Method of producing 2-alkyl-5,6,7,8,9,10-hexahydro-4h-cyclonone [b]thiophenes

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonone[b]thiophenes of general formula : (1), where R=n-C5H11, n-C7H15, n-C9H19, characterised by that the mixture of cyclonone-1,2-diene and alka-1,2-diene (octa-1,2-diene, deca-1,2-diene, dodeca-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 : alka-1,2-diene : EtMgBr : Mg : Cp2TiCl2= 10:10:(22-26):20:(1.0-1.4), preferably 10:10:24:20:1.2, in an argon atomosphere at room temperature (20-22°C) and atmospheric pressure for 6-8 hours and 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 6 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 the food industry as components of flavour boosters, biologically active compounds, dyes, oil additives and hydraulic liquids.

1 cl, 1 tbl, 1 ex

 

The invention relates to organic chemistry, specifically a method for producing 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]-teofanov General formula (1):

where R=n-C5H11n-C7H15n-C9H19.

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 ([1], J.Chen, Q.Song, Z.Xi. Novel reaction patterns of carbon disulfide with organolithium compounds via cleavage of C=S bonds or via cycloaddition reactions // Tetrahedron Lett., 43 (2002) 3533-3535) obtain tetraallylsilane interaction 1,4-delicio-1,3-dienes (2), obtained by processing 1,2,3,4-tetraalkyl-1,4-diid-1,3-butadiene butyllithium (n-BuLi) at -78°C for 1 hour, with carbon disulfide at -20°C for 1 hour with access 52-68% scheme:

The known method cannot be obtained 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]-tifany General formula (1).

The known method ([2], RJ.Fagan, W.A.Nugent, J.C.Calabrese. Metallacycle transfer from zirconium to main group elements: A versatile synthesis of heterocycles // JACS, 116, (1994), 1880-1890) obtain the bicyclic teofanov (3) with the release of ~55% of the interaction of diacetylenes with the stoichiometric amount of bis-cyclopentadienylzirconium (Cp2ZrCl2and butyllithium (n-BuLi), followed by treatment of p is a promotional mass polularity sulphur (S 2Cl2) according to the scheme:

The known method does not allow to synthesize 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]tiophene General formula (1).

A new method of synthesis of 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]teofanov General formula (1).

The essence of the method lies in the interaction equimole mixture cyclonona-1,2-diene and Alka-1,2-diene (OCTA-1,2-diene, DECA-1,2-diene, dodeca-1,2-diene) with ethylmagnesium (EtMgBr/ether) in the presence of Mg (powder) and catalyst titanzincoated (Cp2TiCl2), taken in a molar ratio of cyclonona-1,2-diene: Alka-1,2-diene: EtMgBr: Mg: Cp2TiCl2=10:10:(22-26):20:(1.0-1.4), preferably 10:10:24:20:1.2, in an argon atmosphere at room temperature (20-22°C) and atmospheric pressure for 6-8 hours in diethyl ether, and then adding equimolar EtMgBr to the number of elemental sulfur S8, benzene as solvent and heating the reaction mixture for 6 hours at a temperature of ~40°C, and then, after evaporation in the lungs solvents, the reaction mass is allowed to stand for 1 hour at a temperature of ~140°C. Receive 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]tiophene General formula (1) with output 44-67%. The reaction proceeds according to the scheme:

Target products (1) are formed only with the participation of cyclonona-1,2-diene and Alka-1,2-dienes, EtMgBr, e is Amantai sulfur S 8, magnesium and catalyst Cp2TiCl2. In the presence of other catalysts based on transition metal complexes (for example, Zr(acac)4Cp2ZrCl2Pd(acac)2, Ni(acac)2, Fe(ASAS)3target products (1) are not formed.

Conducting the reaction in the presence of a catalyst Cp2TiCl2more than 14 mol.% in relation to cyclonona-1,2-diene does not lead to a significant increase in the yield of the target products (1). Use in the reaction of the catalyst Cp2TiCl2less than 10 mol. % reduces the yield of bicyclic teofanov (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 target products (1). The reduction in the number of EtMgBr or elemental sulfur S8in relation to cyclonona-1,2-diene or Alka-1,2-diene reduces the output of the bicyclic teofanov (1).

Significant differences of the proposed method:

In the proposed method are used as starting compounds cyclonona-1,2-diene and Alka-1,2-diene, EtMgBr and elemental sulfur S8. In the known method bicyclic thiophene (3) receive from diacetylene, utility and polularity sulfur (S2Cl2) in what emeniem Cp 2ZrCl2in stoichiometric amounts.

The proposed method has the following advantages:

The method allows to obtain high selectivity to 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]tiophene General formula (1), the synthesis of which are 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 Cp2TiCl2, 10 mmol cyclonona-1,2-diene, 10 mmol OCTA-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 6 hours at a temperature of ~40°C, then 1 hour at a temperature of ~140°C. Receive individual 2-hexyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]thiophene to yield 58%.

The spectral characteristics of 2-hexyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]thiophene (1).

An NMR spectrum1H (400 MHz, CDCl3): 6.41 (1 H, s); 2.80 (2H, t, J=6.0 Hz); 2.71 (2H, t,
J=7.6 Hz); 2.62 (2H, t, J=6.0 Hz); 1.65 (6 H, m), 1.34-1.46 (12 H, m), 0.92 (3H, t, J=6.0 Hz). An NMR spectrum13(100 MHz, l3): 141.6, 137.9, 136.2, 126.3, 31.4, 31.3, 30.1, 29.5, 29.3,28.3, 27.8, 27.4, 26.5, 25.1, 24.4, 22.4.14.0.

Other examples of the method shown in the table.

№№ p/pAlka-1,2-DienThe molar ratio of cyclonona-1,2-diene: Alka-1,2-diene: EtMgBr:Mg:S8:Cp2TiCl2mmolReaction time, hoursOutput (1), %
1OCTA-1,2-Dien10:10:24:20:24:1.21458
210:10:26:20:26:1.21461
310:10:22:20:22:1.21453
410:10:24:20:24:1.41467
510:10:24:20:24:1.01444
610:10:24:20:24:1.2 1565
710:10:24:20:24:1.21349
8DECA-1,2-Dien10:10:24:20:24:1.21456
9dodeca-1,2-Dien10:10:24:20:24:1.21451

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

The method of obtaining 2-alkyl-5,6,7,8,9,10-hexahydro-4H-cyclonona[b]-teofanov General formula (1):
,
where R=n-C5H11n-C7H15the h9H19,
characterized in that the mixture of cyclonona-1,2-diene and Alka-1,2-diene (OCTA-1,2-diene, DECA-1,2-diene, dodeca-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-the yen : Alka-1,2-diene : EtMgBr : Mg : Cp 2TiCl2=10:10:(22-26):20:(1.0-1.4), preferably 10:10:24:20:1.2, 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 6 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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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%.

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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.

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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.

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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%.

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