RU2402542C2 - 1,2,3,4,5,6,7,9,10,11,12,13,14,15-TETRADECAHYDRO-DICYCLONONE[b,d]THIOPHENE SYNTHESIS METHOD - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclonone[b,d]thiophene of general formula (1):

, characterised by that cyclonone-1,2-diene reacts with ethylaluminium dichloride (EtAlCl₂) in the presence of Mg (powder) and a zirconocene dichloride (Cp₂ZrCl₂) catalyst in molar ratio cyclonone-1,2-diene : EtAlCl₂ : Mg : Cp₂ZrCl₂ = 20:(11-13):20:(1.0-1.4), preferably 20:12:20:1.2, in an argon atmosphere at room temperature (20-22°C) and atmospheric pressure for 6-8 hours in tetrahydrofuran, and subsequent addition of an amount of elementary sulphur S₈ which is equimolar to EtAlCl₂, benzene as a solvent and heating the reaction mass for 6 hours at approximately 80°C and the reaction mass is kept at approximately 140°C for 1 hour after evaporation of light solvents.

EFFECT: method for synthesis of a novel compound which can be used in fine organic synthesis and synthesis of biologically active heterocyclic compounds.

1 cl, 1 tbl, 1 ex

Description

The present invention relates to organic chemistry, specifically, a method for producing 1,2,3,4,5,6,7,7,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene of the General formula (1 ):

Substituted thiophenes can find application in the food industry as components of food flavor enhancers, biologically active compounds, dyes, additives to oils and hydraulic fluids.

A known method (Dzhemilev U.M., Ibragimov A.G., Zolotarev A.P., Khalilov L.M., Musloukhov PP Synthesis and transformation of metalcycles. Message 9. Synthesis of polycyclic aluminocyclopentanes with the participation of (η ⁵ -C ₅ H ₅ ) ₂ ZrCl _2. Izv. AN Ser. Khim., 1992, No. 2, 386-391) the production of tricyclic thiophanes, for example, 3-thiatetracyclo [5.2.1.0 ^2,6 ] decane (2) by the interaction of norbornene with AlEt ₃ under the action of 3-5 mol.% catalyst Cp ₂ ZrCl ₂ in hydrocarbon solvents, or without solvent at a temperature of 25 ° C for 12-14 hours, followed by addition of slurry threefold excess of concern w AlEt ₃ to elemental sulfur in benzene and maintaining the reaction mixture for 8 hours in refluxing benzene at ~ 80 ° C. The reaction proceeds according to the scheme:

In a known manner, 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene of the formula (1) cannot be obtained.

A known method (Dzhemilev U.M., Gubaidullin L.Yu., Tolstikov G.A. Cyclic co-oligomerization of 2-vinylthiophene with butadiene catalyzed by nickel complexes // Izv. thiophanes, for example, 1,4,4a, 7,8,11,11a, 11b-octahydrocyclooct [b] [1] benzothiophene (3) by the interaction of 2-vinylthiophene with butadiene at a temperature of 60 ° C for 4 hours under the action of phosphine Nickel complex according to the scheme:

In a known manner, 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene of the general formula (1) cannot be obtained.

A new method is proposed for the synthesis of 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene of the general formula (1).

The essence of the method consists in the interaction of cyclone-1,2-diene with ethyl aluminum dichloride (EtAlCl ₂ ) in the presence of Mg (powder) and a catalyst of zirconacide dichloride (Cp ₂ ZrCl ₂ ), taken in a molar ratio of cyclone-1,2-diene: EtAlCl ₂ : Mg : Cp ₂ ZrCl ₂ = 20: (11-13): 20: (1.0-1.4), preferably 20: 12: 20: 1.2, in an argon atmosphere at room temperature (20-22 ° C) and atmospheric pressure for 6 -8 hours in tetrahydrofuran, followed by the addition _{of an} amount of elemental sulfur S ₈ equimolar to EtAlCl ₂ , benzene as a solvent and heating the reaction mixture for 6 hours at a temperature of ~ 80 ° C, then, after evaporation of light solvents, the reaction mass is kept for 1 hour at a temperature of -140 ° C. 1,2,3,4,5,6,7,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene of the general formula (1) are obtained in a yield of 45-60%. The reaction proceeds according to the scheme:

The target product (1) is formed only with the participation of cyclonon-1,2-diene, EtAlCl ₂ , elemental sulfur S ₈ , magnesium and a catalyst Cp ₂ ZrCl ₂ . In the presence of other catalysts based on transition metal complexes (for example, Zr (acac) ₄ , Cp ₂ TiCl ₂ , Pd (acac) ₂ , Ni (acac) ₂ , Fe (acac) ₃ ), the target product (1) is not formed.

The reaction in the presence of a catalyst Cp ₂ ZrCl ₂ more than 14 mol.% In relation to cyclone-1,2-diene does not lead to a significant increase in the yield of the target product (1). The use in the reaction of the catalyst Cp ₂ ZrCl ₂ less than 10 mol. % reduces the yield of tricyclic thiophene (1), which is associated with a decrease in catalytically active centers in the reaction mass.

The change in the ratio of the starting reagents in the direction of increasing the content of EtAlCl ₂ or elemental sulfur S ₈ with respect to cyclonon-1,2-diene does not lead to a significant increase in the yield of the target product (1). A decrease in the amount of EtAlCl ₂ or elemental sulfur S ₈ with respect to cyclonon-1,2-diene reduces the yield of tricyclic thiophene (1).

Significant differences of the proposed method:

In the proposed method, cyclone-1,2-diene, EtAlCl ₂ and elemental sulfur S ₈ are used as starting compounds. In the known method, 2-vinylthiophene and butadiene are used as starting reagents, the catalyst being nickel phosphine complexes.

The proposed method has the following advantages:

The method allows to obtain with high selectivity 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene of the general formula (1), the synthesis of which literature not described.

The method is illustrated by the following examples:

EXAMPLE 1. 1.2 mmol of Cp ₂ ZrCl ₂ , 20 mmol of cyclonone-1,2-diene, 20 mmol of magnesium (powder), 10 ml of THF and at ~ 0 ° C are placed in a glass reactor mounted on a magnetic stirrer in an argon atmosphere. 12 mmol EtAlCl ₂ . Stirred at room temperature for 7 hours, then add 12 mmol of elemental sulfur S ₈ , 10 ml of benzene, removed by distillation of THF, maintain the reaction mass for 6 hours at a temperature of ~ 80 ° C, then, after evaporation in light solvents, the reaction mass is maintained 1 hour at a temperature of ~ 140 ° C. An individual 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene is obtained in a yield of 52%. Spectral characteristics of 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene (1).

¹ H NMR spectrum (400 MHz, CDCl ₃ ): 2.83 (4H, t, J = 6.4 Hz); 2.59 (4H, t, J = 6.0 Hz), 1.68 (4 N, m); 1.62 (4 N, m); 1.48 (4 N, m); 1.41 (8 N, m). ¹³ C NMR spectrum (100 MHz, CDCl ₃ ): 137.5, 135.6, 29.4, 27.4, 27.3, 26.6, 26.1, 24.8, 24.2.

Other examples confirming the method are shown in table 1.

Table 1 No. Item No. The molar ratio of cyclonone-1,2-diene: EtAlCl ₂ : Mg: S ₈ : Cp ₂ ZrCl ₂ , mmol Total reaction time, hour Yield (1),% one 20: 12: 20: 12: 1.2 fourteen 52 2 20: 13: 20: 13: 1.2 fourteen 56 3 20: 11: 20: 11: 1.2 fourteen 47 four 20: 12: 20: 12: 1.4 fourteen 60 5 20: 12: 20: 12: 1.0 fourteen 45 6 20: 12: 20: 12: 1.2 fifteen 55 7 20: 12: 20: 12: 1.2 13 48

All experiments were carried out in an argon atmosphere at room temperature (20-22 ° C) and atmospheric pressure for 6-8 hours in tetrahydrofuran, followed by the addition of benzene and heating the reaction mass for 6 hours at a temperature of 80 ° C, then, after evaporation in light solvents, the reaction mass can withstand 1 hour at a temperature of ~ 140 ° C.

Claims (1)

The method of obtaining 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone [b, d] thiophene of the general formula (I):

characterized in that the cyclonone-1,2-diene is reacted with ethyl aluminum dichloride (EtAlCl ₂ ) in the presence of Mg (powder) and a zirconacene dichloride catalyst (Cp ₂ ZrCl ₂ ) taken in a molar ratio of cyclonone-1,2-diene: EtAlCl ₂ : Mg: Cp ₂ ZrCl ₂ = 20: (11-13): 20: (1.0-1.4), preferably 20: 12: 20: 1.2, in an argon atmosphere at room temperature (20-22 ° C) and atmospheric pressure for 6-8 hours in tetrahydrofuran, followed by the addition _{of an} amount of elemental sulfur S ₈ equimolar to EtAlCl ₂ , benzene as a solvent and heating the reaction mixture for 6 hours at a temperature of ~ 80 ° C, then after evaporation of light solvents, the reaction mass is kept for 1 h at a temperature of ~ 140 ° C.