CN105001217A - [1,2,4]triazole[4,3-alpha]pyridine-3(2H)-ketone derivative preparation method - Google Patents
[1,2,4]triazole[4,3-alpha]pyridine-3(2H)-ketone derivative preparation method Download PDFInfo
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Abstract
The invention relates to a [1,2,4] triazole [4,3-alpha] pyridine-3(2H)-ketone derivative preparation method. According to the method, 8-chlorine-[1,2,4] triazole[4,3-alpha] pyridine-3(2H)-ketone shown in a formula (II) and halohydrocarbon or benzyl arylhalostannyl derivatives shown in a formula (III) are subjected to a microwave radiation ring closing reaction in DMF, NaOH at the temperature of 40-80 DEG C, reaction liquid obtained after complete reaction is conducted is subjected to postprocessing, and then the product of [1,2,4] triazole [4,3-alpha] pyridine-3(2H)-ketone derivative is obtained. The preparation method is simple and high in yield, postprocessing is convenient, the novel compound is applied to prevent barnyard grass, green bristlegrass, bluegrass, leaf mustard, piemarker, amaranthus retroflexus and chenopodium serotinum, has the weeding activity and provides a basis for new pesticide research and development.
Description
Technical field
The present invention relates to a kind of novel [1,2,4] triazole [4,3-
a] pyridine-3 (2
h) preparation method of-one derivative.
Background technology
In new compound exploitation instantly, the exploitation of heterogeneous ring compound is an important directions, and wherein nitrogen heterocyclic ring occupies important position.Nitrogen-containing heterocycle compound has excellent biological activity usually, as insecticidal activity, and fungicidal activity, antitumour activity etc.Equally, this compounds also shows good weeding activity.Some of them have been developed becomes commercialization agricultural chemicals, such as, and azafenidin, amicarbazone etc.Due to the multiple biological activity that nitrogen heterocyclic ring has, make [1,2,4] triazole [4,3-
a] pyridine-3 (2
h) preparation of-one derivative, significant in New pesticides discovery research.
[1,2,4] triazole [4,3-
a] pyridine-3 (2
h)-one derivative have multiple method report.As:
2004, Venkatesan, Aranapakam M reported synthesis [1,2,4] triazole [4,3-
a] pyridine-3 (2
h) method of-one:
This reaction needed is carried out under nitrogen is protected.
2006, Sun, Chongqing reported and synthesize [1,2,4] triazole [4,3-by the substitution reaction of halogenide and amine under DMF make solvent
a] pyridine-3 (2
h) method of-one derivative:
2007, Shin, Ming-Hsiang reported a kind of synthesis [1,2,4] triazole [4,3-
a] pyridine-3 (2
h) method of-one derivative:
2013, Lindsley, Craig W reported a kind of stirred at ambient temperature synthesis [1,2,4] triazole [4,3-
a] pyridine-3 (2
h) method of-one derivative:
。
Summary of the invention
For the above-mentioned problems in the prior art, the object of the invention is to provide one [1,2,4] triazole [4,3-a] pyridine-3 (2H)-one derivative and preparation and application thereof, are specially a kind of 8-chloro-[1 with weeding activity, 2,4] triazole [4,3-
a] pyridine-3 (2
h)-one derivative and preparation method thereof and application.
Described one [1, 2, 4] triazole [4, 3-a] preparation method of pyridine-3 (2H)-one derivative, [1, 2, 4] as azoles [4, 3-a] its structural formula of pyridine-3 (2H)-one derivative is as shown in the formula (I), it is characterized in that its preparation method comprises the steps: 3-chloride-2-hydrazinopyridine and urea reaction to be synthesized obtained 8-chloro-[1 as shown in formula II, 2, 4] triazole [4, 3-a] pyridine-3 (2H)-one, 8-chloro-[1, 2, 4] triazole [4, 3-a] pyridine-3 (2H)-one and halohydrocarbon as shown in formula III or benzyl halides be at DMF, microwave radiation ring closure reaction is carried out in 40 ~ 80 DEG C in NaOH, after abundant reaction, namely gained reaction solution obtains product [1 through aftertreatment, 2, 4] triazole [4, 3-a] pyridine-3 (2H)-one derivative,
In formula (I) or formula (III), R represents alkyl, vinyl, cyano group, the substituted-phenyl of C1 ~ C11.
Described [1,2,4] preparation method of triazole [4,3-a] pyridine-3 (2H)-one derivative, is characterized in that the substituting group of described substituted benzyl is independently selected from separately one of following: the tertiary butyl, methoxyl group, cyano group, chlorine atom, bromine atoms, fluorine atom.
The preparation method of described [1,2,4] triazole [4,3-a] pyridine-3 (2H)-one derivative, is characterized in that: described 3-chloride-2-hydrazinopyridine and the molar ratio of urea are 1:2.0 ~ 4.0, and molar ratio is preferably 1:3.0.
Described [1,2,4] triazole [4,3-a] preparation method of pyridine-3 (2H)-one derivative, it is characterized in that: 8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, the molar ratio of RCH2Cl and NaOH is 1:1.0 ~ 1.5:1.0 ~ 2.0., and molar ratio is preferably 1:1.1:1.2.
Described [1,2,4] triazole [4,3-a] preparation method of pyridine-3 (2H)-one derivative, it is characterized in that: the temperature of reaction of 3-chloride-2-hydrazinopyridine and urea is 120-180 DEG C, be preferably 160 DEG C, reaction times is 20-40 min, is preferably 30min.
Described [1,2,4] preparation method of triazole [4,3-a] pyridine-3 (2H)-one derivative, is characterized in that: 8-chloro-[1,2,4] the ring closure reaction temperature of triazole [4,3-a] pyridine-3 (2H)-one and RCH2Cl is 80-100 DEG C, and the reaction times is 10-20 min., temperature of reaction is preferably 90 DEG C, and the reaction times is preferably 15 min.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: the invention provides one [1,2,4] triazole [4,3-a] its preparation method of pyridine-3 (2H)-one derivative and intermediate and application, its preparation method is simple, easy to operate, low for equipment requirements, reaction yield is high, product convenient post-treatment, purity is high, and this compound is the new compound with weeding activity, good effect is had, for the research and development of novel pesticide provide the foundation especially for preventing and treating on barnyard grass, Herba Setariae Viridis, annual bluegrass, leaf mustard, piemarker, Amaranthus retroflexus or little lamb's-quarters.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
(4) embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1 8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
3-chloride-2-hydrazinopyridine (143 mg, 1mmol) and urea (3 mmol) are joined in the microwave reaction bottle of CEM Discovery single mold microwave synthesizer, under 160 ° of C, reacts 30min.Then mixture is joined filtration, recrystallization after forming precipitation in 40ml water and obtain intermediate 8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, yield is 95%.
Embodiment 2
The synthesis of 4-((the chloro-3-oxo of 8--[1,2,4] triazole [4,3-a] pyridine-2 (3H)-Ji) methyl) benzonitrile
8-chloro-[1,2,4] triazole 4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), 4-chloromethyl cyanophenyl (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.I.e. 4-((the chloro-3-oxo of 8--[1,2,4] triazole [4,3-a] pyridine-2 (3H)-Ji) methyl) benzonitrile, productive rate 95%, m.p.216-218 DEG C; 1H NMR (CDCl3,400 MHz), δ: 5.25 (s; 2H, NCH2), 6.52 (t; J=6.8Hz, 1H, Py-H); 7.20 (d, J=7.2Hz, 1H; Py-H), 7.52 (d, J=8.4Hz; 2H; Ar-H), 7.64 (d, J=8.0Hz; 2H; Ar-H), 7.75 (d, J=6.8Hz; 1H, Py-H). HR-ESI-MS for C14H9ClN4NaO:calcd. 307.0357 [M+Na]+; Found:307.0360 [M+Na]+.
The synthesis of the chloro-2-of embodiment 3 8-(4-chlorophenylmethyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), the chloro-4-chloromethylbenzene of 1-(1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.The i.e. chloro-2-of 8-(4-chlorophenylmethyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 94%, m.p.166-168 DEG C; 1H NMR (CDCl3,400 MHz), δ: 5.17 (s; 2H, NCH2), 6.48 (t; J=7.2Hz, 1H, Py-H); 7.17 (d, J=7.2Hz, 1H; Py-H), 7.30 (d, J=8.4Hz; 2H; Ar-H), 7.48 (d, J=8.4Hz; 2H; Ar-H), 7.73 (d, J=6.8Hz; 1H, Py-H). HR-ESI-MS for C13H10Cl2N3O:calcd. 294.0195 [M+H]+; Found:294.0190 [M+H]+.
The synthesis of the chloro-2-of embodiment 4 8-(4-methoxybenzyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), 1-chloromethyl-4-anisole (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.The i.e. chloro-2-of 8-(4-methoxybenzyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 98%, m.p.116-118 DEG C; 1H NMR (CDCl3,400 MHz), δ: 3.78 (S; 3H, OCH3), 5.17 (s; 2H, NCH2), 6.44 (t; J=7.2Hz, 1H, Py-H); 6.86 (d, J=8.0Hz, 2H; Ar-H), 7.14 (d, J=6.8Hz; 1H, Py-H), 7.40 (d; J=8.4Hz, 2H, Ar-H); 7.72 (d; J=7.2Hz, 1H, Py-H). HR-ESI-MS for C17H19ClN3O:calcd. 316.1211 [M+H]+; Found:316.1212 [M+H]+.
The synthesis of the chloro-2-of embodiment 5 8-(3-chlorophenylmethyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), the chloro-4-chloromethylbenzene of 1-(1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.The i.e. chloro-2-of 8-(3-chlorophenylmethyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 95%, m.p.155-156 DEG C; 1H NMR (CDCl3,400 MHz), δ: 5.18 (s, 2H; NCH2), 6.48 (t, J=7.2Hz, 1H; Py-H), 7.18 (d, J=7.2Hz, 1H; Py-H), 7.28-7.31 (m, 3H, Ar-H); (7.41 s, 1H, Ar-H), 7.75 (d; J=7.2Hz, 1H, Py-H). HR-ESI-MS for C13H9Cl2N3NaO:calcd. 316.0015 [M+Na]+; Found:316.0021 [M+Na]+.
The synthesis of embodiment 6 2-phenmethyl-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), chloromethylbenzene (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.I.e. 2-phenmethyl-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 97%, m.p.115-117 DEG C; 1H NMR (CDCl3,400 MHz), δ: 5.21 (s; 2H, NCH2), 6.45 (t; J=6.8Hz, 1H, Py-H); 7.15 (d, J=7.2Hz, 1H; Py-H), 7.31-7.34 (m, 3H; Ar-H); (7.43-7.45 m, 2H, Ar-H); 7.75 (d; J=7.2Hz, 1H, Py-H). Elemental analysis for C13H10ClN3O:found C 59.99; H 3.76, N 16.01; Calcd. C, 60.12; H, 3.88; N, 16.18.
The synthesis of the chloro-2-of embodiment 7 8-(2-chlorophenylmethyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), the chloro-2-chloromethylbenzene of 1-(1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.The i.e. chloro-2-of 8-(2-chlorophenylmethyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 98%, m.p.184-186 DEG C; 1H NMR (CDCl3,400 MHz), δ: 5.35 (s, 2H; NCH2), 6.48 (t, J=7.2Hz; 1H, Py-H), 7.17-7.24 (m; 4H, Py-H and Ar-H), 7.38 (s; 1H, Ar-H), 7.77 (d; J=5.2Hz, 1H, Py-H). HR-ESI-MS for C13H10Cl2N3O:calcd. 294.0195 [M+H]+; Found:294.0195 [M+H]+.
The synthesis of the chloro-2-of embodiment 8 8-(2-benzyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), the fluoro-2-chloromethylbenzene of 1-(1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.The i.e. chloro-2-of 8-(2-benzyl)-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 95%, m.p.170-172 DEG C; 1H NMR (CDCl3,400 MHz), δ: 5.30 (s; 2H, NCH2), 6.47 (t; J=7.2Hz, 1H, Py-H); 7.07-7.11 (m; 2H, Ar-H), 7.16 (d; J=6.4Hz; 1H, Py-H), 7.27-7.32 (m; 2H; Ar-H), 7.75 (d, J=6.8Hz; 1H, Py-H). HR-ESI-MS for C10H11ClF2N3O2:calcd. 278.0502 [M+H]+; Found:278.0499 [M+H]+.
The synthesis of embodiment 9 2-(4-Brombenzyl)-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), the bromo-4-chloromethylbenzene of 1-(1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.I.e. 2-(4-Brombenzyl)-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 98%, m.p.224-226 DEG C; 1H NMR (CDCl3,400 MHz), δ: 5.16 (s; 2H, NCH2), 6.47 (t; J=7.2Hz, 1H, Py-H); 7.17 (d, J=7.2Hz, 1H; Py-H), 7.31 (d, J=8.4Hz; 2H; Ar-H), 7.46 (d, J=8.4Hz; 2H; Ar-H), 7.73 (d, J=6.8Hz; 1H, Py-H). HR-ESI-MS for C13H9BrClN3NaO:calcd. 359.9510 [M+Na]+; Found:359.9515 [M+Na]+.
The synthesis of embodiment 10 2-(4-ter .-butylbenzyl)-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5 mL), the 1-tertiary butyl-4-chloromethylbenzene (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.I.e. 2-(4-ter .-butylbenzyl)-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 95%, m.p.160-162 DEG C; 1H NMR (CDCl3,400 MHz), δ: 1.29 (s, 9H; t-Bu), 5.18 (s, 2H, NCH2); (6.42 t, J=7.2Hz, 1H, Py-H); (7.12 d, J=7.2Hz, 1H, Py-H); (7.34-7.40 m, 4H, Ar-H), 7.72 (d; J=7.2Hz, 1H, Py-H). HR-ESI-MS for C10H13ClN3O5:calcd. 290.0538 [M+H]+; Found:290.0543 [M+H]+.
The synthesis of embodiment 11 2-(the chloro-3-oxo of 8--[1,2,4] triazole [4,3-a] pyridine-2 (3H)-Ji) acetonitrile
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5mL), 2-chloromethyl cyanide (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.I.e. 2-(the chloro-3-oxo of 8--[1,2,4] triazole [4,3-a] pyridine-2 (3H)-Ji) acetonitrile, productive rate 95%, m.p.180-182 DEG C; 1H NMR (CDCl3,400 MHz), δ: 4.97 (s, 2H; NCH2), 6.56 (t, J=7.2Hz; 1H, Py-H), 7.26 (d; J=7.2Hz, 1H, Py-H); 7.73 (d, J=7.2Hz, 1H; Py-H). Elemental analysis for C8H5ClN4O:found C 45.89, H 2.65, N 26.78; Calcd. C, 46.06; H, 2.42; N, 26.86.
The synthesis of the chloro-2-propyl group of embodiment 12 8--[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5mL), n-propyl chloride (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.The i.e. chloro-2-propyl group of 8--[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 94%, m.p.120-122 DEG C; 1H NMR (CDCl3,400 MHz), δ: 0.98 (t; J=7.6Hz, CH3), 1.90 (q; J=7.2Hz, 2H, CH2); 4.01 (t, J=7.6Hz, 2H; NCH2), 6.47 (t, J=7.2Hz; 1H, Py-H), 7.17 (d; J=7.2Hz, 1H, Py-H); 7.75 (d; J=7.2Hz, 1H, Py-H). Elemental analysis for C9H10ClN3O:found C 50.89; H 4.97, N 19.99; Calcd. C, 51.07; H, 4.76; N, 19.85.,
The synthesis of the chloro-2-undecyl of embodiment 13 8--[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5mL), the chloro-undecane hydrocarbon of 1-(1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.The i.e. chloro-2-undecyl of 8--[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 94%, m.p.131-132 DEG C; 1H NMR (CDCl3,400 MHz), δ: 0.87 (t; J=7.2Hz, CH3), 1.25-1.33 (m; 16H, CH2), 1.85-1.88 (m; 2H, CH2), 4.03 (t; J=7.2Hz, 2H, NCH2); 6.46 (t, J=7.2Hz, 1H; Py-H), 7.17 (d, J=7.2Hz; 1H, Py-H), 7.74 (d; J=7.2Hz, 1H, Py-H). Elemental analysis for C17H26ClN3O:found C 62.99; H 8.03, N 13.01; Calcd. C, 63.05; H, 8.09; N, 12.97.
The synthesis of embodiment 14 2-butyl-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5mL), 1-chlorobutane (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.I.e. 2-butyl-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, productive rate 93%, m.p.113-115 DEG C; 1H NMR (CDCl3,400 MHz), δ: 0.97 (t; J=1.8Hz, CH3), 1.37-1.43 (m; 2H, CH2), 1.84-1.88 (m; 2H, CH2), 4.05 (t; J=7.2Hz, 2H, NCH2); 6.47 (t, J=7.2Hz, 1H; Py-H), 7.17 (d, J=7.2Hz; 1H, Py-H), 7.74 (d; J=7.2Hz, 1H, Py-H). Elemental analysis for C10H12ClN3O:found C 53.41; H 5.44, N 18.76; Calcd. C, 53.22; H, 5.36; N, 18.62.
The synthesis of embodiment 15 2-allyl group-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one
8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one (1mmol), DMF (5mL), chlorallylene (1.1 mmol) and NaOH (0.05 g, 1.2mmol) in CEM Discovery single mold microwave synthesizer under 90 ° of C microwave radiation reaction 15min.After reaction terminates, mixture is poured in trash ice into recrystallization after forming sedimentation and filtration and collect.I.e. 2-allyl group-8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, yield 95%, m.p.99-100 DEG C; 1H NMR (CDCl3,400 MHz), δ: 4.66 (d; J=5.6Hz, 2H, NCH2); 5.31 (d, J=9.2Hz, 2H;=CH2), 5.95-6.06 (m, 1H;=CH), 6.48 (t, J=7.2Hz; 1H; Py-H), 7.18 (d, J=7.2Hz; 1H; Py-H), 7.75 (d, J=7.2Hz; 1H, Py-H). HR-ESI-MS for C8H6ClN4O:calcd. 209.0225 [M+H]+; Found:209.0226 [M+H]+.
The compound that the embodiment of the present invention obtains is the new compound with weeding activity, has good effect, for the research and development of novel pesticide provide the foundation especially for preventing and treating on barnyard grass, Herba Setariae Viridis, annual bluegrass, leaf mustard, piemarker, Amaranthus retroflexus or little lamb's-quarters.
Claims (6)
1. one kind [1, 2, 4] triazole [4, 3-a] preparation method of pyridine-3 (2H)-one derivative, [1, 2, 4] as azoles [4, 3-a] its structural formula of pyridine-3 (2H)-one derivative is as shown in the formula (I), it is characterized in that its preparation method comprises the steps: 3-chloride-2-hydrazinopyridine and urea reaction to be synthesized obtained 8-chloro-[1 as shown in formula II, 2, 4] triazole [4, 3-a] pyridine-3 (2H)-one, 8-chloro-[1, 2, 4] triazole [4, 3-a] pyridine-3 (2H)-one and halohydrocarbon as shown in formula III or benzyl halides be at DMF, microwave radiation ring closure reaction is carried out in 40 ~ 80 DEG C in NaOH, after abundant reaction, namely gained reaction solution obtains product [1 through aftertreatment, 2, 4] triazole [4, 3-a] pyridine-3 (2H)-one derivative,
In formula (I) or formula (III), R represents alkyl, vinyl, cyano group, the substituted-phenyl of C1 ~ C11.
2. as claimed in claim 1 [1,2,4] triazole [4,3-a] preparation method of pyridine-3 (2H)-one derivative, it is characterized in that the substituting group of described substituted benzyl is independently selected from separately one of following: the tertiary butyl, methoxyl group, cyano group, chlorine atom, bromine atoms, fluorine atom.
3. as claimed in claim 1 [1,2,4] preparation method of triazole [4,3-a] pyridine-3 (2H)-one derivative, it is characterized in that: described 3-chloride-2-hydrazinopyridine and the molar ratio of urea are 1:2.0 ~ 4.0, and molar ratio is preferably 1:3.0.
4. as claimed in claim 1 [1,2,4] triazole [4,3-a] preparation method of pyridine-3 (2H)-one derivative, it is characterized in that: 8-chloro-[1,2,4] triazole [4,3-a] pyridine-3 (2H)-one, the molar ratio of RCH2Cl and NaOH is 1:1.0 ~ 1.5:1.0 ~ 2.0., and molar ratio is preferably 1:1.1:1.2.
5. as claimed in claim 1 [1,2,4] triazole [4,3-a] preparation method of pyridine-3 (2H)-one derivative, it is characterized in that: the temperature of reaction of 3-chloride-2-hydrazinopyridine and urea is 120-180 DEG C, be preferably 160 DEG C, the reaction times is 20-40 min, is preferably 30min.
6. as claimed in claim 1 [1,2,4] preparation method of triazole [4,3-a] pyridine-3 (2H)-one derivative, is characterized in that: 8-chloro-[1,2,4] the ring closure reaction temperature of triazole [4,3-a] pyridine-3 (2H)-one and RCH2Cl is 80-100 DEG C, and the reaction times is 10-20 min., temperature of reaction is preferably 90 DEG C, and the reaction times is preferably 15 min.
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| CN1473162A (en) * | 2000-11-08 | 2004-02-04 | ס������ũҩ��ʽ���� | Bicyclic triazolone derivatives and herbicides containing the same |
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| CN103096977A (en) * | 2010-07-02 | 2013-05-08 | 吉利德科学股份有限公司 | Fused heterocyclic compounds as ion channel modulators |
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| CN1473162A (en) * | 2000-11-08 | 2004-02-04 | ס������ũҩ��ʽ���� | Bicyclic triazolone derivatives and herbicides containing the same |
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