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RU2192424C1 - Method of synthesis of optically active dimeric complexes of (1s,2s)-1,7,7-trimethyl-2-[(dialkyl-alumina)oxy]- bicyclo[2,2,1]heptanes - Google Patents

Method of synthesis of optically active dimeric complexes of (1s,2s)-1,7,7-trimethyl-2-[(dialkyl-alumina)oxy]- bicyclo[2,2,1]heptanes Download PDF

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RU2192424C1
RU2192424C1 RU2001109192A RU2001109192A RU2192424C1 RU 2192424 C1 RU2192424 C1 RU 2192424C1 RU 2001109192 A RU2001109192 A RU 2001109192A RU 2001109192 A RU2001109192 A RU 2001109192A RU 2192424 C1 RU2192424 C1 RU 2192424C1
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bicyclo
trimethyl
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У.М. Джемилев
Л.В. Парфенова
Л.М. Халилов
Ф.Г. Валямова
С.В. Иванова
Е.В. Никитина
Л.О. Хафизова
А.Г. Ибрагимов
И.П. Белецкая
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Институт нефтехимии и катализа АН РБ и УНЦ РАН
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Abstract

FIELD: organic chemistry, chemical technology. SUBSTANCE: invention relates to method of synthesis of optically active dimeric complexes of (1S, 2S)-1,7,7- trimethyl-2-[(dialkylalumina)oxy] -bicyclo[2.2.1]heptanes of the general formula (I)
Figure 00000002
where R means C2H5, n-C3H7, i-C4H9 that involves interaction of (1S,2S)-1,7,7-trimethylbicyclo[2.2.1]heptane-2- one (camphor) with aluminum dialkylhydrides HAlR2 where R is given above taken in the mole ratio = 10 : (10-12), respectively, in argon atmosphere, at the room temperature (~ 20 C), under normal pressure, in benzene medium for 0.5-1.5 h. New compounds can be used in fine organic and organometallic synthesis, in part, for synthesis of pure enantiomeric products with high optical yields. EFFECT: improved method of synthesis, enhanced purity, increased yield. 1 tbl

Description

Изобретение относится к способам получения новых производных алюминия, конкретно к способу получения оптически активных димерных комплексов (1S, 2S)-1,7,7-триметил-2-[(диалкилалюмина)окси] бицикло[2.2.1] гептанов общей формулы (I):

Figure 00000003

где R = С2Н5, н-С3Н7, i-С4Н9.The invention relates to methods for producing new derivatives of aluminum, specifically to a method for producing optically active dimeric complexes (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylalumin) oxy] bicyclo [2.2.1] heptanes of the general formula (I ):
Figure 00000003

where R = C 2 H 5 , nC 3 H 7 , i-C 4 H 9 .

Предлагаемый способ может найти применение в тонком органическом и металлорганическом синтезе, в частности при получении энантиомерно чистых продуктов с высокими оптическими выходами. The proposed method can find application in fine organic and organometallic synthesis, in particular in the production of enantiomerically pure products with high optical yields.

Известен способ ([1] G. Giacomelli, L. Bertero, L. Lardicci. Nickel Catalyzed Stereodifferentiating Displacement Reaction Between Prochiral 1 - Alkenes and Optically Active Organoaluminium Solvates// Tetrahedron Lett., v. 22, 1981, p. 883-886) получения оптически активных алюминийорганических соединений (2) взаимодействием дизамещенных терминальных алкенов с триизобутилалюминием в присутствии Ni-содержащих катализаторов и хиральных лигандов при комнатной температуре в течение 40 ч по схеме 1 (см. в конце описания). The known method ([1] G. Giacomelli, L. Bertero, L. Lardicci. Nickel Catalyzed Stereodifferentiating Displacement Reaction Between Prochiral 1 - Alkenes and Optically Active Organoaluminium Solvates // Tetrahedron Lett., V. 22, 1981, p. 883-886 ) obtaining optically active organoaluminum compounds (2) by reacting disubstituted terminal alkenes with triisobutylaluminum in the presence of Ni-containing catalysts and chiral ligands at room temperature for 40 hours according to Scheme 1 (see the end of the description).

Известным способом не могут быть получены оптически активные димерные комплексы (1S,2S)-1,7,7-триметил-2-[(диалкилалюмина)окси]бицикло[2.2.1]гептанов (1). In a known manner, optically active dimeric complexes of (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylalumin) oxy] bicyclo [2.2.1] heptanes (1) cannot be obtained.

Известен способ ([2] M.L. Sierra, R. Kumar, V. Srini, J. Mel, J.P. Oliver. Synthesis and Spectroscopic Investigations of Alkylaluminium Alkoxides Derived from Optically Active Alcohols// Organometallics, v. l1, 1992, р. 206-214) получения оптически активных алкоксидов алюминия (3) взаимодействием триалкилаланов с оптически активным спиртом при комнатной температуре по схеме 2 (см. в конце описания). The known method ([2] ML Sierra, R. Kumar, V. Srini, J. Mel, JP Oliver. Synthesis and Spectroscopic Investigations of Alkylaluminium Alkoxides Derived from Optically Active Alcohols // Organometallics, v. L1, 1992, p. 206- 214) obtaining optically active aluminum alkoxides (3) by the interaction of trialkylalanes with optically active alcohol at room temperature according to Scheme 2 (see the end of the description).

Известный способ не позволяет получать оптически активные димерные комплексы (1S,2S)-1,7,7-триметил-2-[(диалкилалюмина)окси]бицикло[2.2.1]гептанов (1). The known method does not allow to obtain optically active dimeric complexes of (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylalumin) oxy] bicyclo [2.2.1] heptanes (1).

Таким образом, в литературе совершенно отсутствуют сведения по региоселективному синтезу оптически активных димерных комплексов (1S,2S)-1,7,7-триметил-2-[(диалкилалюмина)окси]бицикло[2.2.1] гептанов (1). Thus, in the literature there is absolutely no information on the regioselective synthesis of optically active dimeric complexes (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylalumin) oxy] bicyclo [2.2.1] heptanes (1).

Предлагается способ получения новых типов оптически активных алюминийорганических соединений, а именно, димерных комплексов (1S,2S)-1,7,7-триметил-2-[(диалкилалюмина)окси]бицикло[2.2.1]гептанов (1). A method is proposed for producing new types of optically active organoaluminum compounds, namely, dimeric complexes (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylalumin) oxy] bicyclo [2.2.1] heptanes (1).

Предлагаемый способ осуществляется взаимодействием (1S,2S)-1,7,7-триметил-бицикло[2.2.1]гептан-2-она (камфоры) с диалкилгидридами алюминия НАlR2 (R = С2Н5, н-С3Н7, i-C4H9), взятыми в мольном соотношении 10:(10-12), предпочтительно 10:11, в атмосфере аргона при комнатной температуре (~20oС) и нормальном давлении в бензоле. Время реакции 0,5-1,5 ч, предпочтительно 1 ч. Выход димерных комплексов (1S,2S)-1,7,7-триметил-2-[(диалкилалюмина)окси] бицикло[2.2.1] гептанов 82-98%. Реакция протекает по схеме 3 (см. в конце описания).The proposed method is carried out by the interaction of (1S, 2S) -1,7,7-trimethyl-bicyclo [2.2.1] heptan-2-one (camphor) with dialkylhydrides of aluminum HAlR 2 (R = C 2 H 5 , n-C 3 N 7 , iC 4 H 9 ), taken in a molar ratio of 10: (10-12), preferably 10:11, in an argon atmosphere at room temperature (~ 20 ° C) and normal pressure in benzene. The reaction time is 0.5-1.5 hours, preferably 1 hour. The yield of dimer complexes (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylaluminium) oxy] bicyclo [2.2.1] heptanes 82-98 % The reaction proceeds according to scheme 3 (see the end of the description).

Оптически активные димерные комплексы (1S, 2S)-1,7,7-триметил-2-[(диалкилалюмина)окси] бицикло[2.2.1] гептанов (1) образуются только лишь с участием (1S,2S)-1,7,7-триметил-бицикло[2.2.1]гептан-2-она и диалкилгидридов алюминия HAlR2. В присутствии других хиральных кетонов или других соединений алюминия (например, АlЕt3, АlВui3, Et2AlCl, EtAlCl2) целевые продукты (1) не образуются.Optically active dimeric complexes (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylalumin) oxy] bicyclo [2.2.1] heptanes (1) are formed only with the participation of (1S, 2S) -1,7 , 7-trimethyl-bicyclo [2.2.1] heptan-2-one and aluminum dialkyl hydrides HAlR 2 . In the presence of other chiral ketones or other aluminum compounds (e.g. AlEt 3 , AlBu i 3 , Et 2 AlCl, EtAlCl 2 ), the desired products (1) are not formed.

Изменение соотношения исходных реагентов в сторону увеличения содержания HAlR2 по отношению к камфоре не приводит к дальнейшему повышению выхода целевых продуктов (1). Синтезы осуществляли при комнатной температуре (~ 20oС). При более высокой температуре (например, 40oС) не наблюдается увеличение выхода целевых продуктов, а при меньшей температуре (например, 0oС) снижается скорость реакции.A change in the ratio of the starting reagents in the direction of increasing the HAlR 2 content with respect to camphor does not lead to a further increase in the yield of the target products (1). The syntheses were carried out at room temperature (~ 20 o C). At a higher temperature (for example, 40 o C) there is no increase in the yield of the target products, and at a lower temperature (for example, 0 o C) the reaction rate decreases.

Существенные отличия предлагаемого способа:
1. В предлагаемом способе используются в качестве исходных реагентов диалкилалюминийгидриды (HAlR2) и оптически активный кетон (камфора). В известном способе применяются в качестве исходных реагентов триалкилаланы (AlR3) и оптически активный спирт.
Significant differences of the proposed method:
1. In the proposed method, dialkylaluminum hydrides (HAlR 2 ) and optically active ketone (camphor) are used as starting reagents. In the known method, trialkylalanes (AlR 3 ) and optically active alcohol are used as starting reagents.

Предлагаемый способ обладает следующими преимуществами:
1. Способ позволяет получать с высокой региоселективностью оптически активные димерные комплексы (1S,2S)-1,7,7-триметил-2-[(диалкилалюмина)окси]бицикло[2.2.1]гептанов (1), синтез которых в литературе не описан.
The proposed method has the following advantages:
1. The method allows to obtain with high regioselectivity optically active dimeric complexes (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylaluminium) oxy] bicyclo [2.2.1] heptanes (1), the synthesis of which is not available in the literature described.

Способ поясняется следующими примерами:
Пример 1. В стеклянный реактор объемом 50 мл, установленный на магнитной мешалке, в атмосфере аргона помещают 11 ммолей HAl(i-Bu)2 в 9 мл С6Н6. К данной смеси небольшими порциями добавляют 10 ммолей (1S,2S)-1,7,7-триметил-бицикло[2.2.1] гептан-2-она(камфора), перемешивают 1 ч при комнатной температуре (~20oС). Получают димер (1S,2S)-1,7,7-триметил-2-[(диизобутилалюмина)окси] бицикло[2.2.1] гептана с выходом 94%. [α] 20 D = +26,94o.
The method is illustrated by the following examples:
Example 1. In a 50 ml glass reactor mounted on a magnetic stirrer, 11 mmol of HAl (i-Bu) 2 in 9 ml of C 6 H 6 are placed in an argon atmosphere. To this mixture, 10 mmoles of (1S, 2S) -1,7,7-trimethyl-bicyclo [2.2.1] heptan-2-one (camphor) are added in small portions, stirred for 1 h at room temperature (~ 20 ° C). A dimer of (1S, 2S) -1,7,7-trimethyl-2 - [(diisobutylaluminium) oxy] bicyclo [2.2.1] heptane is obtained in a yield of 94%. [α] 20 D = +26.94 o .

Спектр ЯМР 13С димера (1S,2S)-1,7,7-триметил-2-[(диизобутилалюмина)окси] бицикло[2.2.1]гептана (δ, м.д., 22,5 МГц, С6D6):

Figure 00000004

Другие примеры, подтверждающие способ, приведены в табл. 1. 13 C NMR spectrum of (1S, 2S) -1,7,7-trimethyl-2 - [(diisobutylaluminium) oxy] bicyclo [2.2.1] heptane dimer (δ, ppm, 22.5 MHz, C 6 D 6 ):
Figure 00000004

Other examples confirming the method are given in table. 1.

Claims (1)

Способ получения оптически активных димерных комплексов (1S, 2S)-1,7,7-триметил-2-[(диалкилалюмина)окси] -бицикло[2.2.1] гептанов общей формулы I (см. графическую часть),
где R= С2Н5, н-С3Н7, i-C4H9,
отличающийся тем, что (1S, 2S)-1,7,7-триметилбицикло[2.2.1] гептан-2-он (камфора) взаимодействует с диалкилгидридами алюминия HAlR2, R определено выше, при мольном соотношении 10: (10-12) в атмосфере аргона при комнатной температуре (~ 20oC) и нормальном давлении в среде бензола в течение 0,5 - 1,5 ч.
A method of obtaining optically active dimeric complexes of (1S, 2S) -1,7,7-trimethyl-2 - [(dialkylalumin) oxy] -bicyclo [2.2.1] heptanes of the general formula I (see graphic part),
where R = C 2 H 5 , nC 3 H 7 , iC 4 H 9 ,
characterized in that (1S, 2S) -1,7,7-trimethylbicyclo [2.2.1] heptan-2-one (camphor) interacts with aluminum dialkyl hydrides HAlR 2 , R as defined above, with a molar ratio of 10: (10-12 ) in an argon atmosphere at room temperature (~ 20 o C) and normal pressure in benzene for 0.5 to 1.5 hours
RU2001109192A 2001-04-05 2001-04-05 Method of synthesis of optically active dimeric complexes of (1s,2s)-1,7,7-trimethyl-2-[(dialkyl-alumina)oxy]- bicyclo[2,2,1]heptanes RU2192424C1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2373212C2 (en) * 2007-10-23 2009-11-20 Институт нефтехимии и катализа РАН Method of producing optically active (1r,2s,5r)-[[5-methyl-2-(1-methylethyl)cyclohexyl]oxy] dichloralane

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EP0342444A2 (en) * 1988-05-19 1989-11-23 MERCK PATENT GmbH Cyclical organic-metal compounds
RU2079499C1 (en) * 1994-11-22 1997-05-20 Институт общей и неорганической химии им.Н.С.Курнакова РАН Method for production of complex compound of aluminium with tetra-crawn-phthalocyanine
RU2139880C1 (en) * 1998-04-30 1999-10-20 Институт нефтехимии и катализа АН Республики Башкортостан Method of preparing 2-chloro-2-alumabicyclo [3,2,2,] nonane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342444A2 (en) * 1988-05-19 1989-11-23 MERCK PATENT GmbH Cyclical organic-metal compounds
RU2079499C1 (en) * 1994-11-22 1997-05-20 Институт общей и неорганической химии им.Н.С.Курнакова РАН Method for production of complex compound of aluminium with tetra-crawn-phthalocyanine
RU2139880C1 (en) * 1998-04-30 1999-10-20 Институт нефтехимии и катализа АН Республики Башкортостан Method of preparing 2-chloro-2-alumabicyclo [3,2,2,] nonane

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2373212C2 (en) * 2007-10-23 2009-11-20 Институт нефтехимии и катализа РАН Method of producing optically active (1r,2s,5r)-[[5-methyl-2-(1-methylethyl)cyclohexyl]oxy] dichloralane

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