Tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds as well as preparation method and applications thereof

Abstract

The invention belongs to a pesticide and discloses tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds shown in a general formula (I) as well as a preparation method and applications thereof. The preparation method comprises the following steps: using ethanol as solvent, and adding neonicotine compounds, aldehyde and Meldrum's acid; and adding piperidine used as a catalyst, and refluxing to react. In the method, a tetrahydropyridone structure is introduced in the neonicotine compounds for the first time. The tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds have the following advantages: the preparation process is simple, and the yield is high; the preparation process has no pollution; and the compounds have good insecticidal effects and are safe for human and livestock.

Description

technical field

[0001] The invention belongs to pesticides and insecticides, in particular to a class of tetrahydropyridone 1,3-diazacyclic cis-neonicotinoid compounds. Background technique

[0002] Neonicotinoid insecticides are the fourth generation of insecticides following organophosphorus, carbamate, and pyrethroid insecticides. As nicotinic acetylcholine receptors (nAChRs) agonists, neonicotinoids act selectively on the nervous system (nAChRs) of insects, and it not only shows high affinity for (nAChRs), but also shows Physicochemical properties such as ionization and moderate water solubility. Due to its unique insecticidal mechanism and high efficiency and low toxicity performance, it has quickly become a new variety of high efficiency and low toxicity pesticides in modern agriculture.

[0003] Due to the serious resistance problem caused by the excessive and frequent use of neonicotinoid insecticides and the cross-resistance between neonicotinoid insecticides due ...

Examples

Embodiment 1

[0040] Preparation of cis-1-(6-chloro-3-pyridylmethyl)-7-phenyl-8-nitro-1,2,3,5,6,7-hexahydroimidazol[1,2-a] Pyridin-5-one;

[0041] The raw material 2-chloro-5-(2-nitromethylene-1-imidazolylmethyl)-pyridine was synthesized according to the literature method: (a) Zhong Li; Wenwen Zhang; Zewen Liu; J.Agric.Food. Chem.2010.58.6296-6299; (b) Xusheng Shao, Zhong Li, XuHong, Qian, and Xiaoyong Xu.J.Agric.Food.Chem.2009.57.951-957.

[0042] The specific steps are:

[0043]

[0044] (1) Synthesis of N'-(6-chloro-3 pyridylmethyl)-1,2-ethylenediamine:

[0045] Get 16.1g (100mmol) 2-chloro-5-chloromethylpyridine and dissolve it in 100ml acetonitrile, and slowly add it dropwise to the mixed solution composed of 30.30g (500mmol) ethylenediamine and 80ml acetonitrile under the condition of ice bath, Adding time is two and a half hours. After continuing the reaction for 8 hours, the reaction was stopped, and part of the acetonitrile was removed by rotary evaporation. Add 100ml of wa...

Embodiment 2

[0058] Preparation of cis-1-(6-chloro-3-pyridylmethyl)-7-(4-chlorophenyl)-8-nitro-1,2,3,5,6,7-hexahydroimidazolium[ 1,2-a]pyridin-5-one.

[0059] The benzaldehyde in Example 1 was replaced by 4-chlorobenzaldehyde, and the other conditions were the same as in Example 1 to obtain a yellow solid with a yield of 90.2%.

[0060] Elemental analysis: found value C% 54.40 H% 3.85 N% 13.35

[0061] Calculated C% 54.43 H% 3.85 N% 13.36

[0062] IR (KBr, cm -1 )v max 2978, 2359, 1685, 1650, 1481, 1423, 1418, 1257, 1226, 1095, 892.

[0063] 1 H NMR (CDCl 3 , 400MHz) δ8.29(s, 1H, Pyridine), 7.51(dd, J=2.5, 8.5Hz, 1H), 7.22-7.28(m, 2H), 7.22(d, J=8.2Hz, 1H), 7.07 -7.13(m, 2H), 4.89(t, J=4.4Hz, 1H), 4.95(d, J=3.9Hz, 2H), 3.64-4.46(m, 4H), 3.12(d, J=4.5Hz, 2H).

[0064] The product prepared in this embodiment is made into an aqueous suspension, sprayed with water, and has a killing rate of more than 95% against spider mite, has high-efficiency insecticidal activity, and is...

Embodiment 3

[0066] Preparation of cis-1-(6-chloro-3-pyridylmethyl)-7-(3-chlorophenyl)-8-nitro-1,2,3,5,6,7-hexahydroimidazol[1 , 2-a] pyridin-5-one.

[0067] The benzaldehyde in Example 1 was replaced by m-chlorobenzaldehyde, and other conditions were the same as in Example 1 to obtain a yellow solid with a yield of 83.5%.

[0068] Elemental analysis: found value C% 54.41 H% 3.82 N% 13.33

[0069] Calculated C% 54.43 H% 3.85 N% 13.36

[0070] IR (KBr, cm -1 )v max 2998, 2367, 1783, 1648, 1485, 1313, 1248, 1227, 1216, 1007, 880.

[0071] 1 H NMR (CDCl 3 , 400MHz) δ8.20(s, 1H, Pyridine), 7.28-7.38(m, 3H), 7.20(d, J=8.2Hz, 1H), 7.08-7.16(m, 2H), 4.97(t, J= 4.3Hz, 1H), 4.79(d, J=3.9Hz, 2H), 3.72-4.45(m, 4H), 3.10(d, J=4.5Hz, 2H).

[0072] The product prepared in this embodiment is made into water-emulsion insecticide, mixed with water and sprayed, and the killing rate to rice planthopper is more than 90%, has high-efficiency insecticidal activity, and is safe for humans and ...

technical field

[0001] The invention belongs to pesticides and insecticides, in particular to a class of tetrahydropyridone 1,3-diazacyclic cis-neonicotinoid compounds. Background technique

[0002] Neonicotinoid insecticides are the fourth generation of insecticides following organophosphorus, carbamate, and pyrethroid insecticides. As nicotinic acetylcholine receptors (nAChRs) agonists, neonicotinoids act selectively on the nervous system (nAChRs) of insects, and it not only shows high affinity for (nAChRs), but also shows Physicochemical properties such as ionization and moderate water solubility. Due to its unique insecticidal mechanism and high efficiency and low toxicity performance, it has quickly become a new variety of high efficiency and low toxicity pesticides in modern agriculture.

[0003] Due to the serious resistance problem caused by the excessive and frequent use of neonicotinoid insecticides and the cross-resistance between neonicotinoid insecticides due ...

Examples

Embodiment 1

[0040] Preparation of cis-1-(6-chloro-3-pyridylmethyl)-7-phenyl-8-nitro-1,2,3,5,6,7-hexahydroimidazol[1,2-a] Pyridin-5-one;

[0041] The raw material 2-chloro-5-(2-nitromethylene-1-imidazolylmethyl)-pyridine was synthesized according to the literature method: (a) Zhong Li; Wenwen Zhang; Zewen Liu; J.Agric.Food. Chem.2010.58.6296-6299; (b) Xusheng Shao, Zhong Li, XuHong, Qian, and Xiaoyong Xu.J.Agric.Food.Chem.2009.57.951-957.

[0042] The specific steps are:

[0043]

[0044] (1) Synthesis of N'-(6-chloro-3 pyridylmethyl)-1,2-ethylenediamine:

[0045] Get 16.1g (100mmol) 2-chloro-5-chloromethylpyridine and dissolve it in 100ml acetonitrile, and slowly add it dropwise to the mixed solution composed of 30.30g (500mmol) ethylenediamine and 80ml acetonitrile under the condition of ice bath, Adding time is two and a half hours. After continuing the reaction for 8 hours, the reaction was stopped, and part of the acetonitrile was removed by rotary evaporation. Add 100ml of wa...

Embodiment 2

[0058] Preparation of cis-1-(6-chloro-3-pyridylmethyl)-7-(4-chlorophenyl)-8-nitro-1,2,3,5,6,7-hexahydroimidazolium[ 1,2-a]pyridin-5-one.

[0059] The benzaldehyde in Example 1 was replaced by 4-chlorobenzaldehyde, and the other conditions were the same as in Example 1 to obtain a yellow solid with a yield of 90.2%.

[0060] Elemental analysis: found value C% 54.40 H% 3.85 N% 13.35

[0061] Calculated C% 54.43 H% 3.85 N% 13.36

[0062] IR (KBr, cm -1 )v max 2978, 2359, 1685, 1650, 1481, 1423, 1418, 1257, 1226, 1095, 892.

[0063] 1 H NMR (CDCl 3 , 400MHz) δ8.29(s, 1H, Pyridine), 7.51(dd, J=2.5, 8.5Hz, 1H), 7.22-7.28(m, 2H), 7.22(d, J=8.2Hz, 1H), 7.07 -7.13(m, 2H), 4.89(t, J=4.4Hz, 1H), 4.95(d, J=3.9Hz, 2H), 3.64-4.46(m, 4H), 3.12(d, J=4.5Hz, 2H).

[0064] The product prepared in this embodiment is made into an aqueous suspension, sprayed with water, and has a killing rate of more than 95% against spider mite, has high-efficiency insecticidal activity, and is...

Embodiment 3

[0066] Preparation of cis-1-(6-chloro-3-pyridylmethyl)-7-(3-chlorophenyl)-8-nitro-1,2,3,5,6,7-hexahydroimidazol[1 , 2-a] pyridin-5-one.

[0067] The benzaldehyde in Example 1 was replaced by m-chlorobenzaldehyde, and other conditions were the same as in Example 1 to obtain a yellow solid with a yield of 83.5%.

[0068] Elemental analysis: found value C% 54.41 H% 3.82 N% 13.33

[0069] Calculated C% 54.43 H% 3.85 N% 13.36

[0070] IR (KBr, cm -1 )v max 2998, 2367, 1783, 1648, 1485, 1313, 1248, 1227, 1216, 1007, 880.

[0071] 1 H NMR (CDCl 3 , 400MHz) δ8.20(s, 1H, Pyridine), 7.28-7.38(m, 3H), 7.20(d, J=8.2Hz, 1H), 7.08-7.16(m, 2H), 4.97(t, J= 4.3Hz, 1H), 4.79(d, J=3.9Hz, 2H), 3.72-4.45(m, 4H), 3.10(d, J=4.5Hz, 2H).

[0072] The product prepared in this embodiment is made into water-emulsion insecticide, mixed with water and sprayed, and the killing rate to rice planthopper is more than 90%, has high-efficiency insecticidal activity, and is safe for humans and ...

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