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RU2664661C2 - 2,3-dialkyl-2-cyclooctene-1-one preparation process - Google Patents

2,3-dialkyl-2-cyclooctene-1-one preparation process Download PDF

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RU2664661C2
RU2664661C2 RU2016100787A RU2016100787A RU2664661C2 RU 2664661 C2 RU2664661 C2 RU 2664661C2 RU 2016100787 A RU2016100787 A RU 2016100787A RU 2016100787 A RU2016100787 A RU 2016100787A RU 2664661 C2 RU2664661 C2 RU 2664661C2
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dialkyl
ticl
etalcl
cycloocten
general formula
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Лейла Османовна Хафизова
Мария Геннадьевна Шайбакова
Нури Мамедеевич Чобанов
Усеин Меметович Джемилев
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Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

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Abstract

FIELD: chemistry.
SUBSTANCE: present invention relates to a process for the preparation of 2,3-dialkyl-2-cycloocten-1-ones of general formula :
Figure 00000011
, which are used as initial synthons for the creation of biologically active compounds, exhibiting antiviral, antifungal and antitumor properties. Process is characterized in that dialkylacetylenes of general formula R-C≡C-R, where R=C3H7 or C4H9, are reacted with a double excess of adipic acid methyl ester CH3CO2(CH2)4CO2CH3 and EtAlCl2 in the presence of magnesium (Mg, powder) and catalyst Cp2TiCl2, the reaction is carried out at a molar ratio RC≡CR : CH3CO2(CH2)4CO2CH3 : EtAlCl2 : Mg : Cp2TiCl2=10:20:(40-60):(40-60):(1.8-2.2), in tetrahydrofuran under argon at 60°C and atmospheric pressure for 4-8 hours.
EFFECT: proposed method allows to obtain the target product with a yield of 59 to 83%.
1 cl, 1 tbl, 10 ex

Description

Предлагаемое изобретение относится к области органической химии, в частности к новому способу получения циклических кетонов формулы (1):The present invention relates to the field of organic chemistry, in particular to a new method for producing cyclic ketones of the formula (1):

Figure 00000001
Figure 00000001

Предлагаемые соединения представляют интерес в качестве исходных синтонов для создания биологически активных соединений медицинского назначения, проявляющих противовирусные, противогрибковые, противоопухолевые, свойства ([1] S.F. Brady, М.P. Singh, J.Е. Janso, Clardy guanacastepene, a fungal-derived diterpene antibiotic with a new carbon skeleton. J. Am. Chem. Soc. 2000, 122, 2116-2117; [2] K.R. Gustafson, J.H. Cardellina, J.B. McMahon, RJ. Gulakowski, J. Ishitoya, Z. Szallasi, N.E. Lewin, P.M. Blumberg, O.S. Weislow, J.A. Beutler, R.W. Buckheit, G.M. Cragg, P.A. Cox, J.P. Bader, M.R. Boyd. A nonpromoting phorbol from the samoan medicinal plant homalanthus nutans inhibits cell killing by HIV-1. J. Med. Chem. 1992, 35, 1978-1986. [3] R. Wada, Y. Suto, M. Kanai, M. Shibasaki. Dramatic switching of protein kinase с agonist/antagonist activity by modifying the 12-ester side chain of phorbol esters. J. Am. Chem. Soc. 2002, 124, 10658-10659).The proposed compounds are of interest as starting synthons for the creation of biologically active compounds for medical purposes, exhibiting antiviral, antifungal, antitumor, properties ([1] SF Brady, P. P. Singh, J.E. Janso, Clardy guanacastepene, a fungal-derived diterpene antibiotic with a new carbon skeleton. J. Am. Chem. Soc. 2000, 122, 2116-2117; [2] KR Gustafson, JH Cardellina, JB McMahon, RJ. Gulakowski, J. Ishitoya, Z. Szallasi, NE Lewin , PM Blumberg, OS Weislow, JA Beutler, RW Buckheit, GM Cragg, PA Cox, JP Bader, MR Boyd. A nonpromoting phorbol from the samoan medicinal plant homalanthus nutans inhibits cell killing by HIV-1. J. Med. Chem. 1992 35, 1978-1986. [3] R. Wada, Y. Suto, M. Kanai, M. Shibasaki. Dramatic switchin g of protein kinase with agonist / antagonist activity by modifying the 12-ester side chain of phorbol esters. J. Am. Chem. Soc. 2002, 124, 10658-10659).

Известен способ ([4] Т. Hashimoto, Y. Naganawa, K. Maruoka. Stereoselective construction of seven-membered rings with an all-carbon quaternary center by direct Tiffeneau-Demjanov-type ring expansion. J. Am. Chem. Soc. 2009, 131, 6614-6617) получения циклических кетонов (2) путем взаимодействия циклогексанонов с α-замещенными диазоацетатами в присутствии эфирата трехфтористого бора в хлористом метилене в течение 30 минут при температуре -78°С с выходом 68-80%.A known method ([4] T. Hashimoto, Y. Naganawa, K. Maruoka. Stereoselective construction of seven-membered rings with an all-carbon quaternary center by direct Tiffeneau-Demjanov-type ring expansion. J. Am. Chem. Soc. 2009, 131, 6614-6617) for producing cyclic ketones (2) by reacting cyclohexanones with α-substituted diazoacetates in the presence of boron trifluoride etherate in methylene chloride for 30 minutes at a temperature of -78 ° C with a yield of 68-80%.

Figure 00000002
Figure 00000002

Известным способом не могут быть получены 2,3-диалкил-2-циклооктен-1-оны формулы (1).The 2,3-dialkyl-2-cycloocten-1-ones of the formula (1) cannot be obtained in a known manner.

Известен способ ([5] Y. Takada, K. Nomura, S. Matsubara. Preparation of a cycloheptane ring from a 1,2-diketone with high stereoselectivity. Org. Let. 2010, 12, 22, 5204-5205) получения циклических кетонов (4) реакцией 1,6-диалкилгекса-1,5-диен-3,4-дионов с бис(йодцинк)метаном в тетрагидрофуране в течение 3 часов при температуре -78°С с выходом 41-99%.A known method ([5] Y. Takada, K. Nomura, S. Matsubara. Preparation of a cycloheptane ring from a 1,2-diketone with high stereoselectivity. Org. Let. 2010, 12, 22, 5204-5205) to obtain cyclic ketones (4) by the reaction of 1,6-dialkylhexa-1,5-diene-3,4-dione with bis (iodzinc) methane in tetrahydrofuran for 3 hours at a temperature of -78 ° C with a yield of 41-99%.

Figure 00000003
Figure 00000003

Известным способом не могут быть получены 2,3-диалкил-2-циклооктен-1-оны формулы (1).The 2,3-dialkyl-2-cycloocten-1-ones of the formula (1) cannot be obtained in a known manner.

Известен способ ([6] Y. Kuninobu, A. Kawata, K. Takai. Efficient catalytic insertion of acetylenes into a carbon-carbon single bond of nonstrained cyclic compounds under mild conditions. J. Am. Chem. Soc. 2006, 128, 11368-11369) получения циклических кетонов (5) реакцией этил-2-оксоциклогексанкарбоксилата с терминальными ацетиленами в присутствии бензилизоцианида катализируемой комплексом [ReBr(CO)3(THF)]2 в течение 24 ч при температуре 40°С с выходом 86-99%.The known method ([6] Y. Kuninobu, A. Kawata, K. Takai. Efficient catalytic insertion of acetylenes into a carbon-carbon single bond of nonstrained cyclic compounds under mild conditions. J. Am. Chem. Soc. 2006, 128, 11368-11369) for the preparation of cyclic ketones (5) by reaction of ethyl 2-oxocyclohexanecarboxylate with terminal acetylenes in the presence of benzyl isocyanide catalyzed by the complex [ReBr (CO) 3 (THF)] 2 for 24 h at a temperature of 40 ° C with a yield of 86-99% .

Figure 00000004
Figure 00000004

Известным способом не могут быть получены 2,3-диалкил-2-циклооктен-1-оны формулы (1).The 2,3-dialkyl-2-cycloocten-1-ones of the formula (1) cannot be obtained in a known manner.

Предлагается новый способ получения 2,3-диалкил-2-циклооктен-1-онов формулы (1). Сущность способа заключается во взаимодействии дизамещенного ацетилена RC≡CR, где R=Pr или Bu с двойным избытком метилового эфира адипиновой кислоты и EtAlCl2 в присутствии магния (Mg, порошок) и катализатора Cp2TiCl2, взятых в мольном соотношении ацетилен: CH3CO2(СН2)4CO2CH3 : EtAlCl2 : Mg : Cp2TiCl2 = 10:20:(40-60):(40-60):(1.8-2.2), предпочтительно 10:20:50:50:2 ммоль. Реакцию проводят в тетрагидрофуране, в атмосфере аргона при температуре 60°С и атмосферном давлении. Время реакции 4-8 ч. Целевые продукты образуются в виде смеси 2,3-диалкил-2-циклооктен-1-онов (1) в соотношении 1:1 с общим выходом 59-83%. Реакция протекает по схеме:A new method is proposed for producing 2,3-dialkyl-2-cycloocten-1-ones of formula (1). The essence of the method consists in the interaction of disubstituted acetylene RC≡CR, where R = Pr or Bu with a double excess of adipic acid methyl ester and EtAlCl 2 in the presence of magnesium (Mg, powder) and a Cp 2 TiCl 2 catalyst taken in the molar ratio of acetylene: CH 3 CO 2 (CH 2 ) 4 CO 2 CH 3 : EtAlCl 2 : Mg: Cp 2 TiCl 2 = 10:20: (40-60) :( 40-60) :( 1.8-2.2), preferably 10:20:50 : 50: 2 mmol. The reaction is carried out in tetrahydrofuran, in an argon atmosphere at a temperature of 60 ° C and atmospheric pressure. The reaction time is 4-8 hours. The target products are formed as a mixture of 2,3-dialkyl-2-cycloocten-1-ones (1) in a 1: 1 ratio with a total yield of 59-83%. The reaction proceeds according to the scheme:

Figure 00000005
Figure 00000005

Целевые продукты (1) образуются только лишь с участием дизамещенных ацетиленов RC≡CR, этилалюминийдихлорида (EtAlCl2), метилового эфира адипиновой кислоты CH3CO2(СН2)4CO2CH3 и магния (акцептор ионов хлора). В присутствии других соединений алюминия (например, Et2AlCl, Et3Al, Bui 3Al, i-Bu2AlH), других эфиров (например простые эфиры, эфиры монокарбоновых кислот), других непредельных соединений (например, терминальные ацетилены, дизамещенные олефины) или других металлов (например Al, Cu, Fe) целевые продукты (1) не образуются.Target products (1) are formed only with the participation of RC-CR disubstituted acetylenes, ethyl aluminum dichloride (EtAlCl 2 ), adipic acid methyl ester CH 3 CO 2 (CH 2 ) 4 CO 2 CH 3 and magnesium (chlorine ion acceptor). In the presence of other aluminum compounds (e.g. Et 2 AlCl, Et 3 Al, Bu i 3 Al, i-Bu 2 AlH), other ethers (e.g. ethers, monocarboxylic acid esters), other unsaturated compounds (e.g., terminal acetylenes, disubstituted olefins) or other metals (e.g. Al, Cu, Fe), the target products (1) are not formed.

Изменение соотношения исходных реагентов в сторону увеличения их содержания по отношению к диалкилзамещенному ацетилену не приводит к существенному повышению выхода целевых продуктов (1). Снижение количества EtAlCl2, CH3CO2(CH2)4CO2CH3 или Mg по отношению к диалкилзамещенному ацетилену уменьшает выход 2,3-диалкил-2-циклооктен-1-онов (1).A change in the ratio of the starting reagents in the direction of increasing their content relative to dialkyl substituted acetylene does not lead to a significant increase in the yield of the target products (1). A decrease in the amount of EtAlCl 2 , CH 3 CO 2 (CH 2 ) 4 CO 2 CH 3 or Mg relative to the dialkyl substituted acetylene reduces the yield of 2,3-dialkyl-2-cycloocten-1-ones (1).

Проведение указанной реакции в присутствии катализатора Cp2TiCl2 больше 2.2 ммолей приводит к образованию побочных продуктов (гексазамещенных бензолов) и существенному уменьшению выхода целевых продуктов (1). Использование катализатора Cp2TiCl2 менее 1.8 ммолей снижает выход 2,3-диалкил-2-циклооктен-1-онов (1), что связано, возможно, со снижением каталитически активных центров в реакционной массе. Реакции проводили при температуре 60°С. При более высокой температуре (например, 80°С) увеличиваются энергозатраты на проведение процесса, а при меньшей температуре (например, 40°С) снижается скорость реакции.Carrying out this reaction in the presence of a catalyst Cp 2 TiCl 2 is greater than 2.2 mmol leads to the formation of by-products (geksazameschennyh benzenes) and a substantial decrease in the yield of the target products (1). The use of the catalyst Cp 2 TiCl 2 less than 1.8 mmol reduces the yield of 2,3-dialkyl-2-cycloocten-1-ones (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 60 ° C. At a higher temperature (for example, 80 ° C), the energy consumption for carrying out the process increases, and at a lower temperature (for example, 40 ° C), the reaction rate decreases.

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

В известном способе используются в качестве исходных реагентов терминальные ацетилены и этил-2-оксоциклогексанкарбоксилат. Предлагаемый способ базируется на использовании в качестве исходных реагентов диалкилацетиленов (RC≡CR), метилового эфира адипиновой кислоты CH3CO2(СН2)4СО2СН3 этилалюминийдихлорида, магния (Mg порошок) и катализатора Cp2TiCl2, взятых в мольном соотношении 10:20:50:40:2 ммоль.In the known method, terminal acetylenes and ethyl 2-oxocyclohexanecarboxylate are used as starting reagents. The proposed method is based on the use of dialkylacetylene (RC≡CR), adipic acid methyl ester CH 3 CO 2 (СН 2 ) 4 СО 2 СН 3 , ethyl aluminum dichloride, magnesium (Mg powder) and Cp 2 TiCl 2 catalyst taken in molar as starting reagents the ratio of 10: 20: 50: 40: 2 mmol.

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

ПРИМЕР 1. В стеклянный реактор, установленный на магнитной мешалке, при охлаждении до 0°С, в атмосфере аргона помещают 20 мл тетрагидрофурана, 7,1 мл (50 ммолей) EtAlCl2, 0,97 г (40 ммоль) магния, 0,5 г (2 ммоль) катализатора Cp2TiCl2. Перемешивают при 0°С в течение 1 ч, после чего добавляют 1,1 г (10 ммоль) окт-4-ина и 4,04 г (20 ммоль) диметилового эфира адипиновой кислоты CH3CO2(СН2)4CO2CH3. Реакционную массу нагревают с обратным холодильником до 60°С в течение 6 часов. Получают смесь 2,3-диалкил-2-циклооктен-1-онов в соотношении 1:1 с общим выходом 79%.EXAMPLE 1. In a glass reactor mounted on a magnetic stirrer, while cooling to 0 ° C, in an argon atmosphere, 20 ml of tetrahydrofuran, 7.1 ml (50 mmol) of EtAlCl 2 , 0.97 g (40 mmol) of magnesium, 0, 5 g (2 mmol) of Cp 2 TiCl 2 catalyst. Stir at 0 ° C for 1 hour, after which 1.1 g (10 mmol) oct-4-yne and 4.04 g (20 mmol) of dimethyl ester of adipic acid CH 3 CO 2 (CH 2) 4 CO 2 CH 3 . The reaction mass is heated under reflux to 60 ° C for 6 hours. A mixture of 2,3-dialkyl-2-cycloocten-1-ones is obtained in a 1: 1 ratio with a total yield of 79%.

Спектральные характеристики 2,3-дипропил-2-циклооктен-1-онов (1а).Spectral characteristics of 2,3-dipropyl-2-cycloocten-1-ones (1a).

Figure 00000006
Figure 00000006

Спектр ЯМР 1Н, CDCl3, δ, м.д.: 0.90-0.95 (м, 6Н, СН3), 1.28-1.48 (м, 6Н, СН2), 1.71-1.79 (м, 2Н, СН2), 1.85-1.92 (м, 2Н, СН2), 2.05-2.09 (м, 2Н, СН2), 2.21-2.26 (м, 2Н, СН2), 2.41 (т, J=6 Гц, 2Н, СН2), 2.49 (т, J=6.0 Гц, 2Н, СН2). Спектр ЯМР 13С, δ, м.д.: 13.98, 14.35, 14.44, 21.54, 22.47, 23.03, 23.09, 25.24, 25.31, 29.96, 29.99, 30.45, 31.47, 32.80, 33.75, 35.13, 36.00, 43.32, 133.42, 148.25, 205.44. ИК: 1742, 1673, 2951, 2930, 2873, 1462. Масс-спектр, m/z: 208 (М+). Вычислено, (%): С 80.71; Н 11.61, C14H24O. Найдено: С 80.46; Н 11.48. Удвоение сигналов в спектре ЯМР 13С связано с наличием конформеров с различным положением кетогруппы относительно плоскости двойной связи. 1 H NMR, CDCl 3, δ, ppm .: 0.90-0.95 (m, 6H, CH 3), 1.28-1.48 (m, 6H, CH2), 1.71-1.79 (m, 2H, CH 2) , 1.85-1.92 (m, 2Н, СН 2 ), 2.05-2.09 (m, 2Н, СН 2 ), 2.21-2.26 (m, 2Н, СН 2 ), 2.41 (t, J = 6 Hz, 2Н, СН 2) ), 2.49 (t, J = 6.0 Hz, 2H, CH 2 ). 13 C NMR spectrum, δ, ppm: 13.98, 14.35, 14.44, 21.54, 22.47, 23.03, 23.09, 25.24, 25.31, 29.96, 29.99, 30.45, 31.47, 32.80, 33.75, 35.13, 36.00, 43.32, 133.42, 148.25, 205.44. IR: 1742, 1673, 2951, 2930, 2873, 1462. Mass spectrum, m / z: 208 (M + ). Calculated, (%): C 80.71; H, 11.61, C 14 H 24 O. Found: C, 80.46; H, 11.48. Doubling of signals in the 13 C NMR spectrum is associated with the presence of conformers with different positions of the keto group relative to the double bond plane.

ПРИМЕР 2. Аналогично примеру 1, но в качестве ацетиленового производного используется дец-5-ин.EXAMPLE 2. Analogously to example 1, but dec-5-in is used as the acetylene derivative.

Спектральные характеристики 2,3-дибутил-2-циклооктен-1-онов (1б).Spectral characteristics of 2,3-dibutyl-2-cycloocten-1-ones (1b).

Figure 00000007
Figure 00000007

Спектр ЯМР 1Н, CDCl3, δ, м.д.: 0.89-0.95 (м, 6Н, СН3), 1.26-1.46 (м, 10Н, СН2), 1.70-1.82 (м, 2Н, СН2), 1.80-1.96 (м, 2Н, СН2), 2.05-2.10 (м, 2Н, СН2), 2.21-2.28 (м, 2Н, СН2), 2.41 (т, J=6.8 Гц, 2Н, СН2), 2.48 (т, J=6.8 Гц, 2Н, СН2). Спектр ЯМР 13С, δ, м.д.: 14.00, 14.03, 22.45, 22.54, 23.06, 23.09, 25.20, 25.29, 27.84, 27.95, 30.63, 30.93, 32.70, 32.85, 33.07, 33.78, 34.00, 43.27, 133.17, 148.84, 206.02. Масс-спектр: m/z 236 [М]+. Вычислено, (%): С 81.29; Н 11.94, C16H28O. Найдено, (%): С 81.11; Н 11.82. 1 H NMR, CDCl 3, δ, ppm .: 0.89-0.95 (m, 6H, CH 3), 1.26-1.46 (m, 10H, CH2), 1.70-1.82 (m, 2H, CH 2) , 1.80-1.96 (m, 2Н, СН 2 ), 2.05-2.10 (m, 2Н, СН 2 ), 2.21-2.28 (m, 2Н, СН 2 ), 2.41 (t, J = 6.8 Hz, 2Н, СН 2) ), 2.48 (t, J = 6.8 Hz, 2H, CH 2 ). 13 C NMR spectrum, δ, ppm: 14.00, 14.03, 22.45, 22.54, 23.06, 23.09, 25.20, 25.29, 27.84, 27.95, 30.63, 30.93, 32.70, 32.85, 33.07, 33.78, 34.00, 43.27, 133.17, 148.84, 206.02. Mass spectrum: m / z 236 [M] + . Calculated, (%): C 81.29; H 11.94, C 16 H 28 O. Found, (%): C 81.11; H, 11.82.

Удвоение сигналов в спектре ЯМР 13С связано с наличием конформеров с различным положением кетогруппы относительно плоскости двойной связи. Другие примеры, подтверждающие способ, приведены в табл. 1.Doubling of signals in the 13 C NMR spectrum is associated with the presence of conformers with different positions of the keto group relative to the double bond plane. Other examples confirming the method are given in table. one.

Figure 00000008
Figure 00000008

Реакции проводили при температуре 60°C в тетрагидрофуране.Reactions were carried out at a temperature of 60 ° C in tetrahydrofuran.

Claims (3)

Способ получения 2,3-диалкил-2-циклооктен-1-онов общей формулы (1):The method of obtaining 2,3-dialkyl-2-cycloocten-1-ones of the general formula (1):
Figure 00000009
Figure 00000009
 характеризующийся тем, что диалкилацетилены общей формулы R-C≡C-R, где R=С3Н7 или С4Н9, подвергают взаимодействию с двукратным избытком метилового эфира адипиновой кислоты CH3CO2(СН2)4СО2СН3 и EtAlCl2 в присутствии магния (Mg, порошок) и катализатора Cp2TiCl2, реакцию проводят при мольном соотношении RC≡CR : CH3CO2(СН2)4СО2СН3 : EtAlCl2 : Mg : Cp2TiCl2=10:20:(40-60):(40-60):(1.8-2.2), в тетрагидрофуране в атмосфере аргона при 60°С и атмосферном давлении в течение 4-8 ч.characterized in that the dialkylacetylenes of the general formula RC≡CR, where R = C 3 H 7 or C 4 H 9 , are reacted with a twofold excess of adipic acid methyl ester CH 3 CO 2 (CH 2 ) 4 CO 2 CH 3 and EtAlCl 2 in in the presence of magnesium (Mg, powder) and a Cp 2 TiCl 2 catalyst, the reaction is carried out at a molar ratio of RC≡CR: CH 3 CO 2 (CH 2 ) 4 CO 2 CH 3 : EtAlCl 2 : Mg: Cp 2 TiCl 2 = 10: 20 : (40-60) :( 40-60) :( 1.8-2.2), in tetrahydrofuran in an argon atmosphere at 60 ° C and atmospheric pressure for 4-8 hours.
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US8940940B2 (en) * 2012-06-13 2015-01-27 Basf Se Process for preparing macrocyclic ketones
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