RU2727138C1 - N,n'-di(alkadinyl)diazacycloalkanes and method of producing n,n'-di(alkadinyl)diazacycloalkanes exhibiting fungicidal activity with respect to fungi bipolaris sorokiniana and rhizoctonia solani - Google Patents

N,n'-di(alkadinyl)diazacycloalkanes and method of producing n,n'-di(alkadinyl)diazacycloalkanes exhibiting fungicidal activity with respect to fungi bipolaris sorokiniana and rhizoctonia solani Download PDF

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RU2727138C1
RU2727138C1 RU2019116558A RU2019116558A RU2727138C1 RU 2727138 C1 RU2727138 C1 RU 2727138C1 RU 2019116558 A RU2019116558 A RU 2019116558A RU 2019116558 A RU2019116558 A RU 2019116558A RU 2727138 C1 RU2727138 C1 RU 2727138C1
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diazacycloalkanes
alkadinyl
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fungicidal activity
rhizoctonia solani
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Усеин Меметович Джемилев
Асхат Габдрахманович Ибрагимов
Гузель Ражаповна Хабибуллина
Фируза Тимирьяновна Зайнуллина
Наиля Фауатовна Галимзянова
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Федеральное государственное бюджетное научное учреждение Уфимский федеральный исследовательский центр Российской академии наук
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    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
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    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/62—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms three- or four-membered rings or rings with more than six members
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    • C07D233/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C07D295/073—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings

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Abstract

FIELD: chemistry.SUBSTANCE: invention relates to organic chemistry, in particular to N,N'-di(alkadinyl)diazacycloalkanes of general formula (1) given below. Invention also relates to a method of producing N, N'-di(alkadinyl)diazacycloalkanes of general formula (1) and use thereof as an agent with fungicidal activity on phytopathogenic fungi Bipolaris sorokiniana and Rhizoctonia solani.EFFECT: compounds can be used as an agent with fungicidal activity towards phytopathogenic fungi Bipolaris sorokiniana and Rhizoctonia solani.3 cl, 2 tbl, 1 ex

Description

Предлагаемое изобретение относится к органической химии, в частности, к способу получения N,N'-ди(алкадиинил)диазациклоалканов общей формулы (1), обладающих фунгицидной активностью против фитопатогенных грибов Bipolaris sorokiniana, Rhizoctonia solani.The present invention relates to organic chemistry, in particular, to a method for producing N, N'-di (alkadiinyl) diazacycloalkanes of general formula (1), which have fungicidal activity against phytopathogenic fungi Bipolaris sorokiniana, Rhizoctonia solani.

Figure 00000001
Figure 00000001

Соединения общей формулы (1) могут быть использованы в качестве универсальных прекурсоров для тонкого органического синтеза [Groaz Е., Banti D., North М. Tetrahedron, 2008, 64, 204-218; Kashid V.S., Balakrishna M S. Catalysis Comm., 2018, 103, 78-82] и получения биологически активных соединений [Afrakssou Z., Haoudi A., Capet F., Mazzah A., Rolandoc C, Amman L. El // J. Acta Cryst. 2013, E69. 944].Compounds of general formula (1) can be used as universal precursors for fine organic synthesis [Groaz E., Banti D., North M. Tetrahedron, 2008, 64, 204-218; Kashid VS, Balakrishna M S. Catalysis Comm., 2018, 103, 78-82] and obtaining biologically active compounds [Afrakssou Z., Haoudi A., Capet F., Mazzah A., Rolandoc C, Amman L. El // J. Acta Cryst. 2013, E69. 944].

Известен способ (Kabalka G. W., Wang L., Pagni R. M. Microwave-Enhanced, Solventless Mannich Condensation on Cul-Doped Alumina. J. Synlett, 2001, 5, 676-678; Kabalka G.W, Zhou Li-Li, Wang L., Pagni R. M. J. Tetrahedron, 2006, 62, 857-867) получения диацетилендиаминов общей формулы (2) взаимодействием терминальных ацетиленов с пиперазином и формальдегидом под действием стехиометрических количеств иодида меди на окиси алюминия при ультразвуковом облучении с выходом 49-65% по схеме:The known method (Kabalka GW, Wang L., Pagni RM Microwave-Enhanced, Solventless Mannich Condensation on Cul-Doped Alumina. J. Synlett, 2001, 5, 676-678; Kabalka GW, Zhou Li-Li, Wang L., Pagni RMJ Tetrahedron, 2006, 62, 857-867) for the preparation of diacetylenediamines of general formula (2) by the interaction of terminal acetylenes with piperazine and formaldehyde under the action of stoichiometric amounts of copper iodide on alumina under ultrasonic irradiation with a yield of 49-65% according to the scheme:

Figure 00000002
Figure 00000002

Известным способом не могут быть получены N,N'-ди(алкадиинил)диазациклоалканы общей формулы (1).N, N'-di (alcadinyl) diazacycloalkanes of general formula (1) cannot be obtained by a known method.

Известен способ [Zhang Y., Feng H., Liu X., Liliang H. Eur. J. Org. Chem., 2018, 2039-2046 DOI: 10.1002/ejoc.201800393] получения диацетилендиаминов общей формулы (3) с выходом 39-96% конденсацией α,ω-диаминов, 37%-ного формальдегида и α-ацетиленов в диоксане под действием CuCl (20 мол %) в условиях микроволнового облучения (максимальная мощность 100 Вт) при 70°С в течение 30 минут по схеме:The known method [Zhang Y., Feng H., Liu X., Liliang H. Eur. J. Org. Chem., 2018, 2039-2046 DOI: 10.1002 / ejoc.201800393] for the preparation of diacetylenediamines of general formula (3) in a yield of 39-96% by condensation of α, ω-diamines, 37% formaldehyde and α-acetylenes in dioxane under the action of CuCl (20 mol%) under microwave irradiation (maximum power 100 W) at 70 ° C for 30 minutes according to the scheme:

Figure 00000003
Figure 00000003

Известным способом не могут быть получены N,N'-ди(алкадиинил)диазациклоалканы общей формулы (1), сведения о которых в литературе отсутствуют.N, N'-di (alkadinyl) diazacycloalkanes of general formula (1) cannot be obtained by a known method, information about which is absent in the literature.

Предлагается новый способ получения N,N'-ди(алкадиинил)диазациклоалканов общей формулы (1), проявляющих фунгицидную активность.A new method for producing N, N'-di (alkadinyl) diazacycloalkanes of general formula (1) exhibiting fungicidal activity is proposed.

Сущность способа заключается во взаимодействии циклических вторичных диаминов (имидазолидин, пиперазин, 1,4-диазепан) с α,ω-диацетиленами общей формулы НС≡С-СН2-(СН2)n-СН2-С≡СН (где n=1-4) и альдегидами (RCHO, R=Н, p-F-C6H4) при мольном соотношении диамин : α,ω-диацетилен : альдегид, равном 1:2:2, в присутствии катализатора CuCl (10 мол %) в атмосфере аргона при температуре 100°С в среде толуола в течение 8 ч. Выход N,N'-ди(алкадиинил)диазациклоалканов формулы (1) составляет 31-68%. Реакция протекает по схеме:The essence of the method lies in the interaction of cyclic secondary diamines (imidazolidine, piperazine, 1,4-diazepane) with α, ω-diacetylenes of the general formula HC≡C-CH 2 - (CH 2 ) n -CH 2 -C≡CH (where n = 1-4) and aldehydes (RCHO, R = H, pFC 6 H 4 ) at a molar ratio of diamine: α, ω-diacetylene: aldehyde equal to 1: 2: 2 in the presence of a CuCl catalyst (10 mol%) in an argon atmosphere at a temperature of 100 ° C in a toluene environment for 8 hours. The yield of N, N'-di (alkadiinyl) diazacycloalkanes of formula (1) is 31-68%. The reaction proceeds according to the scheme:

Figure 00000004
Figure 00000004

N,N'-Ди(алкадиинил)диазациклоалканы (1) образуются только лишь с участием циклических вторичных диаминов (имидазолидин, пиперазин, 1,4-диазепан), α,ω-диацетиленов и альдегидов, взятых в стехиометрическом соотношении 1:2:2, под действием катализатора CuCl (10 мол. %). При другом соотношении исходных реагентов или в присутствии других Cu-содержащих катализаторов (CuCl2, CuBr) снижается выход целевого продукта (1). При использовании в качестве катализатора CuBr2 реакция проходит с образованием целевых продуктов с выходами, не превышающими 25%. Реакции проводили при температуре 100°С. При более высокой температуре (например, 110°С) увеличиваются энергозатраты. При температуре ниже 100°С (например, 80°С) снижается скорость реакции. Опыты проводили в толуоле, т.к. в нем хорошо растворяются исходные реагенты и целевые продукты.N, N'-Di (alkadinyl) diazacycloalkanes (1) are formed only with the participation of cyclic secondary diamines (imidazolidine, piperazine, 1,4-diazepane), α, ω-diacetylenes, and aldehydes taken in a stoichiometric ratio of 1: 2: 2 , under the action of a CuCl catalyst (10 mol.%). At a different ratio of the starting reagents or in the presence of other Cu-containing catalysts (CuCl 2 , CuBr), the yield of the target product decreases (1). When using CuBr 2 as a catalyst, the reaction proceeds with the formation of the target products with yields not exceeding 25%. The reactions were carried out at a temperature of 100 ° C. Higher temperatures (for example 110 ° C) increase energy consumption. At temperatures below 100 ° C (eg 80 ° C), the reaction rate decreases. The experiments were carried out in toluene, because initial reagents and target products are well soluble in it.

Существенные отличия предлагаемого способа:Significant differences of the proposed method:

В известных способах в качестве исходных реагентов применяются 1-алкины (фенилацетилен, 1-октан, 4-этинилтолуол, 1-этил-4-этинилбензол, циклопропилацетилен). Известные способы не позволяют получать индивидуальные N,N'-ди(алкадиинил)диазациклоалканы общей формулы (1). В предлагаемом способе в качестве исходных реагентов применяются α,ω-диацетилены. Предлагаемый способ позволяет селективно получать индивидуальные N,N'-ди(алкадиинил)диазациклоалканы общей формулы (1).In known methods, 1-alkynes (phenylacetylene, 1-octane, 4-ethynyltoluene, 1-ethyl-4-ethynylbenzene, cyclopropylacetylene) are used as starting reagents. The known methods do not allow one to obtain individual N, N'-di (alkadiinyl) diazacycloalkanes of general formula (1). In the proposed method, α, ω-diacetylenes are used as starting reagents. The proposed method allows you to selectively obtain individual N, N'-di (alkadiinyl) diazacycloalkanes of general formula (1).

Способ поясняется следующими примерами:The method is illustrated by the following examples:

Пример 1. В сосуд Шленка, установленный на магнитной мешалке, в атмосфере аргона помещают 0.085 г (1 ммоль) пиперазина, 3 мл толуола, 0.06 г (2 ммоль) параформа и 0.3 г (2 ммоль) 1,7-октадиина, добавляют CuCl (0.0099 г, 10 мол. %), перемешивают при температуре 100°С в течение 8 ч, отфильтровывают через слой SiO2, промывают хлороформом 3×5 мл, упаривают, целевой продукт очищают методом колоночной хроматографии. Выход 1,4-ди(2,7-октадиинил)пиперазина (1а) составляет 102 мг (68%). Другие примеры, подтверждающие способ, приведены в табл. 1.Example 1. In a Schlenk vessel, mounted on a magnetic stirrer, in an argon atmosphere are placed 0.085 g (1 mmol) of piperazine, 3 ml of toluene, 0.06 g (2 mmol) of paraform and 0.3 g (2 mmol) of 1,7-octadiine, add CuCl (0.0099 g, 10 mol.%) was stirred at 100 ° C for 8 h, filtered through a pad of SiO 2, was washed with chloroform 3 × 5 mL, evaporated, the desired product is purified by column chromatography. The yield of 1,4-di (2,7-octadiynyl) piperazine (1а) is 102 mg (68%). Other examples confirming the method are given in table. 1.

Figure 00000005
Figure 00000005

Физико-химические характеристики соединений 1а-и:*Physicochemical characteristics of compounds 1a-i: *

Figure 00000006
Figure 00000006

1,4-Ди(2,7-октадиинил)пиперазин (1а).1,4-Di (2,7-octadiynyl) piperazine (1а).

Figure 00000007
Figure 00000007

Белый порошок, выход 0.199 г (68%); т. пл. 39-42°С. Rf 0.63 (бензол - ацетон, 1:1). ИК-спектр, v/см-1 (пленка): 3307, 2939, 2912, 2820, 2251, 2197, 1618, 1457, 1432, 1334, 1151, 1131, 1150, 1131, 1007, 908, 813, 733, 649. Спектр ЯМР 1Н (400 МГц, CDC13, δ, м.д., J/Гц): 1.65-1.69 (м, 4Н, CH2CH 2CH2), 1.92 (с, 2Н, С≡СН), 2.23-2.26 (м, 8Н, CH 2CH2CH 2), 2.57 (уш.с, 8Н, N(CH 2CH 2)2), 3.21 (уш с, 4Н, NCH 2C≡C). Спектр ЯМР 13С (100 МГц, δ, м.д.): 17.6 (СН2С≡СН), 17.8 (СН2С≡ССН2СН2), 27.6 (С≡СН2 СН2), 47.2 (NCH2C≡C), 51.8(N(CH2 CH2)N), 68.8 (-С≡СН), 75.4 (NCH2 C≡C-), 83.5 (С≡СН), 84.2 (NCH2C≡C-). Масс-спектр MALDI-TOF, m/z: 295.2355 [М+Н]+ C20H27N2, 317.2100 [M+Na]+C20H26N2Na, 333.1723 [М+К]+C20H26N2K. Вычислено: 295.2174 [М+Н]+, 317.1994 [M+Na]+, 333.1733 [М+K]+.White powder, yield 0.199 g (68%); t. pl. 39-42 ° C. R f 0.63 (benzene - acetone, 1: 1). IR spectrum, v / cm -1 (film): 3307, 2939, 2912, 2820, 2251, 2197, 1618, 1457, 1432, 1334, 1151, 1131, 1150, 1131, 1007, 908, 813, 733, 649 1 H NMR spectrum (400 MHz, CDCl 3 , δ, ppm, J / Hz): 1.65-1.69 (m, 4H, CH 2 C H 2 CH 2 ), 1.92 (s, 2H, C≡C H ), 2.23-2.26 (m, 8H, C H 2 CH 2 C H 2 ), 2.57 (br.s, 8H, N (C H 2 C H 2 ) 2 ), 3.21 (br.s, 4H, NC H 2 C≡C). 13 С NMR spectrum (100 MHz, δ, ppm): 17.6 ( С Н 2 С≡СН), 17.8 (СН 2 С≡С С Н 2 СН 2 ), 27.6 (С≡СН 2 С Н 2 ) , 47.2 (N C H 2 C≡C), 51.8 (N ( C H 2 C H 2 ) N), 68.8 (-C≡ C H), 75.4 (NCH 2 C ≡C-), 83.5 ( C ≡CH ), 84.2 (NCH 2 C≡ C -). Mass spectrum MALDI-TOF, m / z: 295.2355 [М + Н] + C 20 H 27 N 2 , 317.2100 [M + Na] + C 20 H 26 N 2 Na, 333.1723 [М + К] + C 20 H 26 N 2 K. Calculated: 295.2174 [M + H] + , 317.1994 [M + Na] + , 333.1733 [M + K] + .

1,4-Ди(2,8-нонадиинил)пиперазин (1б).1,4-Di (2,8-nonadiynyl) piperazine (1b).

Figure 00000008
Figure 00000008

Белый порошок, выход 0.189 г (59%); т.пл. 62-65°С.Rf 0.45 (Et2O - С6Нб - изо-PrOH, 4:2:1). ИК-спектр, v/см-1 (пленка): 3302 (≡С-Н); 2928, 2858, 2814, 2767 (СН2), 2117 (-С≡С-); 1133, 1009 (-C-N-), 1456, 1384, 1331, 812 (-СН3). Спектр ЯМР 1H (500 МГц, CDCl3, δ, м.д., J/Гц): 1.62-1.64 (м, 8Н, СН2(СН 2)2СН2), 1.95-1.96 (т, 2Н, 4J=2.7, С≡СН), 2.20-2.23 (м, 8Н, CH 2(CH2)2CH 2), 2.64 (уш с, 8Н, W1/2=50, N(CH 2CH 2)2), 3.27 (т, 4Н, 4J=2, NCH 2C≡C). Спектр ЯМР 13С (125 МГц, δ, м.д.): 17.9 (СН2С≡СН), 18.3 (СН2С≡ССН2СН2), 27.6 (С=СН2 СН2), 27.7 (СН2СН2С≡СН), 47.3 (NCH2C≡C), 51.9 (N(CH2 CH2)N), 68.5 (-С≡СН), 75.1 (NCH2 C≡C-), 84.2 (С≡СН), 84.9 (NCH2C≡C-). Масс-спектр MALDI-TOF, m/z: 323.2941 [М+Н]+ C22H31N2, 345.2606 [M+Na]+ C22H30N2Na, 361.2262 [M+K]+ C22H30N2K. Вычислено: 323.2487 [M+H]+, 345.2307 [M+Na]+, 361.2046 [M+K]+.White powder, yield 0.189 g (59%); m.p. 62-65 ° С R f 0.45 (Et 2 O - С 6 Н b - iso-PrOH, 4: 2: 1). IR spectrum, v / cm -1 (film): 3302 (≡С-Н); 2928, 2858, 2814, 2767 (CH 2 ), 2117 (—C≡C—); 1133, 1009 (-CN-), 1456, 1384, 1331, 812 (-CH 3 ). 1 H NMR spectrum (500 MHz, CDCl 3 , δ, ppm, J / Hz): 1.62-1.64 (m, 8H, CH 2 ( CH 2 ) 2 CH 2 ), 1.95-1.96 (t, 2H , 4 J = 2.7, C≡C H ), 2.20-2.23 (m, 8H, C H 2 (CH 2 ) 2 C H 2 ), 2.64 (br s, 8H, W 1/2 = 50, N (C H 2 C H 2 ) 2 ), 3.27 (t, 4H, 4 J = 2, NC H 2 C≡C). 13 С NMR spectrum (125 MHz, δ, ppm): 17.9 ( С Н 2 С≡СН), 18.3 (СН 2 С≡С С Н 2 СН 2 ), 27.6 (С = СН 2 С Н 2 ) , 27.7 ( С Н 2 СН 2 С≡СН), 47.3 (N C H 2 C≡C), 51.9 (N ( C H 2 C H 2 ) N), 68.5 (-С≡ С Н), 75.1 (NCH 2 C C-), 84.2 ( C CH), 84.9 (NCH 2 C≡ C -). Mass spectrum MALDI-TOF, m / z: 323.2941 [М + Н] + C 22 H 31 N 2 , 345.2606 [M + Na] + C 22 H 30 N 2 Na, 361.2262 [M + K] + C 22 H 30 N 2 K. Calculated: 323.2487 [M + H] + , 345.2307 [M + Na] + , 361.2046 [M + K] + .

1,4-Ди(2,9-декадиинил)пиперазин (1в).1,4-Di (2,9-decadiinyl) piperazine (1c).

Figure 00000009
Figure 00000009

Коричневое масло, выход 0.15 г (43%); Rf 0.3 (С6Н6 - СО(СН3)2 - изо-PrOH, 1:2:0.5). ИК-спектр, v/см-1 (пленка): 636, 755, 812, 1009, 1133, 1150, 1332, 1455, 1680, 2116, 2230, 2254, 2814, 2860, 2932. Спектр ЯМР 1Н (500 МГц, CDC13, δ, м.д., J/Гц): 1.45-1.48 (м, 12Н, СН2(СН 2)3СН2), 1.92 (с, 2Н, С≡CH), 2.13-2.15 (м, 8Н, CH 2(CH2)3CH 2), 2.57 (уш с, 8Н, N(CH 2CH 2)2), 3.20 (с, 8Н, NCH 2C≡C). Спектр ЯМР 13С (125 МГц, δ, м.д.): 18.3 (СН2С≡СН), 18.6 (СН2С≡ССН2СН2), 27.9, 28.2, 28.3 (СН2(СН2)3СН2), 47.2 (NCH2C≡C), 51.8 (N(CH2 CH2)2N), 68.3 (-С≡СН), 74.9 (NCH2 C≡C-), 84.5 (С≡СН), 85.2 (NCH2C≡C-). Масс-спектр MALDI-TOF, m/z: 351.2679 [М+Н]+ C24H35N2, 373.2450 [M+Na]+ C24H34N2Na, 389.2048 [M+K]+ C24H34N2K. Вычислено: 351.2800 [M+H]+, 373.2620 [M+Na]+, 389.2359 [M+K]+.Brown oil, yield 0.15 g (43%); R f 0.3 (C 6 H 6 - CO (CH 3 ) 2 - iso-PrOH, 1: 2: 0.5). IR, v / cm -1 (film): 636, 755, 812, 1009, 1133, 1150, 1332, 1455, 1680, 2116, 2230, 2254, 2814, 2860, 2932. 1 H NMR (500 MHz , CDCl 3 , δ, ppm, J / Hz): 1.45-1.48 (m, 12H, CH 2 (C H 2 ) 3 CH 2 ), 1.92 (s, 2H, C≡C H ), 2.13- 2.15 (m, 8H, C H 2 (CH 2 ) 3 C H 2 ), 2.57 (br s, 8H, N (C H 2 C H 2 ) 2 ), 3.20 (s, 8H, NC H 2 C≡C ). 13 С NMR spectrum (125 MHz, δ, ppm): 18.3 ( С Н 2 С≡СН), 18.6 (СН 2 С≡С С Н 2 СН 2 ), 27.9, 28.2, 28.3 (СН 2 ( С Н 2 ) 3 СН 2 ), 47.2 (N C H 2 C≡C), 51.8 (N ( C H 2 C H 2 ) 2 N), 68.3 (-С≡ С Н), 74.9 (NCH 2 C ≡C -), 84.5 ( C CH), 85.2 (NCH 2 C≡ C -). Mass spectrum MALDI-TOF, m / z: 351.2679 [М + Н] + C 24 H 35 N 2 , 373.2450 [M + Na] + C 24 H 34 N 2 Na, 389.2048 [M + K] + C 24 H 34 N 2 K. Calculated: 351.2800 [M + H] + , 373.2620 [M + Na] + , 389.2359 [M + K] + .

1,4-Ди(2,10-ундекадиинил)пиперазин (1г).1,4-Di (2,10-undecadiynyl) piperazine (1d).

Figure 00000010
Figure 00000010

Светло-коричневый порошок, выход 0.117 г (31%); т пл 46-48° Rf 0.63 (С6Н6 - EtOAc -изо-PrOH, 2:3:0.5). ИК-спектр, v/см-1 (пленка): 3295, 2931, 2858, 2814, 2767, 2117; 1455, 1338, 1289, 1133, 1009 (-C-N-), 1456, 1384, 1331, 812 (-СН3). Спектр ЯМР 1Н (500 МГц, CDC13, δ, м.д., J/Гц): 1.39-1.42 (м, 8Н, CH2CH 2(CH2)2CH 2CH2), 1.50-1.53 (м, 8Н, СН2СН2(СН 2)2СН2 СН2), 1.94 (м, 2Н, С=СН), 2.17-2.20 (м, 8Н, CH 2(CH2)4CH 2), 2.64 (уш с, 8Н, W1/2=40, N(CH 2CH 2)2N), 3.27 (с, 4Н, NCH 2C≡C). Спектр ЯМР 13С (125 МГц, δ, м.д.): 18.3 (СН2С≡СН), 18.7 (СН2С≡ССН2СН2), 28.2 (СН2), 28.3 (СН2), 28.4 (СН2), 28.6 (СН2), 47.3 (NCH2C≡C), 51.9 (N(CH2 CH2)N), 68.2 (-С≡СН), 74.8 (NCH2C≡C-), 84.6 (С≡СН), 85.5 (NCH2C≡C-). Масс-спектр MALDI-TOF, m/z: 379.4382 [М+Н]+; C26H39N2. Вычислено: 379.3113Light brown powder, yield 0.117 g (31%); mp 46-48 ° R f 0.63 (C 6 H 6 - EtOAc -iso-PrOH, 2: 3: 0.5). IR spectrum, v / cm -1 (film): 3295, 2931, 2858, 2814, 2767, 2117; 1455, 1338, 1289, 1133, 1009 (-CN-), 1456, 1384, 1331, 812 (-CH 3 ). 1 H NMR spectrum (500 MHz, CDCl 3 , δ, ppm, J / Hz): 1.39-1.42 (m, 8H, CH 2 C H 2 (CH 2 ) 2 C H 2 CH 2 ), 1.50- 1.53 (m, 8H, CH 2 CH 2 ( CH 2 ) 2 CH 2 CH 2 ), 1.94 (m, 2H, C = CH ), 2.17-2.20 (m, 8H, C H 2 (CH 2 ) 4 C H 2 ), 2.64 (br s, 8H, W 1/2 = 40, N (C H 2 C H 2 ) 2 N), 3.27 (s, 4H, NC H 2 C≡C). 13 С NMR spectrum (125 MHz, δ, ppm): 18.3 ( С Н 2 С≡СН), 18.7 (СН 2 С≡С С Н 2 СН 2 ), 28.2 ( С Н 2 ), 28.3 ( С H 2 ), 28.4 ( C H 2 ), 28.6 ( C H 2 ), 47.3 (N C H 2 C≡C), 51.9 (N ( C H 2 C H 2 ) N), 68.2 (-C≡ C H ), 74.8 (NCH 2 C≡ C -), 84.6 ( C ≡ CH), 85.5 (NCH 2 C≡ C -). Mass spectrum MALDI-TOF, m / z: 379.4382 [M + H] + ; C 26 H 39 N 2 . Calculated: 379.3113

1,4-Бис[1-(4-фторфенил)-2,8-нонадиинил]пиперазин (1д).1,4-Bis [1- (4-fluorophenyl) -2,8-nonadiynyl] piperazine (1e).

Figure 00000011
Figure 00000011

Коричневое масло, выход 0.239 мг (47%); Rf 0.75 (гексан - EtOAc, 2:1). ИК-спектр, v/см-1 (пленка): 3305 (≡С-Н); 3069, 2928, 2861 (СН2), 2237 (-С≡С-); 1604 (Ph); 1227, 1156, 1094, 1015 (-C-N-), 998 (-CF), 757, 636 (≡С-Н). Спектр ЯМР 1Н (500 МГц, CDC13, δ, м.д., J/Гц): 1.67-1.75 (м, 8Н, СН2(СН 2)2СН2), 1.97-1.99 (д, 2Н, J=7, C≡СН), 2.24-2.28 (м, 4Н, СНС≡ССН 2), 2.34-2.38 (м, 4Н, СН 2С≡СН), 2.53 (уш с, 8Н, N(CH 2CH 2)2N), 4.53 (с, 2Н, NCH(Ar)C≡C), 6.99-7.05 (м, 4Н, (СН(Ar)), 7.48-7.55 (м, 4Н, СН(Ar)). Спектр ЯМР 13С (125 МГц, δ, м.д., J/Гц): 18.0 (СН2С≡СН), 18.4 (СН2С≡ССН2СН2), 27.6 (СН2С≡ССН2 СН2), 27.9 (СН2СН2С≡C), 49.3 (уш. с. N(CH2 CH2)2N), 60.5 (NCH(Ar)C≡C), 68.5 (C≡C), 76.2 (NCH(Ar)C≡C), 84.1 (NCH(Ar)C≡C), 87.8 (C≡C), 114.8 (д, J=21.1, CH(Ar)), 130.1 (д, J=7.9, CH(Ar)), 134.4 (C(Ar)), 162.2 (д, J=244.5, CF(Ar)). Масс-спектр MALDI-TOF, m/z: 509.2870 [M-H]+. C34H35F2N2. Вычислено: 509.2768.Brown oil, yield 0.239 mg (47%); R f 0.75 (hexane - EtOAc, 2: 1). IR spectrum, v / cm -1 (film): 3305 (≡C-H); 3069, 2928, 2861 (CH 2 ), 2237 (—C≡C—); 1604 (Ph); 1227, 1156, 1094, 1015 (-CN-), 998 (-CF), 757, 636 (C-H). 1 H NMR spectrum (500 MHz, CDCl 3 , δ, ppm, J / Hz): 1.67-1.75 (m, 8H, CH 2 ( CH 2 ) 2 CH 2 ), 1.97-1.99 (d, 2H , J = 7, C≡C H ), 2.24-2.28 (m, 4H, SNS≡SS H 2 ), 2.34-2.38 (m, 4H, C H 2 C≡CH), 2.53 (br s, 8H, N (C H 2 C H 2 ) 2 N), 4.53 (s, 2H, NC H (Ar) C≡C), 6.99-7.05 (m, 4H, ( CH (Ar)), 7.48-7.55 (m, 4Н, С Н (Ar)). 13 С NMR spectrum (125 MHz, δ, ppm, J / Hz): 18.0 ( С Н 2 С≡СН), 18.4 (СН 2 С≡С С Н 2 СН 2 ), 27.6 (СН 2 С≡ССН 2 С Н 2 ), 27.9 ( С Н 2 СН 2 С≡C), 49.3 (br.s. N ( C H 2 C H 2 ) 2 N), 60.5 (N C H (Ar) C≡C), 68.5 (C≡ C ), 76.2 (NCH (Ar) C C ), 84.1 (NCH (Ar) C≡ C ), 87.8 ( C ≡C), 114.8 (d, J = 21.1, CH (Ar) ), 130.1 ( d, J = 7.9, C H ( Ar)), 134.4 (C (Ar)), 162.2 ( d, J = 244.5, C F ( Ar)). Mass- MALDI-TOF spectrum, m / z: 509.2870 [MH] + C 34 H 35 F 2 N 2. Calculated: 509.2768.

1,4-Ди(2,7-октадиинил)-1,4-диазепан (1e).1,4-Di (2,7-octadiynyl) -1,4-diazepane (1e).

Figure 00000012
Figure 00000012

Светло-желтое масло, выход 0.308 мг (65%); Rf 0.5 (СбН6 - EtOAc - изо-PrOH, 2:1:0.5). ИК-спектр, v/см-1 (пленка): 3297, 2908, 2118, 16875, 1430, 1345, 1300, 1122, 640. Спектр ЯМР 1Н (400 МГц, CDC13, δ, м.д., J/Гц): 1.65-1.72 (м, 4Н, CH2CH 2CH2), 1.80-1.84 (м, 2Н, NCH2CH 2CH2N), 1.94 (с, 2Н, С≡СН), 2.28-2.37 (м, 8Н, CH 2CH2CH 2), 2.75 (с, 8Н, NCH 2CH 2), 3.30 (с, 4Н, NCH 2C≡C). Спектр ЯМР 13С (100 МГц, δ, м.д.): 17.5 (СН2С=СН), 17.8 (С≡ССН2СН2), 27.4 (С=ССН2 СН2), 27.7 (NCH2 CH2), 47.9 (NCH2C=C), 53.6 (NCH2CH2 CH2N), 54.5 (NCH2 CH2N), 68.8 (C≡CH), 76.5 (NCH2 C≡C-), 83.4 (C≡CH), 83.5 (NCH2C≡C). Масс-спектр MALDI-TOF, m/z: 307.1937 [M-H]+ C21H27N2, 331.2008 [M+Na]+ C21H28NaN2, 347.1736 [M+K]+ C21H28KN2. Вычислено: 307.2174 [M-H]+, 331.2150 [M+Na]+, 347.1890 [M+K]+.Light yellow oil, yield 0.308 mg (65%); R f 0.5 (C b H 6 - EtOAc - iso-PrOH, 2: 1: 0.5). IR, v / cm -1 (film): 3297, 2908, 2118, 16875, 1430, 1345, 1300, 1122, 640. 1 H NMR (400 MHz, CDC1 3, δ, ppm, J / Hz): 1.65-1.72 (m, 4H, CH 2 C H 2 CH 2 ), 1.80-1.84 (m, 2H, NCH 2 C H 2 CH 2 N), 1.94 (s, 2H, C≡C H ) , 2.28-2.37 (m, 8H, C H 2 CH 2 C H 2 ), 2.75 (s, 8H, NC H 2 C H 2 ), 3.30 (s, 4H, NC H 2 C≡C). 13 С NMR spectrum (100 MHz, δ, ppm): 17.5 ( С Н 2 С = СН), 17.8 (С≡С С Н 2 СН 2 ), 27.4 (С = CCH 2 С Н 2 ), 27.7 (NCH 2 C H 2 ), 47.9 (N C H 2 C = C), 53.6 (N C H 2 CH 2 C H 2 N), 54.5 (N C H 2 C H 2 N), 68.8 (C≡ C H), 76.5 (NCH 2 C ≡C-), 83.4 ( C ≡CH), 83.5 (NCH 2 C≡ C) . Mass spectrum MALDI-TOF, m / z: 307.1937 [MH] + C 21 H 27 N 2 , 331.2008 [M + Na] + C 21 H 28 NaN 2 , 347.1736 [M + K] + C 21 H 28 KN 2 ... Calculated: 307.2174 [MH] + , 331.2150 [M + Na] + , 347.1890 [M + K] + .

1,4-Бис[1-(4-фторфенил)-2,8-нонадиинил]-1,4-диазепан (1ж).1,4-Bis [1- (4-fluorophenyl) -2,8-nonadiynyl] -1,4-diazepane (1g).

Figure 00000013
Figure 00000013

Коричневое вязкое масло, выход 0.288 г (53%); Rf 0.59 (гексан - EtOAc, 1:2). ИК-спектр, v/см-1 (пленка): 3304 (С≡С-Н); 3068, 2942, 2869 (СН2), 2254 (-С≡С-); 2117 (С≡С-Н); 1599 (Ph); 1121, 1078, 1008 (-C-N-), 636 (≡С-Н). Спектр ЯМР 1Н (500 МГц, CDC13, δ, м.д., J/Гц): 1.73-1.78 (м, 10Н, CH2(CH 2)2CH2, N(CH2)2CH 2), 1.99 (с, 2Н, С≡СН), 2.28 (с, 4Н, NCH2C≡CCH 2), 2.38 (с, 4Н, СН 2С≡СН), 2.58-2.70 (м, 4Н, N(CH 2)2N), 2.70-2.77 (м, 4Н, (NCH 2)2CH2), 4.64, 4.65 (с, 2Н, 2(NCHC≡C), 6.99-7.05 (м, 4Н, CH(Ph)), 7.56-7.61 (м, 4Н, CH(Ph)). Спектр ЯМР 13С (125 МГц, δ, м.д., J/Гц): 18.0 (СН2С≡СН), 18.4 (СН2С≡ССН2СН2), 27.6, 27.9 (СН2 СН2СН2С≡С), 28.1, 28.2 ((NCH2)2 CH2), 50.9, 51.1 ((NCH2)2CH2), 52.6, 52.7 (N(CH2)2N), 61.0, 61.2 (NCH(Ar)C≡C), 68.6 (C≡CH), 76.7 (C≡C), 84.1 (C≡C), 87.1 (C≡C), 114.7 (д, J=20.7, CH(Ar)), 129.8 (д, J=7.5, CH(Ar)), 135.5 (CHC(Ar)), 162.7 (д, J=243.7, CF(Ar)). Масс-спектр MALDI-TOF, m/z: 523.2397 [M-H]+; C35H37F2N2. Вычислено: 523.2925.Brown viscous oil, yield 0.288 g (53%); R f 0.59 (hexane - EtOAc, 1: 2). IR spectrum, v / cm -1 (film): 3304 (C≡C-H); 3068, 2942, 2869 (CH 2 ), 2254 (—C≡C—); 2117 (C≡C-H); 1599 (Ph); 1121, 1078, 1008 (-CN-), 636 (C-H). 1 H NMR spectrum (500 MHz, CDCl 3 , δ, ppm, J / Hz): 1.73-1.78 (m, 10H, CH 2 (C H 2 ) 2 CH 2 , N (CH 2 ) 2 C H 2 ), 1.99 (s, 2H, C≡C H ), 2.28 (s, 4H, NCH 2 C≡CC H 2 ), 2.38 (s, 4H, C H 2 C≡CH), 2.58-2.70 (m, 4H, N (C H 2 ) 2 N), 2.70-2.77 (m, 4H, (NC H 2 ) 2 CH 2 ), 4.64, 4.65 (s, 2H, 2 (NC H C≡C), 6.99-7.05 (m, 4H, CH (Ph)), 7.56-7.61 (m, 4H, CH (Ph)). 13 С NMR spectrum (125 MHz, δ, ppm, J / Hz): 18.0 ( С Н 2 С≡СН), 18.4 (СН 2 С≡С С Н 2 СН 2 ), 27.6, 27.9 ( С Н 2 С Н 2 СН 2 С≡С), 28.1, 28.2 ((NCH 2 ) 2 C H 2 ), 50.9, 51.1 ((N C H 2 ) 2 CH 2 ), 52.6, 52.7 (N ( C H 2 ) 2 N), 61.0, 61.2 (N C H (Ar) C≡C), 68.6 (C≡CH) , 76.7 (C≡C), 84.1 ( C≡C), 87.1 (C≡C), 114.7 ( d, J = 20.7, C H ( Ar)), 129.8 ( d, J = 7.5, C H ( Ar) ), 135.5 (CH C (Ar)), 162.7 (d, J = 243.7, C F (Ar)). MALDI-TOF mass spectrum, m / z: 523.2397 [MH] + ; C 35 H 37 F 2 N 2. Calculated: 523.2925.

1,3-Ди(2,7-октадиинил)имидазолидин (1з).1,3-Di (2,7-octadiynyl) imidazolidine (1h).

Figure 00000014
Figure 00000014

Желтое прозрачное вязкое масло, выход 0.142 мг (51%); Rf 0.35 (бензол - ацетон, 1:1). ИК-спектр, v/см-1 (пленка): 3295, 2936, 2866, 2258, 2117, 1681, 1432, 1345, 1328, 1127, 642. Спектр ЯМР 1Н (400 МГц, CDC13, δ, м.д., J/Гц): 1.71 (квин, 4Н, 3J=7.2, СН2СН 2СН2), 1.95 (т, 2Н, 4J=2.6, С≡СН), 2.28-2.33 (м, 8Н, СН 2СН2СН 2), 2.91 (с, 4Н, NCH 2CH 2), 3.38 (с, 4Н, NCH 2C≡C), 3.58 (с, 2Н, NCH 2N). Спектр ЯМР 13С (100 МГц, δ, м.д.): 17.5 (СН2С≡СН), 17.8 (С≡ССН2СН2), 27.6 (С≡ССН2 СН2), 42.9 (NCH2C≡C), 51.2 (NCH2 CH2N), 68.8 (-С≡СН), 73.6 (NCH2N), 76.3 (NCH2 C≡C-), 83.3 (С≡СН), 83.5 (NCH2C≡C-). Масс-спектр MALDI-TOF, m/z: 279.2228 [M-H]+ C19H23N2, 303.2210 [M+Na]+ C19H24NaN2, 319.2108 [M+K]+ C19H24KN2. Вычислено: 279.1861 [M-H]+, 303.1837 [M+Na]+, 319.1577 [M+K]+.Yellow transparent viscous oil, yield 0.142 mg (51%); R f 0.35 (benzene - acetone, 1: 1). IR, v / cm -1 (film): 3295, 2936, 2866, 2258, 2117, 1681, 1432, 1345, 1328, 1127, 642. 1 H NMR (400 MHz, CDC1 3, δ, m. d., J / Hz): 1.71 (quinn, 4H, 3 J = 7.2, CH 2 C H 2 CH 2 ), 1.95 (t, 2H, 4 J = 2.6, C≡C H ), 2.28-2.33 (m , 8H, C H 2 CH 2 C H 2 ), 2.91 (s, 4H, NC H 2 C H 2 ), 3.38 (s, 4H, NC H 2 C≡C), 3.58 (s, 2H, NC H 2 N). 13 С NMR spectrum (100 MHz, δ, ppm): 17.5 ( С Н 2 С≡СН), 17.8 (С≡С С Н 2 СН 2 ), 27.6 (С≡ССН 2 С Н 2 ), 42.9 (N C H 2 C≡C), 51.2 (N C H 2 C H 2 N), 68.8 (-C≡ C H), 73.6 (N C H 2 N), 76.3 (NCH 2 C ≡C-), 83.3 ( C CH), 83.5 (NCH 2 C≡ C -). Mass spectrum MALDI-TOF, m / z: 279.2228 [MH] + C 19 H 23 N 2 , 303.2210 [M + Na] + C 19 H 24 NaN 2 , 319.2108 [M + K] + C 19 H 24 KN 2 ... Calculated: 279.1861 [MH] + , 303.1837 [M + Na] + , 319.1577 [M + K] + .

1,3-Ди(2,8-нонадиинил)имидазолидин (1и).1,3-Di (2,8-nonadiynyl) imidazolidine (1i).

Figure 00000015
Figure 00000015

Светло-желтое масло, выход 0.19 мг (62%). Rf 0.45 (гексан - EtOAc, 1:2). ИК-спектр, v/см-1 (пленка): 3292, 2932, 2861, 2115, 1673, 1433, 1327, 1140, 1049, 640. Спектр ЯМР 1Н (400 МГц, CDC13, δ, м.д., J/Гц): 1.62-1.64 (м, 8Н, СН2(СН 2)2СН2), 1.95 (т, 2Н, 4J=2.6, С≡СН), 2.22-2.24 (м, 8Н, CH 2(CH2)2CH 2), 2.96 (с, 4Н, NCH 2CH 2), 3.42 (с, 4Н, NCH 2C≡C), 3.64 (с, 2Н, NCH 2N). Спектр ЯМР 13С (100 МГц, δ, м.д.): 17.9 (СН2С≡СН), 18.2 (С≡ССН2СН2), 27.5, 27.6 (С≡ССН2(СН2)2), 42.9 (NCH2C≡C), 51.1 (NCH2 CH2N), 68.5 (С≡СН), 73.5 (NCH2N), 75.6 (NCH2 C≡C-), 84.1 (C≡CH), 84.3 (NCH2C≡C). Масс-спектр MALDI-TOF, m/z: 307.2240 [M-H]+ C21H27N2, 331.2177 [M+Na]+ C21H28NaN2, 347.1872 [M+K]+ C21H28KN2. Вычислено: 307.2174 [M-H]+, 331.2150 [M+Na]+, 347.1890 [M+K]+.Light yellow oil, yield 0.19 mg (62%). R f 0.45 (hexane - EtOAc, 1: 2). IR spectrum, v / cm -1 (film): 3292, 2932, 2861, 2115, 1673, 1433, 1327, 1140, 1049, 640. 1 H NMR spectrum (400 MHz, CDCl 3 , δ, ppm. , J / Hz): 1.62-1.64 (m, 8H, CH 2 (C H 2 ) 2 CH 2 ), 1.95 (t, 2H, 4 J = 2.6, C≡C H ), 2.22-2.24 (m, 8H , C H 2 (CH 2 ) 2 C H 2 ), 2.96 (s, 4H, NC H 2 C H 2 ), 3.42 (s, 4H, NC H 2 C≡C), 3.64 (s, 2H, NC H 2 N). 13 С NMR spectrum (100 MHz, δ, ppm): 17.9 ( С Н 2 С≡СН), 18.2 (С≡С С Н 2 СН 2 ), 27.5, 27.6 (С≡ССН 2 (СН 2 ) 2 ), 42.9 (N C H 2 C≡C), 51.1 (N C H 2 C H 2 N), 68.5 (C≡ C H), 73.5 (N C H 2 N), 75.6 (NCH 2 C ≡C -), 84.1 ( C ≡CH), 84.3 (NCH 2 C≡ C ). Mass spectrum MALDI-TOF, m / z: 307.2240 [MH] + C 21 H 27 N 2 , 331.2177 [M + Na] + C 21 H 28 NaN 2 , 347.1872 [M + K] + C 21 H 28 KN 2 ... Calculated: 307.2174 [MH] + , 331.2150 [M + Na] + , 347.1890 [M + K] + .

Выявление фунгицидной активности осуществлено с использованием микроскопических грибов Bipolaris sorokiniana, Fusarium oxysporum, Rhizoctonia solani, которые вызывают корневые гнили зерновых культур. Кроме того, фитопатогенный гриб Rhizoctonia solani является возбудителем бурой и сухой гнили (ризоктониоза), поражающий до 230 видов сельскохозяйственных растений (картофель, томат, капуста, редис, свекла, фасоль, чечевица, люцерна, лен и др.) (Микроорганизмы - возбудители болезней растений. / Под ред. Билай В.И. - Киев: Наукова Думка, 1988, 552 с.).The detection of fungicidal activity was carried out using microscopic fungi Bipolaris sorokiniana, Fusarium oxysporum, Rhizoctonia solani, which cause root rot of cereals. In addition, the phytopathogenic fungus Rhizoctonia solani is the causative agent of brown and dry rot (rhizoctoniosis), affecting up to 230 species of agricultural plants (potatoes, tomatoes, cabbage, radishes, beets, beans, lentils, alfalfa, flax, etc.) (Microorganisms - pathogens plants. / Under the editorship of Bilay V.I. - Kiev: Naukova Dumka, 1988, 552 p.).

Оценку фунгицидной активности проводили методом диффузии в агар (Практикум по микробиологии. / Под ред. Егорова Н.С.- М.: Изд-во МГУ, 1976, 307 с.). Для испытания использовали растворы (1) в ДМФА (0.5%). Оценка влияния растворителя на тест-культуры грибков показала отсутствие негативного воздействия ДМФА на развитие микроскопических грибов. Результаты испытаний приведены в таблице 2.Evaluation of fungicidal activity was carried out by the method of diffusion in agar (Workshop on microbiology. / Edited by Egorov N.S. - Moscow: Izd-vo MGU, 1976, 307 p.). For testing, we used solutions (1) in DMF (0.5%). Evaluation of the effect of the solvent on the test cultures of fungi showed the absence of a negative effect of DMF on the development of microscopic fungi. The test results are shown in Table 2.

Figure 00000016
Figure 00000016

Результаты, представленные в табл. 2, показывают, что 1б, в, е в концентрации 0.5% обладают фунгицидной активностью по отношению к Bipolaris sorokiniana, а соединения 1а и 1в угнетают развитие Rhizoctonia solani. Ни одно из испытанных соединений не проявляет фунгицидной активности к Fusarium oxysporum.The results are presented in table. 2 show that 1b, c, f at a concentration of 0.5% exhibit fungicidal activity against Bipolaris sorokiniana, while compounds 1a and 1c inhibit the development of Rhizoctonia solani. None of the compounds tested showed fungicidal activity against Fusarium oxysporum.

Таким образом, испытанные N,N'-ди(алкадиинил)диазациклоалканы (1а-в, е) обладают противогрибковой активностью по отношению к фитопатогенным грибам - Bipolaris sorokiniana и Rhizoctonia solani. Полученные результаты свидетельствуют о том, что соединения (1а), (1б), (1в) и (1е) могут быть использованы для создания на их основе фунгицидного препарата для защиты сельскохозяйственных растений от фитопатогенных грибов.Thus, the tested N, N'-di (alkadinyl) diazacycloalkanes (1a-c, f) exhibit antifungal activity against phytopathogenic fungi - Bipolaris sorokiniana and Rhizoctonia solani. The results obtained indicate that compounds (1a), (1b), (1c), and (1f) can be used to create on their basis a fungicidal preparation for protecting agricultural plants from phytopathogenic fungi.

Claims (6)

1. N,N'-Ди(алкадиинил)диазациклоалканы общей формулы (1)1.N, N'-Di (alkadinyl) diazacycloalkanes of general formula (1)
Figure 00000017
Figure 00000017
 2. Способ получения N,N'-ди(алкадиинил)диазациклоалканов общей формулы (1)2. A method of obtaining N, N'-di (alkadiinyl) diazacycloalkanes of general formula (1)
Figure 00000017
Figure 00000017
 отличающийся тем, что циклические вторичные диамины (имидазолидин, пиперазин, 1,4-диазепан) подвергают взаимодействию с α,ω-диацетиленами общей формулы НС≡С-СН2-(СН2)n-СН2-С≡СН (где n=1-4) и альдегидами RCHO, где R=Н, р-F-C6H4, при мольном соотношении диамин : α,ω-диацетилен : альдегид, равном 1:2:2, в присутствии катализатора CuCl (10 мол.%) в атмосфере аргона при температуре 100°С в среде толуола в течение 8 ч.characterized in that cyclic secondary diamines (imidazolidine, piperazine, 1,4-diazepane) are reacted with α, ω-diacetylenes of the general formula HC≡C-CH 2 - (CH 2 ) n -CH 2 -C≡CH (where n = 1-4) and aldehydes RCHO, where R = H, p-FC 6 H 4 , at a molar ratio of diamine: α, ω-diacetylene: aldehyde equal to 1: 2: 2, in the presence of a CuCl catalyst (10 mol% ) in an argon atmosphere at a temperature of 100 ° C in a toluene medium for 8 h. 3. Применение N,N'-ди(алкадиинил)диазациклоалканов общей формулы (1) в качестве средства с фунгицидной активностью в отношении фитопатогенных грибов Bipolaris sorokiniana и Rhizoctonia solani.3. Application of N, N'-di (alkadiinyl) diazacycloalkanes of general formula (1) as an agent with fungicidal activity against phytopathogenic fungi Bipolaris sorokiniana and Rhizoctonia solani.
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