RU2151772C1 - Method of preparing 1-alkoxy (or dialkylamino)-2,3- diphenyl(alkyl)alumacyclopropenes - Google Patents

Abstract

FIELD: chemical industry. SUBSTANCE: described is method of preparing 1- alkoxy (or dialkylamino)-2,3- diphenyl(alkyl)alumacyclopropene of general formula I:

wherein R is OEt, OBu, NEt₂,

, R¹ is Ph, C₃H₇, C₄H₉. Said method comprises reacting alkoxy (or dialkylamino)aluminium chloride RAlCl₂ with disubstituted acetylene R¹-≡-R¹ and magnesium at (10-12): (1-12) ratio respectively in the presence of titanocene dichloride ((Cp₂TiO₂)), and process is carried out in argon atmosphere under normal conditions in tetrahydrofuran for 10-14 h. Said method make it possible to prepare new 1-alkoxy (or dialkylamino)-2,3-diphenyl(alkyl) alumacyclopentanes having high regioselectivity. EFFECT: more efficient preparation method. 14 ex, 1 tbl

Description

где R представляет OEt, OBu, NEt₂,N,
R' представляет Ph, C₃H₇, C₄H₉.The present invention relates to the field of organic synthesis, methods for producing new organoaluminum compounds, and specifically to a method for producing 1-alkoxy (or dialkylamino) -2,3-phenyl (alkyl) - alumacyclopropenes of the general formula (I):

where R represents OEt, OBu, NEt ₂ , N,
R 'represents Ph, C ₃ H ₇ , C ₄ H ₉ .

 The proposed method can find application in fine organic as well as organometallic synthesis.

где X представляет OCH₃, NEt₂, SC₄H₉, реакцией триэтилалюминия с функциональным N-, О-, S- содержащими 2,7-октадиенами в присутствии биметаллического катализатора (Cp₂ZrCl₂ + i-Bu₂AlH) при комнатной температуре за 8-12 часов с выходом 80-96% по схеме

где X представляет OCH₃, OH, NEt₂, SC₄H₉.The known method (Dzhemilev U.M. et al. Regioselective synthesis of α-substituted aluminacyclopentanes by cyclic metal β-olefins using Et ₃ Al in the presence of Cp ₂ ZrCl _2. - Izv. AN SSSR, chemical series, 1990, N 12, S. 2831 -41) obtaining monosubstituted N-, O-, S- containing aluminacyclopentanes of the general formula

where X represents OCH ₃ , NEt ₂ , SC ₄ H ₉ , by the reaction of triethylaluminum with functional N-, O-, S- containing 2,7-octadiene in the presence of a bimetallic catalyst (Cp ₂ ZrCl ₂ + i-Bu ₂ AlH) at room temperature for 8-12 hours with an output of 80-96% according to the scheme

where X represents OCH ₃ , OH, NEt ₂ , SC ₄ H ₉ .

 In a known manner it is possible to obtain only monosubstituted aluminacyclopentanes containing heteroatoms (N, O, S) in the side chain. It is not possible to synthesize 1-alkoxy (or dialkylamino) -2,3-phenyl (alkyl) -alumacyclopropenes in a known manner.

где R представляет C₃H₇, C₅H₁₁, C₈H₁₇; R' = OEt, NEt₂,
реакцией α-олефинов (1-октен, 1-гексен, 1-ундецен) с соответствующими дигалогенидами алюминия (EtO-AlCl₂, Et₂N-AlCl₂) в присутствии металлического магния (Mg) и катализатора (5 мол.%) Cp₂ZrCl₂ при комнатной температуре 20-25^oC за 6-8 часов в ТТФ с выходом 70-85%.A known method (DZHEMILEV UM et.al, Mendeleev Commun., 1992, N 2, pp. 26-8) for producing 1-alkoxy (or dialkylamino) -trans-3,4-dialkyl-substituted aluminacyclopentanes of the general formula:

where R represents C ₃ H ₇ , C ₅ H ₁₁ , C ₈ H ₁₇ ; R '= OEt, NEt ₂ ,
the reaction of α-olefins (1-octene, 1-hexene, 1-undecene) with the corresponding aluminum dihalides (EtO-AlCl ₂ , Et ₂ N-AlCl ₂ ) in the presence of magnesium metal (Mg) and a catalyst (5 mol%) Cp ₂ ZrCl ₂ at room temperature 20-25 ^o C for 6-8 hours in TTF with a yield of 70-85%.

R представляет C₃H₇, C₅H₁₁, C₈H₁₇, R' представляет OEt, NEt₂
Известным способом можно получить лишь транс-3,4-дизамещенные алюмациклопентаны. Синтезировать 1-алкокси (или диалкиламино)- 2,3-дифенил(алкил)-алюмациклопропены известным способом не представляется возможным.

R represents C ₃ H ₇ , C ₅ H ₁₁ , C ₈ H ₁₇ , R 'represents OEt, NEt ₂
In a known manner, only trans-3,4-disubstituted aluminacyclopentanes can be obtained. It is not possible to synthesize 1-alkoxy (or dialkylamino) - 2,3-diphenyl (alkyl) -alumacyclopropenes in a known manner.

 Thus, in the literature there is absolutely no information on the regioselective synthesis of N- and O-containing aluminacyclopronenes, namely, 1-alkoxy (or dialkylamino) -2,3-diphenyl (alkyl) -aluminocyclopropenes.

 A new method for the regioselective synthesis of new types of higher organoaluminum compounds, namely 1-alkoxy (or dialkylamino) -2,3-diphenyl (alkyl) -alumacyclopropenes, is proposed.

NEt₂, с дизамещенными ацетиленами (дифенилацетилен, октин-4, децин-5) и магнием (порошок), взятых в мольном соотношении RAlCl₂: R′-≡-R′; Mg, равном (10-12):1:(10-12), преимущественно 11:1:11, в присутствии катализатора титаноцендихлорида (Cp₂T:Cl₂) в количестве 2-5 мол.% по отношению к дизамещенному ацетилену, предпочтительно 3 мол.%, в атмосфере аргона при комнатной температуре (23-25^oC) и нормальном давлении в ТГФ. Время реакции 10-14 часов. Выход целевых продуктов 74-90%.This goal is achieved by the interaction of alkoxy - or dialkylaminoaluminium dichlorides of the General formula RAlCl ₂ , where R represents OEt, OBu,

NEt ₂ , with disubstituted acetylenes (diphenylacetylene, octin-4, decin-5) and magnesium (powder), taken in a molar ratio of RAlCl ₂ : R′-≡-R ′; Mg equal to (10-12): 1: (10-12), mainly 11: 1: 11, in the presence of a titanocene dichloride catalyst (Cp ₂ T: Cl ₂ ) in an amount of 2-5 mol.% With respect to disubstituted acetylene, preferably 3 mol%, in an argon atmosphere at room temperature (23-25 ^° C.) and normal pressure in THF. The reaction time is 10-14 hours. The yield of target products 74-90%.

R представляет OEt, OBu,

NEt₂, R' представляет Ph, C₃H₇, C₄H₉>
1-алкокси (или диалкиламино)-2,3-дифенил-(алкил)- алюмоциклопропены образуются только лишь с участием алкоксидов или амидов алюминия под действием катализатора Cp₂TiCl₂. В присутствии других соединений алюминия (например, i-Bu₂AlH, i-Bu₃Al, i-Bu₂AlCl, AlEt₂Cl, AlEt₃, или другого катализатора (например, Cp₂ZrCl₂, TiCl₄, Ti(OBu)₄, ZrCl₄, Zr(acac)₄, Zr(OBu)₄) целевые продукты не образуются.The reaction proceeds according to the scheme:

R represents OEt, OBu,

NEt ₂ , R 'represents Ph, C ₃ H ₇ , C ₄ H ₉ >
1-alkoxy (or dialkylamino) -2,3-diphenyl- (alkyl) - alumocyclopropenes are formed only with the participation of aluminum alkoxides or amides under the influence of the catalyst Cp ₂ TiCl ₂ . In the presence of other aluminum compounds (e.g. i-Bu ₂ AlH, i-Bu ₃ Al, i-Bu ₂ AlCl, AlEt ₂ Cl, AlEt ₃ , or another catalyst (e.g. Cp ₂ ZrCl ₂ , TiCl ₄ , Ti (OBu ) ₄ , ZrCl ₄ , Zr (acac) ₄ , Zr (OBu) ₄ ) the target products are not formed.

Carrying out the specified reaction in the presence of Cp ₂ TiCl ₂ more than 5 mol.% Does not lead to a significant increase in the yield of the target products. The use of a catalyst of less than 2 mol.% Reduces the yield of 1-alkoxy (or dialkylamino) -2,3-diphenyl (alkyl) aluminocyclopropenes, which is apparently associated with a decrease in active centers in the reaction mass. The experiments were carried out at room temperature (23-25 ^o C). At a higher temperature, the content of compaction products increases, and at a lower temperature (for example, 0 ^° ), the reaction rate decreases.

 Changing the ratio of the starting reagents in the direction of increasing the content of alkoxy- or dialkylaminoaluminium dichlorides or Mg with respect to disubstituted acetylene does not significantly increase the yield of the target product. A decrease in the starting reagents with respect to disubstituted acetylenes reduces the yield of the target products.

 Significant differences of the proposed method.

и цирконийсодержащий катализатор (Cp₂ZrCl₂).The proposed method uses disubstituted acetylenes (R-≡-R) and a Cp ₂ TiCl ₂ catalyst. In the known method, α-olefins are used

and zirconium-containing catalyst (Cp ₂ ZrCl ₂ ).

 The proposed method has the following advantages.

1. The method allows to obtain with high regioselectivity 1-alkoxy (or dialkylamino) -2,3-diphenyl (alkyl) -alumacyclopropenes, the synthesis of which is not described in the literature,
The method is illustrated by the following examples.

Спектральные характеристики цис-стильбена (II): ИК-спектр (ν, см^-1): 3030, 1600, 1450, 1380, 1090, 980, 780, 710. Спектр ПМР (δ, м.д.): 6.57c (2H, CH=CH), 7,12-7,57 м (10H, Ph) М⁺ 180.Example 1. In a 50 ml glass reactor mounted on a magnetic stirrer in an argon atmosphere at a temperature of -5 ^° C., 15 ml of THF, 11 mmol of ethoxyaluminium dichloride (EtOAlCl ₂ ), 10 mmol of diphenylacetylene, 0.3 mmol of Cp ₂ TiCl ₂ and 11 were placed mmol of magnesium (powder), the temperature was brought to room temperature (23-25 ^o C) and stirred for 12 hours. Individual 1-ethoxy-2,3-diphenylaluminacyclopropene is obtained. The yield of the target product was determined by the hydrolysis product (84%). Upon hydrolysis of 1-ethoxy-2,3-diphenyl aluminacyclopropene, cis-stilbene (II) is formed, and during deuterolysis, respectively, 1,2-didi theostilbene (III) according to the scheme

Spectral characteristics of cis-stilbene (II): IR spectrum (ν, cm ^-1 ): 3030, 1600, 1450, 1380, 1090, 980, 780, 710. PMR spectrum (δ, ppm): 6.57c ( 2H, CH = CH), 7.12-7.57 m (10H, Ph) M ⁺ 180.

Spectral characteristics of 1,2-dideuterostilbene (III): IR spectrum (ν, cm ^-1 ): 3080, 3030. 2240, 1950, 1600, 1500, 1440, 1180, 1150, 1070, 1020, 920, 750, 690, 540. 1 H-NMR spectrum (δ, ppm): 7.21 s (10H, Ph). ¹³ C NMR spectrum (δ, ppm): 130.8t (C'-D, J = 23 Hz), 137.09c (C ² ), 128.13 d (C ³ ), 128.82 d (C ⁴ ), 127.04 d (C ⁵ ). M ⁺ 182.

 Other examples confirming this method are shown in the table.

 Reactions were carried out at room temperature in THF. The increase is impractical, since there is no significant increase in the yield of the target product. At lower temperatures, the reaction rate decreases.

Claims (1)

The method of obtaining 1-alkoxy (or dialkylamino) -2,3-diphenyl (alkyl) -alumacyclopropenes of the General formula

where R represents Oet, OBu, Net ₂ ,

;
R 'represents Ph, C ₃ H ₇ , C ₄ H ₉ ,
characterized in that the alkoxy or dialkylaminoaluminium dichloride of the general formula
RAlCl ₂ ,
where R represents Oet, OBu, Net ₂ ,

,
interacts with disubstituted acetylene of the general formula
R′-≡-R ′
and magnesium, taken in a molar ratio, respectively, of RAlCl ₂ : R′-≡-R ′: Mg, equal to (10-12): 1: (1-12), in the presence of a catalyst of titanocene dichloride (Cp ₂ TiCl ₂ ) in an amount of 2 - 5 mol% with respect to disubstituted acetylene and the process is carried out in an argon atmosphere under normal conditions in tetrahydrofuran medium for 10-14 hours.

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