RU2675505C2 - Method of the n-alkyl(phenyl)-n,n-bis[4-alkoxy(phenoxy-, benzyloxy-, prop-2-ynyloxy)-2-butynyl]amines preparation - Google Patents

Method of the n-alkyl(phenyl)-n,n-bis[4-alkoxy(phenoxy-, benzyloxy-, prop-2-ynyloxy)-2-butynyl]amines preparation Download PDF

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RU2675505C2
RU2675505C2 RU2016146964A RU2016146964A RU2675505C2 RU 2675505 C2 RU2675505 C2 RU 2675505C2 RU 2016146964 A RU2016146964 A RU 2016146964A RU 2016146964 A RU2016146964 A RU 2016146964A RU 2675505 C2 RU2675505 C2 RU 2675505C2
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Усеин Меметович Джемилев
Асхат Габдрахманович Ибрагимов
Гузель Ражаповна Хабибуллина
Фируза Тимирьяновна Зайнуллина
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Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/46—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/52—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups or amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C217/64—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains further substituted by singly-bound oxygen atoms

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Abstract

FIELD: chemistry.SUBSTANCE: compounds of general formula (1) can be used as universal precursors for fine organic synthesis and biologically active compounds. In the general formula (1)method is that N-alkyl(phenyl)-1,5,3-dioxazepane of general formula RN(CHOCH)(where R= Ph, n-Bu, tert-Bu) is subjected to reaction with the propargyl ester of general formula HC≡CCHOR, where R= tert-Bu, Ph, CHC≡CH, Bn, in the presence of a CuCl catalyst at a molar ratio of N-alkyl(phenyl)-1,5,3-dioxazepane : propargyl ether : CuCl = 1:2:(0.03-0.07) under argon atmosphere at a temperature of 80°C and atmospheric pressure under toluene environment for 5-7 hours.EFFECT: invention relates to a novel process of novel N-alkyl(phenyl)-N,N-bis[4-alkoxy(phenoxy, benzyloxy or prop-2-ynyloxy)-2-butynyl]amines preparation of general formula (1).1 cl, 1 tbl, 10 ex

Description

Предлагаемое изобретение относится к органической химии, в частности, к способу получения N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]аминов общей формулы (1).The present invention relates to organic chemistry, in particular, to a method for producing N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynyloxy) -2-butynyl] amines of the general formula (1 )

Figure 00000001
Figure 00000001

Соединения общей формулы (1) могут быть использованы в качестве универсальных прекурсоров для тонкого органического синтеза [Haraburda Е.,

Figure 00000002
, Roglans A., Pla-Quintana A. Org. Lett, 2015, 77, 2882; Tang J., Shinokubo H., Oshima K. Organometallics, 1998, 77, 290; Shibata Т., Uchiyama Т., Endo K. Org. Lett, 2009, 77, 3906] и биологически активных соединений [Dembitsky V.M., Levitsky D.O. Nat. Prod. Commun. 2006, 1, 405; Chen J.J., Swope D.M, Dashtipour K., Clin. Ther., 2007, 29, 1825].Compounds of general formula (1) can be used as universal precursors for fine synthesis [Haraburda E.,
Figure 00000002
, Roglans A., Pla-Quintana A. Org. Lett, 2015, 77, 2882; Tang J., Shinokubo H., Oshima K. Organometallics, 1998, 77, 290; Shibata T., Uchiyama T., Endo K. Org. Lett, 2009, 77, 3906] and biologically active compounds [Dembitsky VM, Levitsky DO Nat. Prod. Commun. 2006, 1, 405; Chen JJ, Swope DM, Dashtipour K., Clin. Ther., 2007, 29, 1825].

Известен способ (Uhlig, N.; Li, C. - J. Site-specific modification of amino acids and peptides by aldehyde-alkyne-amine coupling under ambient aqueous conditions. Organic Letters. 2012, 14, 3000) получения 2-[бис(3-фенил-2-пропинил)амино]карбоновых кислот (2) трехкомпонентной реакцией фенилацетилена, формальдегида и гидрохлоридов эфиров аминокислот под действием 10% CuCl при температуре 35°С в атмосфере аргона:A known method (Uhlig, N .; Li, C. - J. Site-specific modification of amino acids and peptides by aldehyde-alkyne-amine coupling under ambient ambient conditions. Organic Letters. 2012, 14, 3000) to obtain 2- [bis (3-phenyl-2-propynyl) amino] carboxylic acids (2) by a three-way reaction of phenylacetylene, formaldehyde and hydrochlorides of amino acid esters under the influence of 10% CuCl at a temperature of 35 ° C in argon atmosphere:

Figure 00000003
Figure 00000003

Известным способом не могут быть получены N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]амины общей формулы (1).In a known manner, N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynyloxy) -2-butynyl] amines of the general formula (1) cannot be obtained.

Известен способ [Azerbaev, I.N. Izvestiya Academy of Sciences Kazakh. SSR. 1975, 25, 58. (c) Azerbaev, I.N. Izvestiya Academy of Sciences Kazakh. SSR. 1978, 28, 70] получения 5-[(4-гидрокси-4-метил-2-пентинил)(пропил)амино]-2-метил-3-пентин-2-ола (3а) или 5-[(4-гидрокси-4-метил-2-пентинил)(фенил)амино]-2-метил-3-пентин-2-ола (3b) реакцией аминометилирования 2-метил-3-бутин-2-ола с N,N-бис(этоксиметил)-N-пропил(фенил)аминами с выходами 52 и 79% соответственно по схеме:The known method [Azerbaev, I.N. Izvestiya Academy of Sciences Kazakh. SSR 1975, 25, 58. (c) Azerbaev, I.N. Izvestiya Academy of Sciences Kazakh. SSR 1978, 28, 70] obtaining 5 - [(4-hydroxy-4-methyl-2-pentynyl) (propyl) amino] -2-methyl-3-pentin-2-ol (3a) or 5 - [(4- hydroxy-4-methyl-2-pentynyl) (phenyl) amino] -2-methyl-3-pentin-2-ol (3b) by the aminomethylation of 2-methyl-3-butyn-2-ol with N, N-bis ( ethoxymethyl) -N-propyl (phenyl) amines with yields of 52 and 79%, respectively, according to the scheme:

Figure 00000004
Figure 00000004

Известным способом не могут быть получены N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]амины общей формулой (1).In a known manner, N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynyloxy) -2-butynyl] amines of the general formula (1) cannot be obtained.

Таким образом, в литературе отсутствуют сведения о селективном получении N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]аминов общей формулы (1).Thus, in the literature there is no information on the selective preparation of N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynyloxy) -2-butynyl] amines of the general formula (1).

Предлагается новый способ получения N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]аминов общей формулы (1).A new method is proposed for the preparation of N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynyloxy) -2-butynyl] amines of the general formula (1).

Сущность способа заключается во взаимодействии N-алкил(фенил)-1,5,3-диоксазепана общей формулы R1N(CH2OCH2)2, где R1=н-Bu, трет-Bu, Ph, с пропаргиловым эфиром общей формулы HC≡CCH2OR2, где R2=трет-Bu, Ph, Bn, СН2С≡СН в присутствии катализатора CuCl при мольном соотношении 1,5,3-диоксазепан : пропаргиловый эфир : CuCl=1:2:(0.03-0.07), предпочтительно 1:2:0.05, в атмосфере аргона при температуре 80°С и атмосферном давлении в толуоле в качестве растворителя в течение 5-7 ч. Выход N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]аминов (1a-f) составляет 47-95%.The essence of the method consists in the interaction of N-alkyl (phenyl) -1,5,3-dioxazepane of the general formula R 1 N (CH 2 OCH 2 ) 2 , where R 1 = n-Bu, tert-Bu, Ph, with propargyl ether formulas HC≡CCH 2 OR 2 , where R 2 = tert-Bu, Ph, Bn, СН 2 С≡СН in the presence of a CuCl catalyst with a molar ratio of 1,5,3-dioxazepane: propargyl ether: CuCl = 1: 2 :( 0.03-0.07), preferably 1: 2: 0.05, in an argon atmosphere at a temperature of 80 ° C and atmospheric pressure in toluene as a solvent for 5-7 hours. Yield N-alkyl (phenyl) -N, N-bis [4 -alkoxy (phenoxy, benzyloxy, prop-2-ynyloxy) -2-butynyl] amines (1a-f) is 47-95%.

Реакция проходит по схеме:The reaction proceeds according to the scheme:

Figure 00000005
Figure 00000005

N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]амины (1) образуются только лишь с участием 1,5,3-диоксазепанов и пропаргиловых эфиров, взятых в мольном соотношении 1:2 (стехиометрические количества), под действием катализатора CuCl (5 мол. %). При другом соотношении исходных реагентов или в присутствии других Cu-содержащих катализаторов (CuCl2, CuBr, CuBr2, CuCl2⋅2Н2О, CuI, CuSO4) снижается выход целевого продукта (1). Проведение указанной реакции в присутствии катализатора CuCl больше 7 мол. % по отношению к 1,5,3-диоксазепану не приводит к существенному увеличению выхода целевого продукта (1). Использование катализатора CuCl менее 3 мол. % снижает выход (1), что связано, возможно, со снижением каталитически активных центров в реакционной массе. Реакции проводили при температуре 80°С. При температуре выше 80°С (например, 100°С) увеличиваются энергозатраты, а при температуре ниже 80°С (например, 60°С) снижается скорость реакции. Опыты проводили в толуоле, т.к. в нем хорошо растворяются исходные реагенты и целевые продукты.N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynyloxy) -2-butynyl] amines (1) are formed only with the participation of 1,5,3-dioxazepanes and propargyl esters taken in a molar ratio of 1: 2 (stoichiometric amounts) under the influence of a CuCl catalyst (5 mol%). With a different ratio of the starting reagents or in the presence of other Cu-containing catalysts (CuCl 2 , CuBr, CuBr 2 , CuCl 2 ⋅ 2Н 2 О, CuI, CuSO 4 ), the yield of the target product decreases (1). Carrying out the specified reaction in the presence of a catalyst of CuCl more than 7 mol. % with respect to 1,5,3-dioxazepane does not lead to a significant increase in the yield of the target product (1). The use of CuCl catalyst less than 3 mol % reduces the yield (1), which is possibly associated with a decrease in catalytically active centers in the reaction mass. The reaction was carried out at a temperature of 80 ° C. At temperatures above 80 ° C (for example, 100 ° C), energy consumption increases, and at temperatures below 80 ° C (for example, 60 ° C), the reaction rate decreases. The experiments were carried out in toluene, because source reagents and target products dissolve well in it.

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

В известном способе в качестве исходных реагентов применяются бис(этоксиметил)амины и пропаргиловый спирт. Известный способ не позволяет получать N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]амины общей формулы (1). В предлагаемом способе в качестве исходных реагентов применяются N-алкил(фенил)-1,5,3-диоксозепаны и пропаргиловые эфиры. Предлагаемый способ позволяет получать N-алкил(фенил)-N,N-bis[4-алкокси(фенокси, бензилокси, проп-2-инилокси)-2-бутинил]амины общей формулы (1).In the known method, bis (ethoxymethyl) amines and propargyl alcohol are used as starting reagents. The known method does not allow to obtain N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynoxy) -2-butynyl] amines of the general formula (1). In the proposed method, N-alkyl (phenyl) -1,5,3-dioxosepanes and propargyl ethers are used as starting reagents. The proposed method allows to obtain N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy, benzyloxy, prop-2-ynoxy) -2-butynyl] amines of the 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 0.159 гр (1 ммоль) N-трет-бутил-1,5,3-диоксазепана, 3 мл толуола и 0.224 гр трет-бутил-2-пропинилового эфира (2 ммоль), добавляют CuCl (0.005 г, 5 мол. %), перемешивают при температуре 80°С в течение 6 ч, отфильтровывают через слой SiO2, промывают хлороформом 3×5 мл, упаривают, выделяют методом колоночной хроматографии; 0.20 г (63%) N,N-бис(4-трет-бутоксибут-2-инил)-N-(трет-бутил)амина.Example 1. 0.159 g (1 mmol) of N-tert-butyl-1,5,3-dioxazepane, 3 ml of toluene and 0.224 g of tert-butyl-2-propynyl ether are placed in a Schlenk vessel mounted on a magnetic stirrer in an argon atmosphere. (2 mmol), CuCl (0.005 g, 5 mol%) was added, stirred at 80 ° C for 6 hours, filtered through a layer of SiO 2 , washed with 3 × 5 ml chloroform, evaporated, and isolated by column chromatography; 0.20 g (63%) of N, N-bis (4-tert-butoxybut-2-ynyl) -N- (tert-butyl) amine.

Другие примеры, подтверждающие способ, приведены в табл. 1 (растворитель -толуол, температура 80°С).Other examples confirming the method are given in table. 1 (the solvent is toluene, temperature 80 ° C).

Figure 00000006
Figure 00000006

Физико-химические характеристики соединений 1a-1f:* (*Спектры ЯМР 1Н и 13С регистрировали на спектрометре Bruker Avance-400 с рабочими частотами 400.13 и 100.62 МГц, растворитель - CDCl3 (δC 77.10 м.д.). ИК-спектры снимали на спектрометре Bruker Vertex 70 v в суспензии в вазелиновом масле. Анализ методом ГХ-МС проводили на хроматографе Shimadzu GC 2010 с масс-спектрометрическим детектором GCMS-QP2010 Ultra (Shimadzu, Япония). Использовали капиллярную колонку Supelco 5ms (60 м × 0.25 мм × 0.25 мкм). В качестве газа-носителя использовали гелий. Температура инжектора - 260°С, интерфейса - 260°С, ионного источника - 200°С. Элементный состав С, Н и N определяли на приборе Karlo Erba-1106.)Physicochemical characteristics of compounds 1a-1f: * ( * 1 H and 13 C NMR spectra were recorded on a Bruker Avance-400 spectrometer with operating frequencies of 400.13 and 100.62 MHz, and the solvent was CDCl 3 (δ C 77.10 ppm). IR the spectra were recorded on a Bruker Vertex 70 v spectrometer in suspension in liquid paraffin. GC-MS analysis was performed on a Shimadzu GC 2010 chromatograph with a GCMS-QP2010 Ultra mass spectrometer (Shimadzu, Japan). A Supelco 5ms capillary column (60 m × 0.25 was used) mm × 0.25 μm). Helium was used as the carrier gas. The temperature of the injector was 260 ° С, the interface was 260 ° С, and the ion source ka - 200 ° C. The elemental composition of C, H and N was determined on a Karlo Erba-1106 device.)

N,N-бис(4-трет-Бутоксибут-2-инил)-N-(трет-бутил)амин (1а).N, N-bis (4-tert-Butoxybut-2-ynyl) -N- (tert-butyl) amine (1a).

Figure 00000007
Figure 00000007

Желтое прозрачное масло, выход 0.20 г (63%), Rf=0.58 (гексан : EtOAc 1:2), ИК-спектр (νmax, см-1): 931 (С-С), 1129 (C-N), 1467 (СН3), 2227 (-C≡C-), 2972, 2928 (СН3), 2973 (СН2); δН (400 MHz, CDCl3, 25°С) 1.17 (9Н, s, NC(CH 3)3); 1.23 (18Н, s, ОС(СН 3)3); 3.64 (4Н, s, CN(CH 2C≡C)2); 4.09 (4Н, s, СН2C≡ССН 2O); δC (100 MHz, CDCl3) 27.46 (NC(CH3)3); 27.50 (OC(CH3)3); 37.02 (CN(CH2≡C)2); 50.78 (CH2C≡CCH2O); 55.01 (NC(CH3)3); 74.09 (OC(CH3)3); 81.63 (CN(CH2 C≡C)2); 82.55 (CN(CH2C≡C)2); m/z (Iотн, %): 321 (36) [M]+, 265 (11) [M-C(CH3)2CH2], 209 (100) [M-2C(CH3)2CH2]; Вычислено, %: C20H35NO2: C, 74.72; H, 10.97; N, 4.36. Найдено, %: С, 74.77; H, 11.02; N, 4.32.Yellow transparent oil, yield 0.20 g (63%), R f = 0.58 (hexane: EtOAc 1: 2), IR spectrum (ν max , cm -1 ): 931 (С-С), 1129 (CN), 1467 (CH 3 ), 2227 (-C≡C-), 2972, 2928 (CH 3 ), 2973 (CH 2 ); δ H (400 MHz, CDCl 3 , 25 ° C) 1.17 (9H, s, NC (C H 3 ) 3 ); 1.23 (18H, s, OS (C H 3 ) 3 ); 3.64 (4H, s, CN (C H 2 C≡C) 2 ); 4.09 (4H, s, CH 2 C≡CC H 2 O); δ C (100 MHz, CDCl 3 ) 27.46 (NC ( C H 3 ) 3 ); 27.50 (OC ( C H 3 ) 3 ); 37.02 (CN ( C H 2 ≡C) 2 ); 50.78 (CH 2 C≡C C H 2 O); 55.01 (N C (CH 3 ) 3 ); 74.09 (O C (CH 3 ) 3 ); 81.63 (CN (CH 2 C ≡C) 2 ); 82.55 (CN (CH 2 C≡ C ) 2 ); m / z ( Irel ,%): 321 (36) [M] + , 265 (11) [MC (CH 3 ) 2 CH 2 ], 209 (100) [M-2C (CH 3 ) 2 CH 2 ] ; Calculated,%: C 20 H 35 NO 2 : C, 74.72; H, 10.97; N, 4.36. Found,%: C, 74.77; H, 11.02; N, 4.32.

N-(трет-Бутил)-N,N-бис(4-феноксибут-2-инил)амин (1b).N- (tert-Butyl) -N, N-bis (4-phenoxybut-2-ynyl) amine (1b).

Figure 00000008
Figure 00000008

Желтое прозрачное масло, выход 0.27 г (75%), Rƒ 0.65 (гексан : EtOAc, 1:2). ИК-спектр (νmax, см-1): 777 (Ph), 1368 (СН3), 1427 (СН2), 1456 (СН3), 2121 (-C≡С-), 2819, 2871, 2921 (СН3), 3040 (СН2); δН (400 MHz, CDCl3, 25°С) 1.13 (9Н, s, NC(CH 3)3); 3.63 (4Н, s, CN(CH 2C≡C)2); 4.71 (4Н, s, C≡ССН 2O); 6.98-7.30 (10Н, m, Ph); δC (100 MHz, CDCl3) 27.4 (NC(CH3)3); 36.9 (CN(CH2C≡C)2); 55.1 (NC(CH3)3); 56.3 (C≡CCH2O); 79.0 (CN(CH2C≡C)2); 85.2 (CN(CH2 C≡C)2); 115.0 (Ph), 121.3 (Ph); 129.4 (Ph); 157.7 (Ph); m/z (%): 361 (100) [M]+, 268 (23) [M-PhO]+, 254 (36) [M-PhOCH2]+, 207 (17) [M-2Ph]+; Вычислено, %: C24H27NO2: C, 79.74; H, 7.53; N, 3.87. Найдено, %: С, 79.68; H, 7.57; N, 3.91.Yellow transparent oil, yield 0.27 g (75%), R ƒ 0.65 (hexane: EtOAc, 1: 2). IR spectrum (ν max , cm -1 ): 777 (Ph), 1368 (СН 3 ), 1427 (СН 2 ), 1456 (СН 3 ), 2121 (-C≡С-), 2819, 2871, 2921 ( CH 3 ), 3040 (CH 2 ); δ H (400 MHz, CDCl 3 , 25 ° C) 1.13 (9H, s, NC (C H 3 ) 3 ); 3.63 (4H, s, CN (C H 2 C≡C) 2 ); 4.71 (4H, s, C≡CC H 2 O); 6.98-7.30 (10H, m, Ph); δ C (100 MHz, CDCl 3 ) 27.4 (NC ( C H 3 ) 3 ); 36.9 (CN ( C H 2 C≡C) 2 ); 55.1 (N C (CH 3 ) 3 ); 56.3 (C≡C C H 2 O); 79.0 (CN (CH 2 C≡ C ) 2 ); 85.2 (CN (CH 2 C ≡C) 2 ); 115.0 (Ph), 121.3 (Ph); 129.4 (Ph); 157.7 (Ph); m / z (%): 361 (100) [M] + , 268 (23) [M-PhO] + , 254 (36) [M-PhOCH 2 ] + , 207 (17) [M-2Ph] + ; Calculated,%: C 24 H 27 NO 2 : C, 79.74; H, 7.53; N, 3.87. Found,%: C, 79.68; H, 7.57; N, 3.91.

N,N-бис[4-(Бензилокси)бут-2-инил]-N-(трет-бутил)-амин (1c).N, N-bis [4- (Benzyloxy) but-2-ynyl] -N- (tert-butyl) amine (1c).

Figure 00000009
Figure 00000009

Желтое прозрачное масло, выход 0.36 g (93%), Rƒ 0.82 (гексан : EtOAc, 1:2). ИК-спектр (νmax, см-1): 636, 691, 716, 753, 929, 1011, 1174, 1250, 1368, 1392, 1599, 2921, 2971; δН (400 MHz, CDCl3, 25°С) 1.25 (9Н, s, NC(CH 3)3); 3.76 (4Н, s, CN(CH 2C≡C)2); 4.24 (4Н, s, С≡ССН 2O); 4.63 (4Н, s, OCH 2Ph); 7.31-7.34 (10Н, m, Ph); δC (100 MHz, CDCl3) 27.5 (NC(CH3)3); 37.0 (CN(CH2C≡C)2); 55.2 (NC(CH3)3); 57.7 (C≡CCH2O); 71.5 (OCH2Ph); 80.1 (CN(CH2 C≡C)2); 84.3 (CN(CH2C≡C)2); 127.8 (Ph), 128.1 (Ph); 128.5 (Ph); 137.6 (Ph); m/z (%): 389 (43) [M]+, 312 (3) [M-Ph]+, 283 (10) [M-PhCH2O]+, 268 (4) [M-PhCH2OCH2]+, 91 (100) [PhCH2]+; Вычислено, %: C26H31NO2: С, 80.17; H, 8.02; N, 3.60. Найдено, %: С, 80.22; Н, 7.96; N, 3.64.Transparent yellow oil, yield 0.36 g (93%), R ƒ 0.82 (hexane: EtOAc, 1: 2). IR spectrum (ν max , cm -1 ): 636, 691, 716, 753, 929, 1011, 1174, 1250, 1368, 1392, 1599, 2921, 2971; δ H (400 MHz, CDCl 3 , 25 ° C) 1.25 (9H, s, NC (C H 3 ) 3 ); 3.76 (4H, s, CN (C H 2 C≡C) 2 ); 4.24 (4H, s, C≡CC H 2 O); 4.63 (4H, s, OC H 2 Ph); 7.31-7.34 (10H, m, Ph); δ C (100 MHz, CDCl 3 ) 27.5 (NC ( C H 3 ) 3 ); 37.0 (CN ( C H 2 C≡C) 2 ); 55.2 (N C (CH 3 ) 3 ); 57.7 (C≡C C H 2 O); 71.5 (O C H 2 Ph); 80.1 (CN (CH 2 C ≡C) 2 ); 84.3 (CN (CH 2 C≡C) 2 ); 127.8 (Ph), 128.1 (Ph); 128.5 (Ph); 137.6 (Ph); m / z (%): 389 (43) [M] + , 312 (3) [M-Ph] + , 283 (10) [M-PhCH 2 O] + , 268 (4) [M-PhCH 2 OCH 2 ] + , 91 (100) [PhCH 2 ] + ; Calculated,%: C 26 H 31 NO 2 : C, 80.17; H, 8.02; N, 3.60. Found,%: C, 80.22; H, 7.96; N, 3.64.

N,N-бис(4-Феноксибут-2-инил)-N-фениламин (1d).N, N-bis (4-Phenoxybut-2-ynyl) -N-phenylamine (1d).

Figure 00000010
Figure 00000010

Желтое прозрачное масло, выход 0.18 g (47%), Rƒ 0.9 (гексан : EtOAc, 1:2). ИК-спектр (νmax, см-1): 883, 1080, 1262, 1375 (C-N), 1456 (СН2), 1600 (Ph), 1931 (C≡С), 3028 (СН2); δН (400 MHz, CDCl3, 25°С) 4.72 (4Н, s, CN(CH 2C≡C)2); 4.73 (4Н, s, C≡ССН 2O); 7.00-7.04 (10Н, m, Ph); 7.32-7.35 (5Н, m, Ph); δC (100 MHz, CDCl3) 55.7 (CN(CH2C≡C)2); 75.5 (C≡ССН2O); 77.2 (CN(CH2 C≡C)2); 78.6 (CN(CH2C≡C)2); 114.9 (Ph), 121.6 (Ph); 129.5 (Ph); 157.6 (Ph); m/z (%): 381 (43) [M]+, 312 (3) [M-Ph]+, 283 (10) [M-PhCH2O]+, 268 (4) [M-PhCH2OCH2]+, 91 (100) [PhCH2]+; Вычислено, %: C26H23NO2: C, 81.86; H, 6.08; N, 3.67. Найдено, %: С, 81.93; H, 6.01; N, 3.72.Yellow clear oil, yield 0.18 g (47%), R ƒ 0.9 (hexane: EtOAc, 1: 2). IR spectrum (ν max , cm -1 ): 883, 1080, 1262, 1375 (CN), 1456 (СН 2 ), 1600 (Ph), 1931 (С≡С), 3028 (СН 2 ); δ H (400 MHz, CDCl 3 , 25 ° C) 4.72 (4H, s, CN (C H 2 C≡C) 2 ); 4.73 (4H, s, C≡CC H 2 O); 7.00-7.04 (10H, m, Ph); 7.32-7.35 (5H, m, Ph); δ C (100 MHz, CDCl 3 ) 55.7 (CN ( C H 2 C≡C) 2 ); 75.5 (C≡C C H 2 O); 77.2 (CN (CH 2 C ≡C) 2 ); 78.6 (CN (CH 2 C≡ C ) 2 ); 114.9 (Ph), 121.6 (Ph); 129.5 (Ph); 157.6 (Ph); m / z (%): 381 (43) [M] + , 312 (3) [M-Ph] + , 283 (10) [M-PhCH 2 O] + , 268 (4) [M-PhCH 2 OCH 2 ] + , 91 (100) [PhCH 2 ] + ; Calculated,%: C 26 H 23 NO 2 : C, 81.86; H, 6.08; N, 3.67. Found,%: C, 81.93; H, 6.01; N, 3.72.

N-Бутил-N,N-бис[4-(проп-2-инилокси)бут-2-инил]амин (1e).N-Butyl-N, N-bis [4- (prop-2-ynyloxy) but-2-ynyl] amine (1e).

Figure 00000011
Figure 00000011

Желтое прозрачное масло, выход: 0.16 г (56%); Rf=0.70 (CCl4 - i-PrOH, 10:2). ИК-спектр (νmax, см-1): 626 (С-Н), 841 (С-О-С), 935 (С-С), 1101 (C-N), 2125 (С≡С), 2860 (СН3), 3310 (С≡С-Н); δН (400 MHz, CDCl3, 25°С) 0.94 (t, J=7.2 Hz, 3Н, СН3); 1.25-1.50 (m, 4Н, CH 2CH 2CH3); 2.06 (s, 2Н, C≡СН); 2.52 (t, J=7.2 Hz, 2Н, NCH 2CH2); 3.48 (s, 4H, NCH 2C≡C); 4.26-4.27 (m, 4H, C≡CCH 2OCH2C≡CH); 4.31 (m, 4H, C≡CCH2OCH 2C≡CH); δC (100 MHz, CDCl3) 13.96 (CH3); 20.5 (CH2CH3); 29.6 (NCH2 CH2); 42.5 (NCH2C≡C); 52.8 (NCH2CH2); 56.3 (N(CH2C≡CCH2O)2); 56.9 (OCH2C≡CH); 74.9 (C≡CH); 78.9 (C≡С); 79.8 (C≡С); 82.3 (C≡C); m/z (%): 285 (48) [M]+, 246 (15) [M-CH2OCH]+, 216 (100) [M-CH2OCH2C≡CH]+, 207 (15) [CH3(CH2)3N(CH2C≡CCH2O)2]+, 57 (41) [CH3(CH2)3]; Вычислено, %: C18H23NO2: C, 75.76; H, 8.12; N, 4.91; O, 11.21. Найдено, %: С, 75.81; H, 8.05; N, 4.87.Yellow clear oil, yield: 0.16 g (56%); R f = 0.70 (CCl 4 - i-PrOH, 10: 2). IR spectrum (ν max , cm -1 ): 626 (С-Н), 841 (С-О-С), 935 (С-С), 1101 (CN), 2125 (С≡С), 2860 (СН 3 ), 3310 (С≡С-Н); δ H (400 MHz, CDCl 3 , 25 ° C) 0.94 (t, J = 7.2 Hz, 3H, CH 3 ); 1.25-1.50 (m, 4H, C H 2 C H 2 CH 3 ); 2.06 (s, 2H, C≡C H ); 2.52 (t, J = 7.2 Hz, 2H, NC H 2 CH 2 ); 3.48 (s, 4H, NC H 2 C≡C); 4.26-4.27 (m, 4H, C≡CC H 2 OCH 2 C≡CH); 4.31 (m, 4H, C≡CCH 2 OC H 2 C≡CH); δ C (100 MHz, CDCl 3 ) 13.96 (CH 3 ); 20.5 ( C H 2 CH 3 ); 29.6 (NCH 2 C H 2 ); 42.5 (N C H 2 C≡C); 52.8 (N C H 2 CH 2 ); 56.3 (N (CH 2 C≡C C H 2 O) 2 ); 56.9 (O C H 2 C≡CH); 74.9 (C≡ C H); 78.9 ( C ≡С); 79.8 ( C ≡C); 82.3 (C≡ C ); m / z (%): 285 (48) [M] + , 246 (15) [M-CH 2 OCH] + , 216 (100) [M-CH 2 OCH 2 C≡CH] + , 207 (15) [CH 3 (CH 2 ) 3 N (CH 2 C≡CCH 2 O) 2 ] + , 57 (41) [CH 3 (CH 2 ) 3 ]; Calculated,%: C 18 H 23 NO 2 : C, 75.76; H, 8.12; N, 4.91; O, 11.21. Found,%: C, 75.81; H, 8.05; N, 4.87.

N-(трет-Бутил)-N,N-бис[4-(проп-2-инилокси)бут-2-инил]амин (1f).N- (tert-Butyl) -N, N-bis [4- (prop-2-yloxy) but-2-ynyl] amine (1f).

Figure 00000012
Figure 00000012

Желтое прозрачное масло, выход: 0.22 г (79%); Rf=0.90 (Ме2СО - бензол, 1:1). ИК-спектр (νmax, см-1): 888 (C-N), 1078 (С-О-С), 1135 (С-О), 1218 (C-N), 1366 (СН3), 1443 (СН3), 21 15, 2362 (-C≡С-), 2855 (СН2), 2875(СН3), 2914 (СН2) см-1; δН (400 MHz, CDCl3, 25°С) 1.16 (s, 9Н, СН3); 2.43 (s, 2Н, C≡СН); 3.64 (s, 4Н, NCH 2C≡C); 4.23 (NCH2C≡CCH 2OCH2C≡CH); 4.25 (NCH2C≡CCH2OCH 2C≡CH); δC (100 MHz, CDCl3) 27.4 (CCH3); 36.8 (NCH2C≡C); 55.1 (CCH3); 56.3 (NCH2C≡CCH2O); 57.0 (OCH2C≡CH); 74.9 (C≡СН); 79.0 (С≡С); 79.1 (C≡С); 84.8 (C≡С); m/z (%): 285 (44) [М]+, 216 (53) [М-СН2ОСН2≡СН]+, 160 (100) [(CH3)3CN(CH2C≡C)2CH2]+; Вычислено, %: C18H23NO2: С, 75.76; Н, 8.12; N, 4.91. Найдено, %: С, 75.72; Н, 8.09; N, 4.96.Yellow clear oil, yield: 0.22 g (79%); R f = 0.90 (Me 2 CO - benzene, 1: 1). IR spectrum (ν max , cm -1 ): 888 (CN), 1078 (С-О-С), 1135 (С-О), 1218 (CN), 1366 (СН 3 ), 1443 (СН 3 ), 21 15, 2362 (-C≡C-), 2855 (CH 2 ), 2875 (CH 3 ), 2914 (CH 2 ) cm -1 ; δ H (400 MHz, CDCl 3 , 25 ° C) 1.16 (s, 9H, CH 3 ); 2.43 (s, 2H, C≡C H ); 3.64 (s, 4H, NC H 2 C≡C); 4.23 (NCH 2 C≡CC H 2 OCH 2 C≡CH); 4.25 (NCH 2 C≡CCH 2 OC H 2 C≡CH); δ C (100 MHz, CDCl 3 ) 27.4 (C C H 3 ); 36.8 (N C H 2 C≡C); 55.1 ( C CH 3 ); 56.3 (NCH 2 C≡C C H 2 O); 57.0 (O C H 2 C≡CH); 74.9 (C≡ C H); 79.0 ( C ≡C); 79.1 ( C ≡C); 84.8 (C≡ C ); m / z (%): 285 (44) [M] + , 216 (53) [M-CH 2 OCH 2 ≡CH] + , 160 (100) [(CH 3 ) 3 CN (CH 2 C≡C) 2 CH 2 ] + ; Calculated,%: C 18 H 23 NO 2 : C, 75.76; H, 8.12; N, 4.91. Found,%: C, 75.72; H, 8.09; N, 4.96.

Claims (3)

Способ получения N-алкил(фенил)-N,N-бис[4-алкокси(фенокси-, бензилокси- или проп-2-инилокси)-2-бутинил]аминов общей формулы (1)The method of obtaining N-alkyl (phenyl) -N, N-bis [4-alkoxy (phenoxy-, benzyloxy- or prop-2-ynyloxy) -2-butynyl] amines of the general formula (1)
Figure 00000013
Figure 00000013
 отличающийся тем, что N-алкил(фенил)-1,5,3-диоксазепан общей формулы R1N(CH2OCH2)2 (где R1 = Ph, н-Bu, трет-Bu) подвергают взаимодействию с пропаргиловым эфиром общей формулы HC≡CCH2OR2, где R2 = трет-Bu, Ph, СН2С≡СН, Bn, в присутствии катализатора CuCl при мольном соотношении N-алкил(фенил)-1,5,3-диоксазепан : пропаргиловый эфир : CuCl = 1:2:(0.03-0.07) в атмосфере аргона при температуре 80°С и атмосферном давлении в среде толуола в течение 5-7 ч.characterized in that N-alkyl (phenyl) -1,5,3-dioxazepane of the general formula R 1 N (CH 2 OCH 2 ) 2 (where R 1 = Ph, n-Bu, tert-Bu) is reacted with propargyl ether general formula HC≡CCH 2 OR 2 , where R 2 = tert-Bu, Ph, СН 2 С≡СН, Bn, in the presence of a CuCl catalyst with a molar ratio of N-alkyl (phenyl) -1,5,3-dioxazepane: propargyl ether: CuCl = 1: 2: (0.03-0.07) in an argon atmosphere at a temperature of 80 ° C and atmospheric pressure in toluene for 5-7 hours
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