RU2617413C1 - O-substituted 3-pyridylcetoximes, fungiency activity - Google Patents

O-substituted 3-pyridylcetoximes, fungiency activity Download PDF

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RU2617413C1
RU2617413C1 RU2015153086A RU2015153086A RU2617413C1 RU 2617413 C1 RU2617413 C1 RU 2617413C1 RU 2015153086 A RU2015153086 A RU 2015153086A RU 2015153086 A RU2015153086 A RU 2015153086A RU 2617413 C1 RU2617413 C1 RU 2617413C1
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substituted
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pyridyl
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Александр Владимирович Кузенков
Владимир Владимирович Захарычев
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Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева (РХТУ им. Д.И. Менделеева)"
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

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Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to O-substituted 3-pyridylketoksimes general formula I
Figure 00000012
, where R1 It is 4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl or cyclohexyl, R2 means hexyl, cyclohexyl or benzyl, having fungicidal activity.
EFFECT: expansion of the arsenal of agents having fungicidal activity.
3 tbl, 4 ex

Description

Изобретение относится к химии гетероциклических соединений, а именно к O-замещенным 3-пиридилкетоксимам общей формулы I, где R1 означает 4-бромфенил, 4-хлорфенил, 4-фторфенил или циклогексил, R2 означает гексил, циклогексил или бензил, обладающие фунгицидной активностью.The invention relates to the chemistry of heterocyclic compounds, namely to O-substituted 3-pyridyl ketoximes of the general formula I, where R 1 is 4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl or cyclohexyl, R 2 is hexyl, cyclohexyl or benzyl having fungicidal activity .

Figure 00000001
Figure 00000001

Замещенные 3-пиридилкетоксимы общей формулы I могут найти применение для борьбы с вредоносными грибами в медицине, ветеринарии, сельском хозяйстве, приусадебном хозяйстве.Substituted 3-pyridyl ketoximes of the general formula I can find application for combating harmful fungi in medicine, veterinary medicine, agriculture, and homestead farming.

Известен пирифенокс (II), обладающий фунгицидной активностью [Пестициды и регуляторы роста растений / Н.Н. Мельников, К.В. Новожилов, С.Р. Белан. - М.: Химия, 1995. - 576 с.].Known pyrifenox (II) with fungicidal activity [Pesticides and plant growth regulators / N.N. Melnikov, K.V. Novozhilov, S.R. Belan. - M .: Chemistry, 1995. - 576 p.].

Figure 00000002
Figure 00000002

Наиболее близки по структуре к соединениям формулы I O-эфиры оксимов общей формулы III, где R1 означает C1-C6-алкил, C3-C6-циклоалкил, C1-C6-алкокси и др., m означает число от 1 до 4, R3 и R4 независимо друг от друга означают атом водорода, C1-C6-алкил и др., R5 означает атом водорода, и др., R6 означает атом водорода, C1-C6-алкил, C2-C6-алкенил, C2-C6-алкинил, C1-C6-алкокси, атом галогена и др., n означает число от 1 до 4 [Пат. JP 6589967, 2001].The structure closest to the compounds of formula I are O-esters of oximes of the general formula III, where R 1 is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, etc., m is the number from 1 to 4, R 3 and R 4 independently from each other mean a hydrogen atom, C 1 -C 6 -alkyl and others, R 5 means a hydrogen atom, and others, R 6 means a hydrogen atom, C 1 -C 6 -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, halogen atom, etc., n means a number from 1 to 4 [US Pat. JP 6589967, 2001].

Figure 00000003
Figure 00000003

Однако соединения структур II и III имеют не всегда удовлетворительные физико-химические характеристики, узкий спектр действия и показывают фунгицидную активность только в отношении отдельных классов грибов. Кроме того, к фунгицидам у грибов часто развивается устойчивость.However, compounds of structures II and III have not always satisfactory physicochemical characteristics, a narrow spectrum of action and show fungicidal activity only against certain classes of fungi. In addition, fungi often develop resistance to fungicides.

Техническая задача, решаемая настоящим изобретением, состоит в расширении ассортимента фунгицидов для более эффективной борьбы с вредоносными грибами.The technical problem solved by the present invention is to expand the range of fungicides for a more effective fight against harmful fungi.

Поставленная задача решается получением O-замещенных 3-пиридилкетоксимов общей формулы I, обладающих фунгицидной активностью.The problem is solved by the preparation of O-substituted 3-pyridyl ketoximes of the general formula I having fungicidal activity.

O-Замещенные 3-пиридилкетоксимы общей формулы I могут быть получены алкилированием 3-пиридилкетоксимов общей формулы IV, где R1 имеет те же значения, что и в формуле I, галогенидом общей формулы R2X, где R2 имеет те же значения, что и в формуле I, X означает атом галогена, например в присутствии гидрида натрия или в условиях межфазного катализа:O-Substituted 3-pyridyl ketoximes of the general formula I can be obtained by alkylation of 3-pyridyl ketoximes of the general formula IV, where R 1 has the same meanings as in formula I, with a halide of the general formula R 2 X, where R 2 has the same meanings as and in formula I, X represents a halogen atom, for example in the presence of sodium hydride or under conditions of interphase catalysis:

Figure 00000004
Figure 00000004

Аналогичные реакции описаны в литературе [E. Buehler. Alkylation of syn- and anti-benzaldoximes // Journ. Am. Chem. Soc., 1967, V. 32, pp. 261-265].Similar reactions are described in the literature [E. Buehler. Alkylation of syn- and anti-benzaldoximes // Journ. Am. Chem. Soc., 1967, V. 32, pp. 261-265].

Соединения общей формулы IV могут быть получены известным способом взаимодействием пиридилкетонов общей формулы V, где R1 имеет те же значения, что и в формуле I, с гидроксиламином:Compounds of general formula IV can be prepared in a known manner by reacting pyridyl ketones of general formula V, where R 1 has the same meanings as in formula I, with hydroxylamine:

Figure 00000005
Figure 00000005

Аналогичные реакции описаны в литературе [F. Trusell, Н. Diehl. Phenyl-2-pyridilketoxime, a reagent in strong alkalies for iron // Journ. Analit. Chem., 1959, V. 31, No. 12, pp. 1978-1980].Similar reactions are described in the literature [F. Trusell, N. Diehl. Phenyl-2-pyridilketoxime, a reagent in strong alkalies for iron // Journ. Analit. Chem., 1959, V. 31, No. 12, pp. 1978-1980].

Изобретение может быть проиллюстрировано следующими примерами.The invention can be illustrated by the following examples.

Пример 1. К раствору 1,31 г (5 ммоль) 3-пиридил-4-бромфенилкетона в 5 мл этанола прибавляют 0,686 г (9,87 ммоль) гидрохлорида гидроксиламина, растворенного в 1 мл воды. Смесь нагревают на водяной бане в течение 1 ч, охлаждают до комнатной температуры, добавляют раствор 0,399 г (9,97 ммоль) гидроксида натрия в 1 мл воды. Через раствор пропускают углекислый газ, доведя его значение pH до примерно 7. Выпавший осадок отфильтровывают, нагревают с 5 мл этанола до кипения, прибавляют 5 мл тетрагидрофурана, охлаждают до комнатной температуры и вновь отфильтровывают. Органический экстракт упаривают досуха, остаток перекриталлизовывают из этанола. Получают 0,63 г (46,1%) 3-пиридил-4-бромфенилкетоксима. Тпл. 159-161°C.Example 1. To a solution of 1.31 g (5 mmol) of 3-pyridyl-4-bromophenylketone in 5 ml of ethanol was added 0.686 g (9.87 mmol) of hydroxylamine hydrochloride dissolved in 1 ml of water. The mixture is heated in a water bath for 1 h, cooled to room temperature, a solution of 0.399 g (9.97 mmol) of sodium hydroxide in 1 ml of water is added. Carbon dioxide was passed through the solution, bringing its pH to about 7. The precipitate was filtered off, heated with 5 ml of ethanol to a boil, 5 ml of tetrahydrofuran was added, cooled to room temperature and filtered again. The organic extract was evaporated to dryness, the residue was recrystallized from ethanol. 0.63 g (46.1%) of 3-pyridyl-4-bromophenyl ketoxime is obtained. Mp 159-161 ° C.

Пример 2. К раствору 0,554 г (2 ммоль) 3-пиридил-4-бромфенилкетоксима и 2,889 г карбоната калия в 26 мл воды прибавляют раствор 0,3 г (2,375 ммоль) бензилхлорида и 0,23 г (0,1 ммоль) триэтилбензилхлорида в 4,2 мл бензола. Двухфазную систему интенсивно перемешивают при кипении в течение 4 ч. Смесь охлаждают до комнатной температуры, органический слой отделяют, растворитель отгоняют. Остаток разделяют на колонке с силикагелем 35/70, элюент толуол-ацетон 5:1. Получают 0,083 г (11,3%) O-бензилового эфира 3-пиридил-4-бромфенилкетоксима (масло).Example 2. To a solution of 0.554 g (2 mmol) of 3-pyridyl-4-bromophenylketoxime and 2.889 g of potassium carbonate in 26 ml of water, a solution of 0.3 g (2.375 mmol) of benzyl chloride and 0.23 g (0.1 mmol) of triethylbenzyl chloride is added in 4.2 ml of benzene. The two-phase system is intensively stirred at the boil for 4 hours. The mixture is cooled to room temperature, the organic layer is separated, the solvent is distilled off. The residue was separated on a 35/70 silica gel column, 5: 1 toluene-acetone eluent. Obtain 0.083 g (11.3%) of 3-pyridyl-4-bromophenylketoxime O-benzyl ester (oil).

Пример 3. К раствору 0,204 г (1,0 ммоль) 3-пиридилциклогексилкетоксима в 3,6 мл диметилформамида при охлаждении в бане со льдом и солью прибавляют 0,048 г (1,2 ммоль) 60%-ного гидрида натрия. Смесь пемешивают в течение 30 мин, добавляют 0,198 г (1,2 ммоль) 1-бромгексана 0,68 г (3,8 ммоль) и перемешивают в течение 2 ч при комнатной температуре, после чего реакционную массу выливают в ледяную воду. Органическую фазу экстрагируют диэтиловым эфиром, органический слой промывают водой, сушат над сульфатом натрия, растворитель отгоняют. Остаток разделяют на колонке с силикагелем 35/70, элюент толуол-ацетон 5:1. Получают 0,169 г (58,7%) O-гексилового эфира 3-пиридилциклогексилкетоксима (масло).Example 3. To a solution of 0.204 g (1.0 mmol) of 3-pyridylcyclohexylketoxime in 3.6 ml of dimethylformamide, 0.048 g (1.2 mmol) of 60% sodium hydride was added while cooling in an ice and salt bath. The mixture was stirred for 30 minutes, 0.198 g (1.2 mmol) of 1-bromohexane 0.68 g (3.8 mmol) was added and stirred for 2 hours at room temperature, after which the reaction mixture was poured into ice water. The organic phase is extracted with diethyl ether, the organic layer is washed with water, dried over sodium sulfate, the solvent is distilled off. The residue was separated on a 35/70 silica gel column, 5: 1 toluene-acetone eluent. Obtain 0.169 g (58.7%) of 3-pyridylcyclohexylketoxime O-hexyl ester (oil).

Выходы и соотношения E/Z-изомеров соединений формулы I приведены в табл. 1.The yields and ratios of the E / Z isomers of the compounds of formula I are given in table. one.

ЯМР 1H-спектры соединений I зарегистрированы на приборе Bruker AM300 в DMSO-d6 и приведены в табл. 2.NMR 1 H-spectra of compounds I were recorded on a Bruker AM300 instrument in DMSO-d 6 and are shown in table. 2.

Figure 00000006
Figure 00000006

Figure 00000007
Figure 00000007

Figure 00000008
Figure 00000008

Пример 4. Испытания на фунгицидную активность соединений проводили in vitro на грибах Venturia inaequalis (V.i.), Rhizoctonia solani (R.S.), Fuzarium oxysporum (F.o.), Sclerotinia sclerotiorum (S.s.), Helminthosporium sativum (H.s.), Fuzarium moniliforme (F.m.) при концентрации активного компонента 30 мг/л. В качестве питательной среды использовали сахарозно-картофельный агар. Инокулированные среды выдерживали в термостате при 25°C в течение 3 сут. Активность соединений определяли как процент подавления роста мицелия гриба по отношению к контролю. В качестве эталона использовали коммерческий фунгицид триадимефон. Фунгицидная активность O-замещенных 3-пиридилкетоксимов общей формулы I приведена в табл. 3.Example 4. Tests for the fungicidal activity of the compounds were carried out in vitro on fungi Venturia inaequalis (Vi), Rhizoctonia solani (RS), Fuzarium oxysporum (Fo), Sclerotinia sclerotiorum (Ss), Helminthosporium sativum (Hs), Fuzarium moniliforme (Fm) active component 30 mg / l. Sucrose-potato agar was used as a nutrient medium. Inoculated media were kept in a thermostat at 25 ° C for 3 days. The activity of the compounds was determined as the percentage of inhibition of fungal mycelium growth relative to the control. As a reference, the commercial fungicide triadimefon was used. The fungicidal activity of O-substituted 3-pyridyl ketoximes of the general formula I is given in table. 3.

Figure 00000009
Figure 00000009

Claims (1)

О-Замещенные 3-пиридилкетоксимы общей формулы I,
Figure 00000010
где R1 означает 4-бромфенил, 4-хлорфенил, 4-фторфенил или циклогексил, R2 означает гексил, циклогексил или бензил, обладающие фунгицидной активностью.O-Substituted 3-pyridyl ketoximes of the general formula I,
Figure 00000010
where R 1 means 4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl or cyclohexyl, R 2 means hexyl, cyclohexyl or benzyl having fungicidal activity.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4213149A1 (en) * 1992-04-22 1993-10-28 Hoechst Ag Acaricidal, insecticidal and nematicidal substituted (hetero) aryl-alkyl-ketone oxime-O-ether, process for their preparation, compositions containing them and their use as pesticides
RU2024496C1 (en) * 1988-11-21 1994-12-15 Империал Кемикал Индастриз ПЛС. Propenoic acid derivatives showing fungicidic activity
WO2001034568A1 (en) * 1999-11-05 2001-05-17 Nippon Soda Co., Ltd. Oxime o-ether compounds and fungicides for agricultural and horticultural use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2024496C1 (en) * 1988-11-21 1994-12-15 Империал Кемикал Индастриз ПЛС. Propenoic acid derivatives showing fungicidic activity
DE4213149A1 (en) * 1992-04-22 1993-10-28 Hoechst Ag Acaricidal, insecticidal and nematicidal substituted (hetero) aryl-alkyl-ketone oxime-O-ether, process for their preparation, compositions containing them and their use as pesticides
WO2001034568A1 (en) * 1999-11-05 2001-05-17 Nippon Soda Co., Ltd. Oxime o-ether compounds and fungicides for agricultural and horticultural use

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