RU2213745C1 - Method for preparing 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alkylidenecyclohepta-2-oxalanes - Google Patents

Abstract

FIELD: organic chemistry, chemical technology. SUBSTANCE: invention relates to method for preparing a novel organoaluminum compound. Invention describes method for preparing 1-ethyl-3-methyl-3-phenyl-(ethyl-, cyclopropyl-)-4-alkylidenecyclohepta-2- oxalane by interaction of terminal allene with triethylaluminium in the presence of CpZrCl₂ as catalyst, in argon medium, in CH₂Cl₂ with CuCl and CH₃RCO wherein R is Ph, C₂H₅ and cyclo-C₃H₅. Invention provides preparing the novel compound with high regioselectivity. New compound can be used in fine organic synthesis and as co- catalysts in oligo- and polymerization of olefins and coupled dienes. EFFECT: improved preparing method. 1 tbl, 10 ex

Description

где R=Ph, C₂H₅, цикло-C₃H₉; R¹=н-C₆H₁₃, н-C₈H₁₇.The present invention relates to methods for producing new organoaluminum compounds (AOC), specifically to a method for producing 1-ethyl-3-methyl-3-phenyl- (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes of the general formula (1):

where R = Ph, C ₂ H ₅ , cyclo-C ₃ H ₉ ; R ¹ = n-C ₆ H ₁₃ , n-C ₈ H ₁₇ .

 The proposed compounds can be used in fine organic and organometallic synthesis, as well as as cocatalysts in the processes of oligo- and polymerization of olefins and conjugated dienes.

Х=OC₂H₅,NEt₂
Известный способ не позволяет получать 1-этил-3-метил-3-фенил-(этил-, циклопропил-)-4-алкилиденциклогепта-2-оксаланы (1).A known method ([1], L.I. Zakharkin, L.A. Savina. Obtaining and properties of some intra-organoaluminum compounds. Izv. AN SSSR, Ser. Chem., 1960, 6, 1039-1043) for producing intra-organoaluminum compounds ( 2) the interaction of Bu ₂ ⁱ AlH with ω-functionally substituted α-olefins according to the scheme

X = OC ₂ H ₅ , NEt ₂
The known method does not allow to obtain 1-ethyl-3-methyl-3-phenyl- (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1).

Известным способом не могут быть получены 1-этил-3-метил-3-фенил-(этил-, циклопропил-)-4-алкилиденциклогепта-2-оксаланы (1).A known method ([2], L. I. Zakharkin, L. A. Savina. Synthesis of some cyclic alkylaluminium oxides and alkylaluminium amides. Izv. AN SSSR, Okhp. alcohol with triisobutylaluminum (AlBu ₃ ⁱ ) at -5 ÷ -10 ^o С followed by the addition of diisobutylaluminium hydride (Bu ₂ ⁱ AlH) and heating for 6 hours at 125-130 ^o С according to the scheme:

In a known manner, 1-ethyl-3-methyl-3-phenyl- (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1) cannot be obtained.

 Thus, in the literature there is no information on the selective preparation of 1-ethyl-3-methyl-3-phenyl- (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1).

 A new method is proposed for the synthesis of 1-ethyl-3-methyl-3-phenyl - ((ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1).

где R¹=н-С₆Н₁₃, н-С₈Н₁₇, с триэтилалюминием (А1Еt₃), взятыми в соотношении (ммоль)

в присутствии катализатора цирконацендихлорида (Cp₂ZrCl₂) в количестве 0,2-0,6 ммолей, в атмосфере аргона при комнатной температуре (~20^oС) и атмосферном давлении в хлористом метилене (СН₂Сl₂) в качестве растворителя в течение 5 часов с последующим добавлением при температуре -15^oС катализатора однохлористой меди (CuCl) в количестве 0,2-0,6 ммолей и кетона общей формулы CH₃RCO, где R= Ph, C₂H₅, цикло-С₃Н₅, в эквимольном по отношению к AlEt₃ количестве с перемешиванием реакционной массы 6-8 часов при комнатной температуре (~ 20^oС). Реакция протекает с образованием 1-этил-3-метил-3-фенил(этил-, циклопропил-)-4-алкилиденциклогепта-2-оксаланов(1) с выходом 62-81% по схеме

R¹=нC₆H₁₃, н-C₈H₁₇; R=Ph, Et, цикло-C₃H₅
1-Этил-3-метил-3-фенил(этил-, циклопропил-)-4-алкилиденциклогепта-2-оксаланы (1) образуются только лишь с участием AlEt₃, терминальных алленов, кетонов и циркониевого катализатора Cp₂ZrCl₂. В присутствии других соединений алюминия (например, Bu₂ ⁱAlCl, Вu₃ ⁱА1, Bu₂ ⁱAlH, EtAlCl₂, Et₂AlCl), других алленов (например, интернальных), других карбонильных соединений (например, альдегидов) или другого катализатора (например, Zr(acac)₄, ZrCl₄, Cp₂TiCl₂, Pd(acac)₂, Ni(acac)₂, NiCl₂, Fe(acac)₂) целевые продукты (1) не образуются.The essence of the method consists in the interaction of terminal allens of the General formula

where R ¹ = n-C ₆ H ₁₃ , n-C ₈ H ₁₇ , with triethyl aluminum (A1Et ₃ ), taken in the ratio (mmol)

in the presence of a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ) in an amount of 0.2-0.6 mmol, in an argon atmosphere at room temperature (~ 20 ^o C) and atmospheric pressure in methylene chloride (CH ₂ Cl ₂ ) as a solvent for 5 hours followed by the addition of a catalyst of monochloride (CuCl) in an amount of 0.2-0.6 mmol and a ketone of the general formula CH ₃ RCO at -15 ^° C, where R = Ph, C ₂ H ₅ , cyclo-C ₃ N ₅ , in an amount equimolar to AlEt ₃ with stirring of the reaction mass for 6-8 hours at room temperature (~ 20 ^° C). The reaction proceeds with the formation of 1-ethyl-3-methyl-3-phenyl (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1) with a yield of 62-81% according to the scheme

R ¹ = nC ₆ H ₁₃ , n-C ₈ H ₁₇ ; R = Ph, Et, cyclo-C ₃ H ₅
1-Ethyl-3-methyl-3-phenyl (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1) are formed only with the participation of AlEt ₃ , terminal allenes, ketones and a zirconium catalyst Cp ₂ ZrCl ₂ . In the presence of other aluminum compounds (e.g., Bu ₂ ⁱ AlCl, Bu ₃ ⁱ A1, Bu ₂ ⁱ AlH, EtAlCl ₂ , Et ₂ AlCl), other allens (e.g., internal), other carbonyl compounds (e.g., aldehydes) or another catalyst (for example, Zr (acac) ₄ , ZrCl ₄ , Cp ₂ TiCl ₂ , Pd (acac) ₂ , Ni (acac) ₂ , NiCl ₂ , Fe (acac) ₂ ) the target products (1) are not formed.

Carrying out this reaction in the presence of Cp ₂ ZrCl ₂ or CuCl catalysts of more than 0.6 mmol does not lead to a significant increase in the yield of the target products (1). The use of catalysts Cp ₂ ZrCl ₂ or CuCl less than 0.2 mmol reduces the yield of 1-ethyl-3-methyl-3-phenyl- (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1), which is possible , with a decrease in catalytically active centers in the reaction mass. The reaction was carried out at room temperature (~ 20 ^o C). At a higher temperature (for example, 40 ^o C) there is no significant increase in the yield of the target products (1), and at a lower temperature (for example, 0 ^o C) the reaction rate decreases.

A change in the ratio of the starting reagents in the direction of increasing AlEt ₃ content relative to the starting 1-substituted allene does not lead to a significant increase in the yield of the target products (1).

 Reactions were carried out using methylene chloride as a solvent. In other solvents (for example, aliphatic or aromatic), the regioselectivity of the reaction decreases.

 Significant differences of the proposed method.

триэтилалюминия (AlEt₃), кетоны (СН₃RСО), реакция протекает в присутствии катализаторов Cp₂ZrCl₂ и CuCl.1. In the proposed method for the production of cyclic Al-organic compounds, terminal allens are used as starting compounds

triethylaluminium (AlEt ₃ ), ketones (CH ₃ RCO), the reaction proceeds in the presence of Cp ₂ ZrCl ₂ and CuCl catalysts.

In the known method, allyl alcohol, triisobutylaluminum (AlBu ₃ ⁱ ) and diisobutylaluminum hydride (Bu ₂ ⁱ AlH) are used as starting reagents. The reaction proceeds at elevated temperature (120-130 ^o C).

 The proposed method has the following advantages.

 1. The method allows to obtain with high regioselectivity individual 1-ethyl-3-methyl-3-phenyl- (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes (1), the synthesis of which is not described in the literature.

 The method is illustrated by the following examples.

Example 1. In a 50 ml glass reactor mounted on a magnetic stirrer, 10 ml of methylene chloride (CH ₂ Cl ₂ ), 10 mmol of 1,2-nonadiene, 0.4 mmol of a Cp ₂ ZrCl ₂ catalyst were placed under argon atmosphere at a temperature ~ 0 ^o С 12 mmol A1Еt ₃ , stirred for 5 hours at room temperature (~ 20 ^o С), 0.4 mmol of CuCl catalyst and 12 mmol of acetophenone CH ₃ PhCO were added at a temperature of -15 ^o С, stirred for 7 hours at room temperature ( ~ 20 ^o C). Obtain 1-ethyl-3-methyl-3-phenyl-4-heptylidenecyclohepta-2-oxalanes (1) in 71% yield. The yield of the target product is determined by the hydrolysis product.

Спектр ЯМР¹³С(δ, м.д.): 81.31 С(1), 151.20 С(2), 33.19 С(3), 30.99 С(4), 18.36 С(5), 2.76 С(6), 8.73 С(7), 141.98 С(8), 129.50 С(9, 13), 128.72 С(10, 12), 126.70 С(11), 25.51 С(14), 129.76 С(15), 29.68 С(16), 29.87 С(17, 18), 32.28 С(19), 22.98 С(20), 14.26 С(21).Spectral characteristics of 1-ethyl-3-methyl-3-phenyl-4-heptylidenecyclohepta-2-oxalane (1):

¹³ C NMR spectrum (δ, ppm): 81.31 C (1), 151.20 C (2), 33.19 C (3), 30.99 C (4), 18.36 C (5), 2.76 C (6), 8.73 C (7), 141.98 C (8), 129.50 C (9, 13), 128.72 C (10, 12), 126.70 C (11), 25.51 C (14), 129.76 C (15), 29.68 C (16) , 29.87 C (17, 18), 32.28 C (19), 22.98 C (20), 14.26 C (21).

 Other examples confirming the method are given in the table.

The reaction was carried out at room temperature (~ 20 ^o C) in methylene chloride.

Claims (1)

The method of obtaining 1-ethyl-3-methyl-3-phenyl- (ethyl-, cyclopropyl -) - 4-alkylidenecyclohepta-2-oxalanes of the general formula (1)

where R = Ph, C ₂ H ₅ , cyclo-C ₃ H ₅ ;
R ¹ = n-C ₆ H ₁₃ , n-C ₈ H ₁₇ ,
characterized in that the terminal allens of the general formula R ¹ —CH = C = CH ₂ , where R ¹ = n — C ₆ H ₁₃ , n — C ₈ H ₁₇ , interact with AlEt ₃ triethylaluminum in the ratio R ¹ —CH = C = CH ₂ : AlEt ₃ , equal to 10: (10 ÷ 14) mmoles in the presence of a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ), taken in an amount of 0.2-0.6 mmol relative to the 1-substituted allene, in an argon atmosphere at room temperature temperature and atmospheric pressure in methylene chloride as a solvent for 5 hours, followed by the addition of a catalyst of copper monochloride (CuCl) taken at a temperature of -15 ^o С 0.2-0.6 mmol in relation to the starting allene, and a ketone of the formula CH ₃ RCO, where R = Ph, C ₂ H ₅ , cyclo-C ₃ H ₅ in an amount equimolar to AlEt ₃ and stirring the reaction mass for 6-8 hours at room temperature.

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