RU2423364C2 - Method for synthesis of 3,4-dialkylmagnesacyclopentanes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of 3,4-dialkylmagnesacyclopentanes of general formula (I)

. The method involves reaction of organomagnesium compounds

(where R=H-C₃H₇, H-C₄H₉, n-C₆H₁₃) with catalytic amounts of zirconocene dichloride Cp₂ZrCl₂. The cocatalyst used is disubstituted acetylene of formula

(where R¹=C₂H₅, n-C₃H₇) and the reaction is carried out in molar ratio

Cp₂ZrCl₂ :

equal to 10:(0.2-0.5):(0.5-1.0), in an argon atmosphere at atmospheric pressure of ether solvents fro 3-4 hours.

EFFECT: shorter reaction time, high output and selectivity of the end product.

1 ex, 1 tbl

Description

The invention relates to the field of organometallic synthesis, specifically to a method for producing 3,4-dialkylmagnesacyclopentanes of the general formula (I):

,

,

where R = n-C ₃ H ₇ , n-C ₄ H ₉ , n-C ₆ H ₁₃

These compounds are promising reagents for the selective preparation of bifunctional compounds, carbo- and heterocycles, and can also be used as cocatalysts in the processes of oligomerization and polymerization of olefins and dienes in fine industrial organic and organometallic synthesis.

The known method [U.M. Dzhemilev, PMSultanov, R.G. Gaimaldinov, PPMuslukhov, S.I. Lomakin, G.A. Tolstikov. Catalytic synthesis and conversion of magnesiumcycloalkanes. II. Synthesis of substituted magnesium cyclopentanes involving zirconium complexes. // Izv. USSR Academy of Sciences. Ser. Chem. 1991. No8. P.1652] the preparation of limiting cyclic organomagnesium compounds, namely phenyl-, alkyl-substituted magnesacyclopentanes of the general formula (II, III) by the interaction of styrene with dialkyl magnesium derivatives in the presence of Cp ₂ ZrC ₂ (3-4 mol.%) At a temperature of 20-22 ° С for 7 hours in a mixture of THF-Et ₂ O (1: 1) with a yield of 95% according to the scheme:

where R-CH ₃ , C ₂ H ₅ , n-C ₃ H ₅ , n-C ₃ H ₇ , n-C ₄ H ₉ .

The known method does not allow to obtain 3,4-dialkylmagnesacyclopentanes (I).

The known method [U.M. Dzhemilev, PMSultanov, R.G. Gaimaldinov, PPMuslukhov, G.A. Tolstikov. Catalytic synthesis and conversion of magnesiumcycloalkanes. I. New catalytic transformations in the series of magnesium cyclopentanes. // Izv. USSR Academy of Sciences. Ser. Chem. 1991. No.6. S.1388-1393] obtaining substituted magnesacyclopentane, namely 2-phenylmagnesacyclopentane of the general formula (IV) by the interaction of styrene with unsubstituted magnesacyclopentane in the presence of a catalyst Cp ₂ ZrCl ₂ (3 mol%) at a temperature of 22-24 ° C for 1.5 hours in THF with a yield of ~ 75% according to the scheme:

In a known manner, 3,4-dialkylmagnesacyclopentanes (I) cannot be obtained.

Cp₂ZrCl₂=10:10:0,5. Реакцию проводят в атмосфере сухого аргона при комнатной температуре (20-22°С) и атмосферном давлении. Время реакции 20 часов. Суммарный выход целевых продуктов не более 5,0-7,0%. Реакция осуществляется в диэтиловом эфире и протекает по схеме:Closest to the technical solution to the claimed is a method for producing 3,4-dialkylmagnesacyclopentanes (I) [PM Sultanov. New reactions of Zn-, Mg-, and A1-organic compounds with olefins and acetylenes catalyzed by transition metal complexes. The dissertation for the degree of Doctor of Chemical Sciences. Ufa 2001. P.192] the interaction of dialkyl derivatives of magnesium with α-olefins in the presence of Cp ₂ ZrCl ₂ taken in a molar ratio

Cp ₂ ZrCl ₂ = 10: 10: 0.5. The reaction is carried out in an atmosphere of dry argon at room temperature (20-22 ° C) and atmospheric pressure. The reaction time is 20 hours. The total yield of the target products is not more than 5.0-7.0%. The reaction is carried out in diethyl ether and proceeds according to the scheme:

R = n-C ₃ H ₇ , n-C ₄ H ₉ , n-C ₅ H ₁₁

R ¹ = CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , n-C ₄ H ₉ , n-C ₆ H ₁₁

The disadvantages of the method are:

1. Very low yield of 3,4-dialkylmagnesacyclopentanes.

2. Low selectivity.

3. The duration of the reaction.

The aim of the invention is to eliminate the disadvantages noted in the previous section, which allows to obtain compounds (I) with high yields and selectivity, as well as in a shorter time.

(где R=н-С₃Н₇, н-С₄Н₉, н-C₆H₁₃ с каталитическим количеством Cp₂ZrCl₂ в присутствии дизамещенного ацетилена формулы

(где R¹=С₂Н₅, н-С₃Н₇), взятых в мольном соотношении

The essence of the method consists in the interaction of organomagnesium compounds

(where R = n — C ₃ H ₇ , n — C ₄ H ₉ , n — C ₆ H ₁₃ with a catalytic amount of Cp ₂ ZrCl ₂ in the presence of a disubstituted acetylene of the formula

(where R ¹ = C ₂ H ₅ , nC ₃ H ₇ ), taken in molar ratio

The reaction is carried out in an argon atmosphere and at room temperature (20-22 ° C) and atmospheric pressure. The reaction time is 3-4 hours, the yield of the target products is 59-80%.

As a solvent, it is necessary to use ethers (diethyl ether, dipropyl ether, diisopropyl ether).

The reaction proceeds according to the scheme:

R = n-C ₃ H ₇ , n-C ₄ H ₉ , n-C ₆ H ₁₁

R ¹ = C ₃ H ₇ , n-C ₃ H ₇

Distinguished by the proposed method:

(где R=н-С₃Н₇, н-С₄Н₉, н-С₆Н₁₃).1. as a cyclic metal reagent

(where R = n — C ₃ H ₇ , n — C ₄ H ₉ , n — C ₆ H ₁₃ ).

2. Reducing the reaction time to 3-4 hours.

(где R¹=С₂Н₅, н-С₃Н₇) в качестве добавки (сокатализатора) к Cp₂ZrCl₂.3. The use of disubstituted acetylenes of the General formula

(where R ¹ = C ₂ H ₅ , nC ₃ H ₇ ) as an additive (cocatalyst) to Cp ₂ ZrCl ₂ .

The proposed method has the following advantages:

1. The method allows to obtain selectively and with high yields (70-85%) of 3,4-dialkylmagnesacyclopentanes (I).

The method is illustrated by the following examples.

EXAMPLE 1. 10 mmol of n-C ₆ H ₁₃ MgBr (1.0 M solution in diethyl ether) is introduced into a 50 ml glass reactor mounted on a magnetic stirrer in an argon atmosphere, and 0.2 mmol of Cp ₂ ZrCl is added to this solution. ₂ and 0.5 mmol of hex-3-in. The resulting reaction mixture was stirred at room temperature (~ 20 ° C) for 3 hours. 3,4-Dibutylmagnesacyclopentane (I) is obtained in a yield of 59%. The yield of the target product was determined by the hydrolysis product. The hydrolysis of (I) produces 5,6-dimethyldecane (V), and the deuterolysis of 1,4-dideutero-2,3-dibutylbutane (VI).

Spectral characteristics of the products of hydrolysis (V) and deuterolysis (VI).

5,6-dimethyldecane (V). T. bale 72-73 ° C (5 mm Hg). IR spectrum (ν, cm ^-1 ): 2930, 2860, 1460, 1375, 1210, 1140. ¹ H NMR spectrum (δ, ppm): 0.80-1.00 m (12Н, СН ₃ ), 1.06-1.62 m (14H, CH, CH ₂ ). ¹³ C NMR spectrum (δ, ppm): 14.43 k (C ¹ ), 36.76 d (C ² ), 34.81 t (C ³ ), 30.17 t (C ⁴ ), 23.19 t (C ⁵ ), 14.22 k (C ⁶ ). [M] ⁺ 170.

1,4-Dideutero-2,3-dibutylbutane (VI): T. bale. 58-60 ° C (2 mm Hg). IR spectrum (ν, cm ^-1 ): 2970, 2940, 2870, 2160, 1470, 1385, 1070. ¹ H NMR spectrum (δ, ppm): 0.60-0.97 m (10Н, СН ₃ , CH ₂ D), 1.05-1.50 m (14H, CH, CH ₂ ). ¹³ C NMR spectrum (δ, ppm): 14.20 t (J _CD = 18.5 Hz) (C ¹ ), 36.71 d (C ² ), 34.81 t (C ³ ), 30.21 t (C ⁴ ), 22.63 t (C ⁵ ), 14.22 k (C ⁶ ). [M] ⁺ 172.

EXAMPLE 2. In a 50 ml glass reactor mounted on a magnetic stirrer, 10 mmol of n-C ₅ H ₁₁ MgBr (1.0 M solution in diethyl ether) was introduced under argon atmosphere, 0.3 mmol of Cp ₂ ZrCl was added to this solution. ₂ and 0.5 mmol of hex-3-in. The resulting reaction mixture was stirred at room temperature (~ 20 ° C) for 4 hours. 3,4-Dipropylmagnesacyclopentane (I) is obtained in a yield of 70%. The yield (I) was determined by the hydrolysis product. The hydrolysis of (I) produces 4,5-dimethyloctane (VII), and the deuterolysis of 1,4-dideutero-2,3-dipropylbutane (VIII)

Spectral characteristics of the products of hydrolysis (VII) and deuterolysis (VIII).

4,5-Dimethyloctane (VII): T. bale. 159 ° C. IR spectrum (ν, cm ^-1 ): 2930, 2860, 1460, 1375, 1210, 1140. ¹ H NMR spectrum (δ, ppm): 0.85-0.89 m (12Н, СН ₃ ), 1.03-1.33 m (8CH ₂ , 2CH). ¹³ C NMR spectrum (δ, ppm): 14.45 k (C ¹ ), 37.05 d (C ² ), 34.94 t (C ³ ), 23.20 t (C ⁴ ), 14.15 k (C ⁵ ). [M] ⁺ 142.

1,4-Dideutero-2,3-dipropylbutane (VIII): T. bale. 157-159 ° C. IR spectrum (ν, cm ^-1 ): 2960, 2920, 2850, 2160, 1480, 1390, 1060. ¹ H NMR spectrum (δ, ppm): 0.65-0.92 m (10Н, СН ₃ , CH ₂ D), 1.03-1.45 m (10H, CH ₂ , CH). ¹³ C NMR spectrum (δ, ppm): 14.93 t (J _CD = 19.0 Hz) (C ¹ ), 36.65 d (C ² ), 35.15 t (C ³ ), 22.61 t (C ⁴ ), 14.21 to (C ⁵ ). [M] ⁺ 144.

Other examples confirming the method are shown in table 1

Table 1 p / p

Organomagnesium Compound (MOS) Molar ratio

: MOC: Cp ₂ ZrCl ₂ Reaction time, hour Yield (I),% one. hex-3-in n-C ₆ H ₁₃ MgBr 10: 0.2: 0.5 3 59 2. hex-3-in n-C ₅ H ₁₁ MgBr 10: 0.3: 0.5 four 70 3. hex-3-in n-C ₅ H ₁₁ MgBr 10: 0.4: 0.5 four 80 four. hex-3-in n-C ₅ H ₁₁ MgBr 10: 0.5: 0.5 four 80 5. hex-3-in n-C ₅ H ₁₁ MgBr 10: 0.4: 0.5 four 77 6. hex-3-in n-C ₅ H ₁₁ MgBr 10: 0.4: 1.0 four 71 7. hex-3-in n-C ₈ H ₁₇ MgBr 10: 0.4: 0.5 four 75 8. hex-3-in n-C ₆ H ₁₃ MgBr 10: 0.5: 0.5 four 79 9. oct-4-in nC ₅ H ₁₃ MgBr 10: 0.5: 0.5 four 78 10.* hex-3-in n-C ₆ H ₁₃ MgBr 10: 0.5: 0.5 four 76 eleven.** hex-3-in n-C ₆ H ₁₃ MgBr 10: 0.5: 0.5 four 74 * The reaction was carried out in dipropyl ether.
** The reaction was carried out in diisopropyl ether.

Claims (1)

The method of obtaining 3,4-dialkylmagnesacyclopentanes of General formula (I)

characterized in that the organomagnesium compounds

(where R = H — C ₃ H ₇ , HC ₄ H ₉ , n — C ₆ H ₁₃ ) are reacted with catalytic amounts of zirconacene dichloride Cp ₂ ZrCl ₂ , characterized in that a disubstituted acetylene of the formula is used as cocatalyst

(where R ¹ = C ₂ H ₅ , HC ₃ H ₇ ) and the reaction is carried out at a molar ratio

: Cp ₂ ZrCl ₂ :

equal to 10: (0.2-0.5) :( 0.5-1.0), in an argon atmosphere at atmospheric pressure in ether solvents for 3-4 hours