-H),8.16
(m,1H,Ph-H).HRMS(ESI)m/z:Calculated,388.0960,Found,388.0964[M+H]+.
Embodiment 10
1- (4- n-propyls phenyl) -8- methoxyl group -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 57.1%,
128-130 DEG C of fusing point；1H NMR (400MHZ, CDCl3/TMS), δ 0.97 (t, J=6.0Hz, 3H, CH3), 1.70 (m, J=
6.0Hz, 2H, CH2), 2.68 (t, J=6.0Hz, 2H, CH2), 4.00 (s, 3H, OCH3), 7.30 (d, J=6.4Hz, 2H, Ph-
), H 7.47 (m, 2H, Ph-H), 7.56 (m, 2H, Ph-H), 7.64 (m, 1H, Ph-H), 7.70 (d, J=6.4Hz, 1H, Ph-H),
7.87 (m, 1H, Ph-H), 7.97 (m, 1H, Ph-H), 8.15 (d, J=6.4Hz, 2H, Ph-H) .HRMS (ESI) m/z:
Calculated,395.1866,Found,395.1872[M+H]+.
Embodiment 11
1- (furans -2- bases) -8- methoxyl group -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 96.5% melt
149-151 DEG C of point；1H NMR (400MHZ, CDCl3/TMS), δ 4.00 (s, 3H, OCH3), 6.91 (d, J=2.4Hz, 1H,
), furan-H 7.47 (m, 2H, 1Ph-H, 1furan-H), 7.56 (m, 3H, Ph-H), 7.64 (q, J=6.0Hz, 1H, Ph-H),
7.87 (m, 2H, Ph-H), 7.97 (m, 1H, Ph-H), 8.83 (d, J=6.4Hz, 1H, furan-H) .HRMS (ESI) m/z:
Calculated,343.1190,Found,343.1200[M+H]+.
Embodiment 12
8- methoxyl groups -1- (2,4- dichlorophenyl) -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 84.5%,
134-139 DEG C of fusing point；1H NMR (400MHZ, CDCl3/TMS), δ 4.00 (s, 3H, OCH3), 7.37 (d, J=7.2Hz, 1H,
Ph-H),7.48(s,1H,Ph-H),7.55(m,4H,Ph-H),7.64(m,1H,Ph-H),7.71(s,1H,Ph-H),7.88(m,
2H, Ph-H), 7.98 (t, J=7.2Hz, 2H, Ph-H) .HRMS (ESI) m/z:Calculated,421.0617,Found,
421.0630[M+H]+.
Embodiment 13
1- (3- chlorphenyls) -8- methoxyl group -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 70.8%, fusing point
149-151℃；1H NMR(400MHZ,CDCl3/TMS),δ4.00(s,3H,OCH3),7.43-7.48(m,3H,Ph-H),7.56
(m, 3H, Ph-H), 7.62 (d, J=6.4Hz, 1H, Ph-H), 7.88 (m, 2H, Ph-H), 7.97 (d, J=6.4Hz, 1H, Ph-
), H 8.02 (d, J=6.4Hz, 1H, Ph-H), 8.12 (s, 1H, Ph-H) .HRMS (ESI) m/z:Calculated,387.1007,
Found,387.1015[M+H]+.
Embodiment 14
1- (4- fluorophenyls) -8- methoxyl group -4- phenyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 79.7%, fusing point
178-181℃；1H NMR (400MHZ, CDCl3/TMS), δ 4.00 (s, 3H, OCH3), 7.18 (t, J=6.8Hz, 2H, Ph-H),
7.47 (m, 2H, Ph-H), 7.57 (m, 3H, Ph-H), 7.88 (m, 2H, Ph-H), 7.97 (d, J=7.2Hz, 1H, Ph-H), 8.16
(m,2H,Ph-H).HRMS(ESI)m/z:Calculated,371.1307,Found,371.1303[M+H]+.
Embodiment 15
Tolyl-[1,2,4] triazole [4,3-a] quinoxaline, yield 58.2%, fusing point between 8- methoxyl group -4- phenyl -1-
175-179℃；1H NMR(400MHZ,CDCl3/TMS),δ2.45(s,3H,CH3),4.00(s,3H,OCH3),7.44-7.48
(m,3H,Ph-H),7.56(m,4H,Ph-H),7.87(m,2H,Ph-H),7.93-7.98(m,3H,Ph-H).HRMS(ESI)m/
z:Calculated,389.1373,Found,389.1180[M+Na]+.
16 activity of weeding of embodiment is tested
Subjects：Creeping bentgrass, romaine lettuce.
Test method：The filter paper of a diameter 5.6cm is completed in the culture dish of diameter 6cm, 2 milliliters of addition is certain density
Test compounds solution, the rape seed 10 when sowing seed soaking 6 is small.At 28 ± 1 DEG C, dark culturing measures radicle after 7 days long
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%.
The Herbicide activity data of 1 embodiment 1-15 of table
Show that embodiment 4,7,10,12,13,14 pairs of creeping bentgrasses have good activity of weeding from 1 activity of weeding of table, wherein
4,10 pairs of romaine lettuce of embodiment have activity of weeding.
Claims (13)
1. a kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group, it is characterised in that its structural formula is such as shown in (I)：
Wherein：R1For phenyl, undecyl, 3- fluorophenyls, 4- amyl phenyl, 4- nitrobenzophenones, 3- nitrobenzophenones, 4- methoxyl groups
Phenyl, 4- isopropyl phenyls, 2- chloropyridines, 4- n-propyl phenyl, 2- furans, 2,4- dichlorophenyls, 3- chlorphenyls, 4- fluorobenzene
Base, 3- aminomethyl phenyls.
2. a kind of preparation side of the 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 1
Method, it is characterised in that include the following steps：
1) it is solvent in methanol, RaneyNi is under catalysts conditions, and 4- methoxyl group -2- nitroanilines are heated to reflux with hydrazine hydrate
It is made such as formula (II) compound represented (II)；
2) compound (II) and methyl benzoylformate the reaction synthesis obtained step 1) is such as formula (III) compound represented
(III) crude product；
3) compound (III) crude product obtained step 2) washs after purification through ethyl alcohol, uses POCl3Solvent is made, is heated to reflux item
Chlorination reaction is carried out under part, is terminated through TLC monitoring reactions, it is post-treated to obtain such as formula (IV) compound represented (IV), going forward side by side
Row the next step；
4) using ethyl alcohol as solvent, the compound (IV) that step 3) is obtained obtains (the 7- first shown in formula (V) with hydration hydrazine reaction
Oxygroup -3- phenyl quinoxaline -2- bases) hydrazine crude product (V)；
5) compound (V) crude product obtained step 4) is after recrystallization purifying, with POCl3Solvent is made, with substituting acids
Close object react the structure of benzopyrazines containing methoxyl group shown in formula (I) 1,2,4- triazole derivatives；
Preparation process is as follows：
Wherein：R1For phenyl, undecyl, 3- fluorophenyls, 4- amyl phenyl, 4- nitrobenzophenones, 3- nitrobenzophenones, 4- methoxyl groups
Phenyl, 4- isopropyl phenyls, 2- chloropyridines, 4- n-propyl phenyl, 2- furans, 2,4- dichlorophenyls, 3- chlorphenyls, 4- fluorobenzene
Base, 3- aminomethyl phenyls.
3. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
It is characterized in that in step 1), each substance inventory of addition is：0.1mol 4- methoxyl groups ortho-nitraniline, 30-50mL methanol,
Hydrazine hydrate, 0.25~0.45g RaneyNi, RaneyNi of 70-80mL85% is weight in wet base.
4. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
The reaction temperature in step 2) is characterized in that as room temperature, reaction time 30-90min.
5. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
It is characterized in that in step 3) that post-processing approach is：It is poured slowly into after completion of the reaction in ice water, a large amount of yellow solids is precipitated immediately, take out
Filter, washing drying, obtain compound (IV).
6. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
It is characterized in that in step 4), the molar ratio of compound (IV) and 85% hydrazine hydrate is 1：2.5-3.5.
7. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
It is characterized in that compound (V) with substituting the ratio between amount of substance of acid compounds for 1:1：1.2, the time is heated to reflux as 3.5-
4.54h。
8. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
It is characterized in that in step 3), TLC is extracted reaction solution when monitoring, and is added in ice water and is cracked POCl3, then production is extracted with ethyl acetate
Object takes organic layer, with ethyl acetate：Petroleum ether=1:3 mixed liquors are solvent, monitor the carry out degree of reaction.
9. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
Be characterized in that in step 1), each substance inventory of addition is 0.1mol 4- methoxyl groups ortho-nitraniline, 40mL methanol,
Hydrazine hydrate, 0.25~0.45g RaneyNi, RaneyNi of 75mL85% is weight in wet base.
10. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
It is characterized in that in step 4), the molar ratio of compound (IV) and 85% hydrazine hydrate is 1：3.
11. the preparation method of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 2,
It is characterized in that compound (V) with substituting the ratio between amount of substance of acid compounds for 1:1：1.2, the time is heated to reflux as 4h.
12. a kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group according to claim 1 are as weeding
The application of agent.
13. a kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group as described in claim 1 are as herbicide
In the application of prevention creeping bentgrass, romaine lettuce weeds.
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| 含邻氟苯基的1，2，4-三唑类衍生物的合成及杀菌活性研究;童建颖等;《有机化学》;20121231;第32卷;2373-2377 * |
| 新型N-酰基-7-甲氧基-苯并[4，5]噻唑并[2，3-c][1，2，4]三唑-3（2H）-硫酮的合成及其除草活性;王海林等;《有机化学》;20141231;第34卷;419-423 * |
| 新型取代-3-芳基-1，2，4-三唑并[3，4-b]苯并噻唑的合成及其杀菌活性;翁建全等;《有机化学》;20121231;第32卷;957-961 * |
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Application publication date: 20161221 Assignee: Hangzhou Guangyoujiu Enterprise Management Partnership (L.P.) Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033595 Denomination of invention: A 1,2,4-triazole derivative containing methoxybenzopyrazine structure and its preparation method and application Granted publication date: 20180529 License type: Common License Record date: 20230316 Application publication date: 20161221 Assignee: Hangzhou baibeiyou Biotechnology Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033594 Denomination of invention: A 1,2,4-triazole derivative containing methoxybenzopyrazine structure and its preparation method and application Granted publication date: 20180529 License type: Common License Record date: 20230315 Application publication date: 20161221 Assignee: Hangzhou Zhiguo Enterprise Service Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033596 Denomination of invention: A 1,2,4-triazole derivative containing methoxybenzopyrazine structure and its preparation method and application Granted publication date: 20180529 License type: Common License Record date: 20230316 |