CN105017258A - Prepartion and application of pyrazolo[3,4-d][1,2,3]triazine-4-one derivative - Google Patents
Prepartion and application of pyrazolo[3,4-d][1,2,3]triazine-4-one derivative Download PDFInfo
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- CN105017258A CN105017258A CN201410852895.1A CN201410852895A CN105017258A CN 105017258 A CN105017258 A CN 105017258A CN 201410852895 A CN201410852895 A CN 201410852895A CN 105017258 A CN105017258 A CN 105017258A
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- Prior art keywords
- pyrazolo
- compound
- triazin
- derivative
- benzene ring
- Prior art date
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- RTJVWBJAMNGXCI-UHFFFAOYSA-N pyrazolo[3,4-d]triazin-4-one Chemical class O=C1N=NN=C2N=NC=C12 RTJVWBJAMNGXCI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000004009 herbicide Substances 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 5
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 5
- 241000196324 Embryophyta Species 0.000 claims abstract description 4
- -1 propargyloxy Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 108020001991 Protoporphyrinogen Oxidase Proteins 0.000 claims description 6
- 102000005135 Protoporphyrinogen oxidase Human genes 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 3
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 102000004316 Oxidoreductases Human genes 0.000 abstract 1
- 108090000854 Oxidoreductases Proteins 0.000 abstract 1
- 241001233957 eudicotyledons Species 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- 125000006412 propinylene group Chemical group [H]C#CC([H])([H])* 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 0 Cc(c(F)c1)cc(N2*)c1OCC2=O Chemical compound Cc(c(F)c1)cc(N2*)c1OCC2=O 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000007529 inorganic bases Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BFMGSMOYBHOHGI-UHFFFAOYSA-N 5-amino-1-phenylpyrazole-4-carboxylic acid Chemical compound NC1=C(C(O)=O)C=NN1C1=CC=CC=C1 BFMGSMOYBHOHGI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- UHSGPDMIQQYNAX-UHFFFAOYSA-N protoporphyrinogen Chemical compound C1C(=C(C=2C=C)C)NC=2CC(=C(C=2CCC(O)=O)C)NC=2CC(N2)=C(CCC(O)=O)C(C)=C2CC2=C(C)C(C=C)=C1N2 UHSGPDMIQQYNAX-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- PLWOICGVUYAODQ-UHFFFAOYSA-N 5-amino-1-phenylpyrazole-4-carbonyl chloride Chemical compound NC1=C(C(Cl)=O)C=NN1C1=CC=CC=C1 PLWOICGVUYAODQ-UHFFFAOYSA-N 0.000 description 2
- VHRCRGJPHYNVGS-UHFFFAOYSA-N 6-amino-7-fluoro-4-prop-2-ynyl-1,4-benzoxazin-3-one Chemical compound C#CCN1C(=O)COC2=C1C=C(N)C(F)=C2 VHRCRGJPHYNVGS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical group [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000000857 drug effect Effects 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- MOBRMRJUKNQBMY-UHFFFAOYSA-N 1-(chloromethyl)-2-fluorobenzene Chemical compound FC1=CC=CC=C1CCl MOBRMRJUKNQBMY-UHFFFAOYSA-N 0.000 description 1
- JHRWOZRHVYZOBZ-UHFFFAOYSA-N CC(C)(C)[n]1ncc(C(O)=O)c1N Chemical compound CC(C)(C)[n]1ncc(C(O)=O)c1N JHRWOZRHVYZOBZ-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 125000005085 alkoxycarbonylalkoxy group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- AYJIUOZKKTUKKD-UHFFFAOYSA-N ethyl 5-amino-1-phenylpyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=CC=C1 AYJIUOZKKTUKKD-UHFFFAOYSA-N 0.000 description 1
- DJFSJKPXNYYPFK-UHFFFAOYSA-N ethyl 5-amino-1-tert-butylpyrazole-4-carboxylate Chemical compound CCOC(=O)C=1C=NN(C(C)(C)C)C=1N DJFSJKPXNYYPFK-UHFFFAOYSA-N 0.000 description 1
- 238000010228 ex vivo assay Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- 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)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The invention relates to prepartion and application of a pyrazolo[3,4-d][1,2,3]triazine-4-one derivative. The structural formula of the derivative is shown in the formula (1), wherein X1 is hydrogen, halogen and halogenated alkyl; n is 0 and 1; X2 is halogen; X3 is alkoxyl, alkenyloxyl, alkynyloxyl, halogenated alkenyloxyl and the like; X2 and X3 further can form a benzo 6-membered heterocyclic ring with a benzene ring. The compound shown in the formula (I) has excellent protoporphyrinongen oxidase (PPO) inhibitory activity and excellent herbicidal activity. The compound serving as a herbicide is used for controlling and eliminating monocotyledonous weeds and dicotyledon weeds. The formula (I) is shown in the description.
Description
[ technical field ]: the invention relates to the technical field of protoporphyrinogen oxidase (PPO) inhibitors and herbicides and preparation thereof, in particular to pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivatives, a preparation method thereof and application thereof as the PPO inhibitors and the herbicides.
[ background Art ] A method of: CN 1345722A discloses a 3- (substituted phenyl) 1,2, 3-benzotriazin-4-one compound A with herbicidal activity, which is used as a broad-spectrum herbicide with the effective dose of 50-1500 g/ha.
CN 101215289a discloses a 3-substituted phenyl-pyrazolo [3,4-D ] [1,2,3] triazin-4-one compound (B-D) having protoporphyrinogen oxidase (PPO) inhibitory activity and herbicidal activity.
In the formula, R1Are hydrogen, alkyl, haloalkyl,
R2is alkyl, alkenyl, alkynyl, haloalkenyl,
X1hydrogen, halogen; x2Is halogen, nitro; x3Is alkoxy, alkenyloxy, alkynyloxy, haloalkenyloxy, alkoxycarbonylalkoxy;
X2and X3Can form a benzo 6-membered heterocyclic ring with the benzene ring.
[ summary of the invention ]: the invention aims to provide a pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative with PPO (Poly-p-phenylene oxide) inhibitory activity and herbicidal activity, and a preparation method and application thereof. The compound is different from the known compound, has novel structure and excellent PPO (Poly-p-phenylene oxide) inhibition activity and herbicidal activity.
The compound of the invention has high PPO inhibition activity and high weeding activity on monocotyledonous and dicotyledonous weeds.
The compounds of the invention have the general formula (I):
in the formula,
X1is hydrogen, halogen, haloalkyl;
n is 0, 1;
X2is halogen;
X3alkoxy, alkenyloxy, alkynyloxy, haloalkenyloxy, etc.;
X2and X3Can also form a benzo 6-membered heterocyclic ring with a benzene ring, and the general formula is (II);
wherein,
r is alkyl, alkenyl or alkynyl;
said alkyl group being C1～C6Is straight-chain or branched alkyl, alkenyl is C3～C6Alkenyl or alkynyl of (A) is C3～C6Alkynyl group of (1).
Among the pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivatives of the present invention, preferred are:
X1hydrogen, fluorine, chlorine, trifluoromethyl; n is 0, 1; x2Is chlorine; x3Is propoxy, allyloxy, propargyloxy;
X2and X3Or can form a benzo-6-membered heterocycle with the benzene ring, which has the general formula (II), R3Is n-propyl, allyl, propargyl.
The pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative can be prepared by the following method one: dissolving a compound (a) in a solvent, adding an inorganic base, heating to 40-80 ℃, hydrolyzing to obtain a compound (b), performing acyl chlorination on the compound (b) by thionyl chloride to obtain a compound (c), reacting with the compound (d) to obtain a compound (e), acidifying the compound (e) by hydrochloric acid to form a salt, and reacting with sodium nitrite to obtain the pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative (I). The solvent is as follows: toluene, benzene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, water, or a mixed solvent of the above solvents in any proportion; the inorganic base is sodium hydroxide or potassium hydroxide.
The method comprises the following steps:
the pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative can also be prepared by the following method II: dissolving a compound (f) in a solvent I, adding an inorganic base I, heating to 40-80 ℃, hydrolyzing to obtain a compound (g), performing acyl chlorination on the compound (g) by thionyl chloride to obtain a compound (h), reacting with the compound (d) to obtain a compound (I), acidifying the compound (I) by hydrochloric acid to form a salt, reacting with sodium nitrite to obtain a pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative (j), heating to 40-90 ℃ in a solvent II, removing tert-butyl to obtain a compound (k), dissolving the compound (k) in a solvent III, adding an inorganic base II and substituted benzyl halide, and reacting to obtain the pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative (I). The first solvent is as follows: toluene, benzene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, water, or a mixed solvent of the above solvents in any proportion; the second solvent is: methanol, ethanol, tertiary butanol, formic acid, acetic acid or mixed solvent of the above solvents in any proportion; the third solvent is: acetone, acetonitrile, dichloromethane, chloroform, dioxane, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), or a mixture of the above solvents at any ratio; the inorganic base I is: sodium hydroxide, potassium hydroxide; the inorganic base II is: sodium carbonate, potassium carbonate and sodium hydride.
The second method comprises the following steps:
the invention is further illustrated by the compounds listed in Table 1, but is not limited thereto.
The pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative provided by the invention is different from the known compounds, has a completely novel structure, and has excellent PPO (Poly-p-phenylene oxide) inhibition activity and herbicidal activity.
The compound of the invention is applied to pesticides as a herbicide for weeding monocotyledonous and dicotyledonous weeds.
[ embodiments ] of the present invention:
the invention is further illustrated by the following examples in which the melting points are uncorrected.
Example 1: synthesis of 1-phenyl-5-amino-1H-pyrazole-4-carboxylic acid (b1)
In a 500mL round bottom flask, 9.25g of 1-phenyl-5-amino-1H-pyrazole-4-carboxylic acid ethyl ester (a1), 15mL of tetrahydrofuran, 45mL of anhydrous methanol and 25mL of 3mol/L aqueous sodium hydroxide solution were added, heated under reflux for 4 hours, most of the solvent was removed under reduced pressure, the residue was acidified to pH 1 with 6mol/L hydrochloric acid, a milky white precipitate appeared, filtered, washed with water, then with dichloromethane, and dried to give b1(8.10g) as a white solid with a yield of 99.7% and a melting point 243 and 244 ℃.
Example 2: synthesis of 1-phenyl-5-amino-1H-pyrazole-4-carbonyl chloride (c1)
1.02g of 1-phenyl-5-amino-1H-pyrazole-4-carboxylic acid (b1) is added into a 50mL round-bottom flask, 10mL of thionyl chloride is added dropwise under cooling of an ice salt bath, the mixture is naturally warmed to room temperature after being added dropwise, the mixture is stirred for 3 hours, and the thionyl chloride is pumped out under reduced pressure to obtain yellow solid c1(1.11g), and the reaction is quantitatively finished and is directly used for next-step synthesis.
Example 3: synthesis of 1-phenyl-5-amino-N- (3-oxo-4-propargyl-7-fluoro-3, 4-dihydro-2H-benzo [ b ] [1, 4] oxazinyl-6-) -1H-pyrazole-4-carboxamide (e1)
0.24g of 4-propargyl-6-amino-7-fluoro-2H-benzo [ b ] [1, 4] oxazine-3 (4H) -one, 6mL of dichloromethane and 1mL of pyridine are added into a 50mL round-bottom flask, a cold salt bath is cooled to below 0 ℃, 0.22g of 1-phenyl-5-amino-1H-pyrazole-4-formyl chloride (c1) is added, the temperature is naturally raised to room temperature, a TLC detection reaction is carried out, after the reaction is finished, the solvent is removed under reduced pressure, the residual liquid is washed by 20mL of 1mol/L hydrochloric acid, the solid is filtered, the solid is washed by a saturated sodium bicarbonate solution, and the solid is filtered and dried to obtain an off-white solid e1(0.40g), the yield is 98.7%, and the melting point 188 ℃ is 189 ℃.
Example 4: synthesis of target Compound I2
In a four-necked flask equipped with a mechanical stirrer, 0.40g of 1-phenyl-5-amino-N- (3-oxo-4-propargyl-7-fluoro-3, 4-dihydro-2H-benzo [ b ] [1, 4] oxazinyl-6-) -1H-pyrazole-4-carboxamide (e1), 1.2mL of methanol and 10mL of 6mol/L hydrochloric acid were charged, the mixture was stirred for 10 hours, the mixture was cooled to 0 ℃ or lower in an ice salt bath, 0.22g of an aqueous solution of sodium nitrite was added dropwise, the mixture was stirred for 1.5 hours while controlling the temperature below 0 ℃, the reaction mixture was extracted with ethyl acetate (15mL × 3), the organic phase was washed with saturated saline, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure, and then column chromatography was performed [ V (petroleum ether)/V (ethyl acetate) ═ 3/1] to obtain I1(0.29g) as a pale yellow solid, the yield was 69.7%, melting point 204-.
Example 5: synthesis of 1-tert-butyl-5-amino-1H-pyrazole-4-carboxylic acid (g)
In a 500mL round bottom flask, 10.55g of 1-tert-butyl-5-amino-1H-pyrazole-4-carboxylic acid ethyl ester (f), 50mL of tetrahydrofuran, 50mL of anhydrous methanol and 50mL of 2.5mol/L aqueous sodium hydroxide solution were added, the mixture was heated to 60 ℃, the temperature was controlled for 4 hours, most of the solvent was removed under reduced pressure, the residue was acidified to pH 1 with 6mol/L hydrochloric acid, a milky white precipitate appeared, filtered, washed with water, then with dichloromethane, and dried to give g (5.70g) of a pale yellow solid, with a yield of 62.3%.
Example 6: synthesis of 1-tert-butyl-5-amino-1H-pyrazole-4-carbonyl chloride (H)
0.92g of 1-tert-butyl-5-amino-1H-pyrazole-4-carboxylic acid (g) is added into a 50mL round-bottom flask, 10mL of thionyl chloride is added dropwise under cooling of an ice salt bath, the mixture is naturally raised to room temperature after being added dropwise, the mixture is stirred for 3 hours, the thionyl chloride is pumped out under reduced pressure to obtain yellow liquid H (1.03g), and the reaction is quantitatively finished and is directly used for next-step synthesis.
Example 7: synthesis of 1-tert-butyl-5-amino-N- (3-oxo-4-propargyl-7-fluoro-3, 4-dihydro-2H-benzo [ b ] [1, 4] oxazinyl-6-) -1H-pyrazole-4-carboxamide (i)
0.44g of 4-propargyl-6-amino-7-fluoro-2H-benzo [ b ] [1, 4] oxazine-3 (4H) -one, 10mL of dichloromethane and 1.2mL of pyridine are added into a 50mL round bottom flask, the mixture is cooled to below 0 ℃ in an ice salt bath, 0.37g of 1-tert-butyl-5-amino-1H-pyrazole-4-formyl chloride (H) is added, the mixture is naturally warmed to room temperature, a TLC detection reaction is carried out, after the reaction is finished, the solvent is removed under reduced pressure, the residual liquid is washed by 30mL of 1mol/L hydrochloric acid, the solid is filtered, the solid is washed by a saturated sodium bicarbonate solution, and the filtration and the drying are carried out to obtain an off-white solid i (0.44g), the yield is 57.1%, and the melting point is 170 and 172 ℃.
Example 8: synthesis of 3- (7-fluoro-4-propargyl-3, 4-dihydro-2H-benzo [ b ] [1, 4] oxazinyl-6-) -7-tert-butyl-3H-pyrazolo [3,4-d ] [1,2,3] triazin-4 (7H) -one (j)
In a four-necked flask equipped with a mechanical stirrer, 0.39g of 1-tert-butyl-5-amino-N- (3-oxo-4-propargyl-7-fluoro-3, 4-dihydro-2H-benzo [ b ] [1, 4] oxazinyl-6-) -1H-pyrazole-4-carboxamide (i), 1.2mL of methanol and 10mL of 6mol/L hydrochloric acid were charged, stirred for 10 hours, cooled to 0 ℃ or lower with an ice salt bath, 0.22g of an aqueous solution of sodium nitrite was dropped, stirred for 1.5 hours while controlling the temperature below 0 ℃, the reaction solution was extracted with ethyl acetate (15mL × 3), the organic phase was washed with saturated saline, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure, and then separated by column chromatography [ V (petroleum ether)/V (ethyl acetate) ═ 3/1] to obtain a white solid j (0.29g), the yield was 73.2%, melting point 232-.
Example 9: synthesis of 3- (7-fluoro-4-propargyl-3, 4-dihydro-2H-benzo [ b ] [1, 4] oxazinyl-6-) -3H-pyrazolo [3,4-d ] [1,2,3] triazin-4 (7H) -one (k)
0.60g of 3- (7-fluoro-4-propargyl-3, 4-dihydro-2H-benzo [ b ] [1, 4] oxazinyl-6-) -7-tert-butyl-3H-pyrazolo [3,4-d ] [1,2,3] triazin-4 (7H) -one (i) and 20mL of formic acid were mixed in a round-bottomed flask, heated to 60 ℃ with stirring, and kept at the temperature for reaction for 7 hours, after the reaction was completed, extracted with ethyl acetate, and subjected to column chromatography for purification to obtain a pale yellow solid k (0.26g), yield of 51.2%, and melting point 196 ℃ (decomposition).
Example 10: synthesis of target Compound I10
0.10g of 3- (7-fluoro-4-propargyl-3, 4-dihydro-2H-benzo [ b ]][1，4]Oxazinyl-6-) -3H-pyrazolo [3,4-d][1，2，3]Triazin-4 (7H) -one (k), 0.05g K2CO3And 3mL of DMF was mixed in a 25mL round bottom flask. After stirring for 30min, 0.04g of 2-fluorobenzyl chloride was added dropwise. The reaction was stirred at room temperature overnight. After completion of the TLC detection, the reaction mixture was dropped into 20mL of an ice-water mixture to form a white emulsion. Extraction with ethyl acetate and purification by column chromatography gave I10(0.03g) as a pale yellow solid in 25.2% yield, mp 181-.
Similarly, other compounds of the invention can be synthesized in a similar manner, as shown in Table 1.
TABLE 1 characterization of physical Properties of Compound I
| No. | X1 | X2 | X3 | n | Appearance of the product | Melting Point/. degree.C |
| I1 | H | Cl | OCH2CH＝CH2 | 0 | Yellow solid | 158-160 |
| I2 | H | X2And X3Form II with a benzene ring, R is CH2C≡CH | 0 | Pale yellow solid | 204-205 |
| I3 | H | X2And X3Form II with a benzene ring, R is CH2CH2CH3 | 0 | White solid | 182-183 |
| I4 | 2-Cl | X2And X3Form II with a benzene ring, R is CH2C≡CH | 0 | White solid | 191-192 |
| I5 | 3-CF3 | X2And X3Form II with a benzene ring, R is CH2C≡CH | 0 | Yellow solid | 138-141 |
| I6 | 3-CF3 | X2And X3Form II with a benzene ring, R is CH2CH2CH3 | 0 | White solid | 197-198 |
| I7 | 3-CF3 | X2And X3Form II with a benzene ring, R is CH2CH＝CH2 | 0 | White solid | 162-164 |
| I8 | 4-CF3 | X2And X3Form II with a benzene ring, R is CH2C≡CH | 0 | White solid | 143-146 |
| I9 | 4-CF3 | X2And X3Form II with a benzene ring, R is CH2CH＝CH2 | 0 | White solid | 145-147 |
| I10 | 2-F | X2And X3Form II with a benzene ring, R is CH2C≡CH | 1 | Pale yellow solid | 181-183 |
| I11 | 4-F | X2And X3Form II with a benzene ring, R is CH2C≡CH | 1 | White solid | 211-212 |
| I12 | 2-Cl | X2And X3Form II with a benzene ring, R is CH2C≡CH | 1 | White solid | 186-187 |
| I13 | 4-Cl | X2And X3Form II with a benzene ring, R is CH2C≡CH | 1 | White solid | 229-231 |
| I14 | 4-CF3 | X2And X3Form II with a benzene ring, R is CH2C≡CH | 1 | Pale yellow solid | 204-205 |
| I15 | 4-CH3O | X2And X3Form II with a benzene ring, R is CH2C≡CH | 1 | White solid | 158-161 |
Example 11: preliminary determination of biological Activity
Potting method (stem and leaf treatment): putting a certain amount of soil into a plastic small cup with the diameter of 8cm, adding a certain amount of water, covering soil with a certain thickness after sowing, culturing in a greenhouse, and covering seedlings with plastic before emergence. After emergence, a certain amount of clear water was added every day to maintain normal growth. When the seedling grows to a certain period, the stem and leaf spray treatment is carried out. The treatment dose was 1500 g/ha. The results of investigation after 10 days of treatment were measured for the fresh weight of the aerial parts, and the drug effect was expressed as the percentage of the fresh weight inhibition.
Potting method (soil treatment): putting a certain amount of soil into a plastic small cup with the diameter of 8cm, adding a certain amount of water, covering soil with a certain thickness after sowing, applying the pesticide on the day, culturing in a greenhouse, and covering seedlings with plastic before emergence. After emergence, a certain amount of clear water was added every day to maintain normal growth. When the seedling grows to a certain period, the stem and leaf spray treatment is carried out. The treatment dose was 1500 g/ha. The results of investigation after 10 days of treatment were measured for the fresh weight of the aerial parts, and the drug effect was expressed as the percentage of the fresh weight inhibition.
Ex vivo assay of protoporphyrinogen oxidase (PPO) inhibitory activity: taking a maize etiolated seedling cultured in a dark room for 6-7 days, extracting PPO from the maize etiolated seedling, reducing protoporphyrinogen IX into protoporphyrinogen IX, then adding a certain amount of PPO, a compound to be detected with different concentrations, protoporphyrinogen IX and a buffer solution into a reaction system, and measuring the fluorescence intensity at a wavelength of 630nm after dark reaction for 30 minutes. Performing curve fitting according to one site competition equation of GraphPad Prism 4.0 to obtain pI of the compound50。
Table 2: herbicidal Activity inhibition (%) of Compound I (dose 1500 g/ha)
Table 3: pI of PPO inhibition by compound I50
| No. | pI50 | Std.Error | No. | pI50 | Std.Error |
| I1 | 5.77 | 0.05 | I9 | 5.48 | 0.09 |
| I2 | 6.84 | 0.04 | I10 | 7.63 | 0.06 |
| I3 | 5.85 | 0.02 | I11 | 7.22 | 0.03 |
| I4 | 6.84 | 0.06 | I12 | 7.55 | 0.04 |
| I5 | 7.99 | 0.04 | I13 | 7.49 | 0.03 |
| I6 | 7.11 | 0.06 | I14 | 7.44 | 0.05 |
| I7 | 7.42 | 0.10 | I15 | 7.18 | 0.06 |
| I8 | 5.78 | 0.02 |
Example 12: rescreening assay for herbicidal Activity
The reduced dose of the compound with outstanding activity was re-screened. The measurement was carried out in the same manner as in example 11, and the results are shown in Table 4.
Table 4: herbicidal Activity inhibition Rate (%)
Claims (5)
1. A pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivative having protoporphyrinogen oxidase inhibitory activity and herbicidal activity, characterized in that it has a structure represented by the following general formula (I):
in the formula,
X1is hydrogen, halogen, haloalkyl;
n is 0, 1;
X2is halogen;
X3alkoxy, alkenyloxy, alkynyloxy, haloalkenyloxy, etc.;
X2and X3Can also form a benzo 6-membered heterocyclic ring with a benzene ring, and the general formula is (II);
wherein,
r is alkyl, alkenyl or alkynyl;
said alkyl group being C1～C6Is straight-chain or branched alkyl, alkenyl is C3～C6Alkenyl or alkynyl of (A) is C3～C6Alkynyl group of (1).
2. The compound of claim 1, wherein:
X1preferably hydrogen, fluorine, chlorine, trifluoromethyl;
n is preferably 0, 1;
X2preferably chlorine;
X3preferably propoxy, allyloxy, propargyloxy;
X2and X3Or can form a benzo-6-membered heterocycle with the benzene ring, which has the general formula (II), R3Preference is given to n-propyl, allyl, propargyl.
3. A process for the preparation of pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivatives as claimed in claim 1, which comprises the steps of:
wherein X1、X2、X3And R is as defined in the general formulae (I), (II).
4. A process for the preparation of pyrazolo [3,4-d ] [1,2,3] triazin-4-one derivatives as claimed in claim 1, which comprises the steps of:
wherein X1、X2、X3And R is as defined in the general formulae (I), (II).
5. Use of a compound according to claim 1 as protoporphyrinogen oxidase (PPO) inhibitor; can also be used as herbicide for preventing and killing monocotyledonous and dicotyledonous weeds.
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| CN104529900A (en) * | 2014-12-31 | 2015-04-22 | 南开大学 | Bactericidal activity of 1-substituted-N-substituted phenyl-5-amidogen-1H-pyrazole-4-formamide compound |
| CN108484614A (en) * | 2018-05-23 | 2018-09-04 | 南开大学 | Pyrazolo [3,4-d] pyrimidine -4 (5H) -one derivative and its preparation method and application |
| WO2019052359A1 (en) * | 2017-09-14 | 2019-03-21 | 辽宁利锋科技开发有限公司 | Anti-tumor effect and use of diheterocyclic ribavirin analog |
| CN110066282A (en) * | 2019-06-10 | 2019-07-30 | 南开大学 | A kind of pyrazolopyrimidinones and its preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529900A (en) * | 2014-12-31 | 2015-04-22 | 南开大学 | Bactericidal activity of 1-substituted-N-substituted phenyl-5-amidogen-1H-pyrazole-4-formamide compound |
| WO2019052359A1 (en) * | 2017-09-14 | 2019-03-21 | 辽宁利锋科技开发有限公司 | Anti-tumor effect and use of diheterocyclic ribavirin analog |
| CN109503587A (en) * | 2017-09-14 | 2019-03-22 | 辽宁利锋科技开发有限公司 | The antitumor action of double heterocycle ribavirin analogs and application |
| CN109503587B (en) * | 2017-09-14 | 2022-01-11 | 辽宁利锋科技开发有限公司 | Anti-tumor effect and application of diheterocyclic triazole nucleoside analogue |
| CN108484614A (en) * | 2018-05-23 | 2018-09-04 | 南开大学 | Pyrazolo [3,4-d] pyrimidine -4 (5H) -one derivative and its preparation method and application |
| CN110066282A (en) * | 2019-06-10 | 2019-07-30 | 南开大学 | A kind of pyrazolopyrimidinones and its preparation method and application |
| CN110066282B (en) * | 2019-06-10 | 2020-07-10 | 南开大学 | Pyrazolopyrimidinone compound and preparation method and application thereof |
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