Method of producing 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone[b,d]thiophene

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrodicyclonone[b,d]thiophene of general formula : characterised by that, cyclonone-1,2-diene is reacted with ethylmagnesium bromide (EtMgBr/ether) in the presence of Mg (powder) and titanocene dichloride (Cp2TiCl2) catalyst taken in molar ratio cyclonone-1,2-diene : EtMgBr : Mg : Cp2TiCl2 = 20:(22-26):20:(1.0-1.4), preferably 20:24:20:1.2, in an argon atmosphere at room temperature (20-22°C) and atmospheric pressure for 6-8 hours in diethyl ether, with subsequent addition of an amount of elementary sulphur S8 which is equimolar to EtMgBr, benzene as a solvent and heating the reaction mass for 5 hours at temperature of approximately 40°C, then after evaporation of light solvents, the reaction mass is kept for 1 hour at temperature of approximately 140°C.

EFFECT: compounds can be used in fine organic synthesis and in production of biologically active heterocyclic compounds.

1 cl, 1 tbl, 1 ex

 

The present invention relates to organic chemistry, specifically the method of obtaining 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclopenta[b,d]thiophene of the General formula (1):

Substituted tifany can find application in the food industry as components of amplifiers aroma of food, biologically active compounds, dyes, additives to oils and hydraulic fluids.

The known method (Dzhemilev sea level, Ibragimov A.G., Zolotarev A.P., Khalilov L.M., Muslumov P.P. Synthesis and transformations of metallocycles. Message 9. Synthesis of polycyclic almacenamento involving (η5-C5H5)2ZrCl2. WPI. An. The series of chem., 1992, No. 2, 386-391) receiving tricyclic of teofanov, for example 3-teacherciclo[5.2.1.02,6]decane (2) the interaction of norbornene AlEt3under the action of 3-5 mol.% catalyst Cp2ZrCl2in hydrocarbon solvents or without solvent at a temperature of 25°C for 12-14 h followed by addition of a suspension of the three-fold excess relative to AlEt3elemental sulfur in benzene and maintaining the reaction mixture for 8 h in boiling benzene at a temperature of ~80°C. the Reaction proceeds according to the scheme

The known method cannot be obtained 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclopenta[b,d]thiophene forms the crystals (1).

The known method (Dzhemilev sea level, Gubaidullin LU, Tolstikov G.A. Cyclic cooligomerization 2-venitien with butadiene, catalyzed by complexes of Nickel, Izv. THE USSR ACADEMY OF SCIENCES. Ser. chem. (1978) 1469) obtain unsaturated tricyclic of teofanov, for example 1,4,4A,7,8,11,11a,11b-octahydrocyclopenta[b][1]-benzothiophene (3) the interaction of 2-venitien with butadiene at a temperature of 60°C for 4 h under the action of phosphine complex of Nickel scheme

The known method cannot be obtained 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclopenta[b,d]thiophene of the General formula (1).

We propose a new method for the synthesis of 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclopenta[b,d]thiophene of the General formula (1).

The method consists in the interaction of cyclonona-1,2-diene with ethylmagnesium (EtMgBr/ether) in the presence of Mg (powder) and catalyst titanzincoated (Cf2TiCl2), taken in a molar ratio of cyclonona-1,2-diene:EtMgBr:Mg:SR2TiCl2=20:(22-26):20:(1.0-1.4), preferably 20:24:20:1.2, in an argon atmosphere at room temperature (20-22°C) and atmospheric pressure for 6-8 h in diethyl ether followed by the addition equimolar EtMgBr to the number of elemental sulfur S8, benzene as solvent and heating the reaction mixture for 5 hours at a temperature of ~40°C, and then, after evaporation of l is gcih solvents, the reaction mass is allowed to stand for 1 h at a temperature of ~140°C. Receive 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclopenta[b,d]-thiophene of the General formula (1) with output 47-64%. The reaction proceeds according to the scheme

Target product (1) are formed only with the participation of cyclonona-1,2-diene, EtMgBr, elemental sulfur S8, magnesium and catalyst Cf2TiCl2In the presence of other catalysts based on transition metal complexes (for example, Zr(acac)4Cp2ZrCl2Pd(acac)2, Ni(acac)2, Fe(ASAS)3the target product (1) is not formed.

Conducting the reaction in the presence of a catalyst Cf2TiCl2more than 14 mol.% in relation to cyclonona-1,2-diene does not lead to a significant increase in the yield of the target product (1). Use in the reaction of the catalyst Cf2TiCl2less than 10 mol.% reduces the output tricyclic thiophene (1), which is associated with a reduction of catalytically active sites in the reaction mass.

Changing the ratio of initial reagents in the direction of increasing the content of EtMgBr or elemental sulfur S8in relation to cyclonona-1,2-diene or Alka-1,2-diene does not lead to a significant increase in the yield of the target product (1). The reduction in the number of EtMgBr or elemental sulfur S8in relation to cyclonona-1,2-diene reduces the output of the tricyclic thiophene (1).

Being the major difference of the proposed method

In the proposed method are used as starting compounds cyclonona-1,2-diene, EtMgBr and elemental sulfur S8. In the known method are used as initial reagents 2-venitien and butadiene, and a catalyst are phosphine complexes of Nickel.

The proposed method has the following advantages.

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

The method is illustrated by the following examples.

EXAMPLE 1. In a glass reactor, mounted on a magnetic stirrer, an argon atmosphere was placed 1.2 mmol Cf2TiCl2, 20 mmol cyclonona-1,2-diene, 20 mmol of magnesium (powder) and at a temperature of ~0°C, 24 mmol EtMgBr (1.6M solution in

Et2About). Stirred at room temperature for 7 h, then add 24 mmol of elemental sulfur S810 ml benzene is removed by distillation of the ether, able to withstand the reaction mass for 5 hours at a temperature of ~40°C, then 1 h at a temperature of ~140°C. Receive individual 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclopenta[b,d]thiophene with the release of 55%.

Spectral characteristics 1,2,3,4,5,6,7,9,10,11,12,13,14,15-tetradecahydrocyclopenta[b,d]thiophene (1).

An NMR spectrum1H (400 MHz, CDCl3): 2.83 (4H, t, J=6.4 Hz); 2.59 (4H, t, J=6.0 Hz), 1.68 (4 H, m); 1.62 (4H, m); 1.48 (4H, m); 1.41 (8H, m). An NMR spectrum13(100 MHz, CDCl3): 137.5, 135.6, 29.4, 27.4, 27.3, 26.6, 26.1, 24.8, 24.2.

Other examples of the method shown in the table.

№№ p/pThe molar ratio of cyclonona-1,2-diene:EtMgBr:S8:Cp2TiCl2mmolThe total reaction time, hOutput (1), %
120:24:24:1.01355
220:26:26:1.01357
320:22:22:1.01350
420:24:24:1.21364
520:24:24:0.81347
620:24:24:1.01459
7 20:24:24:1.01248

All experiments were performed in an argon atmosphere at room temperature (20-22°C) and atmospheric pressure for 6-8 h in diethyl ether followed by the addition of benzene and heating the reaction mixture for 5 h at 40°C and 1 h at a temperature of ~140°C.

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

characterized in that cyclonona-1,2-diene is subjected to interaction with ethylmagnesium (EtMgBr/ether) in the presence of Mg (powder) and catalyst titanzincoated (Cp2TiCl2), taken in a molar ratio of cyclonona-1,2-diene : EtMgBr : Mg : Cp2TiCl2=20:(22-26):20:(1.0-1.4), preferably 20:24:20:1.2, in an argon atmosphere at room temperature (20-22°C) and atmospheric pressure for 6-8 h in diethyl ether, and then adding equimolar EtMgBr to the number of elemental sulfur S8, benzene as solvent and heating the reaction mixture for 5 hours at a temperature of ~40°C, and then, after evaporation of light solvents, the reaction mass is allowed to stand for 1 h at a temperature of ~140°C.



 

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FIELD: chemistry.

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1 ex, 1 tbl

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1 tbl, 11 ex

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22 cl, 23 ex

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15 cl, 5 tbl, 18 ex

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42 cl, 8 tbl, 8 ex

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22 cl, 23 ex

FIELD: chemistry.

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1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to field of organic chemistry, namely to method of obtaining 2,5-dialkyl-3,4-fullero[60]tetrahydrothiophen-1-ons of general formula (I) . Essence of method lies in interaction of fullereneC60 with dialkylsufoxides in presence of catalyst Cp2ZrCl2 in toluol medium at temperature 140-160°C during 5-7 hours. Target product output is 40-65%.

EFFECT: obtaining compounds, which can be used as complex-forming agents, sorbents, biologically active compounds, as well as in creation of novel materials with set electronic, magnetic and optical properties.

1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to field of organic chemistry, namely to method of obtaining 3,4-fullero(60)tetrahydrothiophene of formula (I) . Essence of method lies in interaction of fullerene C60 with dimethylsulfide in presence of catalyst Cp2TiCl2 in toluol medium at temperature ˜20°C during 66-78 hours. Target product output is 59-82%.

EFFECT: obtaining compound, which can be used as complex-forming agent, sorbent, biologically active compound, as well as in creation of novel materials with set electronic, magnetic and optical properties.

1 tbl, 7 ex

FIELD: chemistry, pharmacology.

SUBSTANCE: claimed invention relates to field of organic chemistry, namely to method of obtaining 2,5-diphenyl-3,4-fullero[60]tetrahydrothiophen of formula (I) . Essence of method lies in interaction of fullerene C60 with dibenzylsulfide in presence of catalyst hafnocene dichloride Cp2HfCl2 in toluol medium at temperature 140-160°C during 4-8 hours. Target product output is 42-64%.

EFFECT: obtaining compound, which can be used as complex-forming agent, sorbent, biologically active compound, as well as in creation of novel materials with set electronic, magnetic and optical properties.

9 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to field of organic chemistry, namely to method of obtaining 2,5-diphenyl-3,4-fullero[60]tetrahydrothiophen-1-on of general formula (I) . Essence of method lies in interaction of fullerene C60 with dibenzylsulfoxide in presence of catalyst Cp2HfCl2 in toluol medium at temperature 140-160°C during 5-7 hours. Target product output is 43-68%.

EFFECT: obtaining compounds, which can be used as complex-forming agents, sorbents, biologically active compounds, as well as in creation of novel materials with set electronic, magnetic and optical properties.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to field of organic chemistry, namely to method of obtaining 3,4-fullero(60)tetrahydrothiophen-1-on of formula (I) . Essence of method lies in interaction of fullerene C60 with dimethylsulfoxide in presence of catalyst Cp2ZrCl2 in toluol medium at temperature ˜20 °C during 66-78 hours. Target product output is 56-79%.

EFFECT: obtaining compound, which can be used as complex-forming agent, sorbent, biologically active compound, as well as in creation of novel materials with set electronic, magnetic and optical properties.

1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: claimed invention relates to field of organic chemistry, namely to method of obtaining 2,5-dialkyl-3,4-fullero[60]tetrahydrothiophenes of formula (I) . Essence of method lies in interaction of fullerene C60 with dialkylsulfide in presence of catalyst Cp2TiCl2 in toluol medium at temperature 140-160°C during 5-7 hours. Target product output is 47-70%.

EFFECT: obtaining compounds, which can be used as complex-forming agents, sorbents, biologically active compounds, as well as in creation of novel materials with set electronic, magnetic and optical properties.

1 ex, 1 tbl

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