RU2188813C2 - Method for joint production of e3,e8-dimethyl-trans-bicyclo[4,4,0]decane and e3,e9- dimethyl-trans-bicyclo[4,4,0]decane - Google Patents

Abstract

FIELD: industrial organic synthesis. SUBSTANCE: in a method of joint production of E3,E8- and E3,E9- dimethyl-trans-bicyclo[4.4.0]decanes, which are applicable as solvents in varnish- and-paint industry as well as high-octane additives for motor fuels, reaction mixture composed by cyclohexane and organoaluminum compounds, in particular R₃Al and R_nAlCl_3-n, wherein R represents ethyl, propyl, or butyl and n = 1; 1.5; 2, is completed by carbon tetrachloride or chloroform. Reaction is conducted in presence of transition metal complex or salt, in particular

Description

Предлагаемые соединения могут найти применение в качестве растворителей в лакокрасочной промышленности, высокооктановых добавок к моторным топливам, сырья в органическом синтезе.The invention relates to a method for producing dimethylbicyclo [4.4.0] decanes (C ₁₂ H ₂₂ ), and specifically to a method for the joint production of E3, E8-dimethyltransbicyclo [4.4.0] decane (I) and E3, E9-dimethyltransbicyclo [4.4.0] decane (Ii)

The proposed compounds can find application as solvents in the paint industry, high-octane additives to motor fuels, raw materials in organic synthesis.

 It is known that hydrocarbons of this series are present in significant quantities in oils. Methyl and dimethyl decalins from oils can be distinguished only in the form of the sum of a large number of structural and stereoisomers (E.I. Bagriy, I.A. Musaev, E. Kh. Kurashova, T.N. Dolgopolova, I.I. Sanin. Petrochemistry, Vol. 8, 6, 1968, 818), which are very difficult to separate in the future.

A known method (E.Kh. Kurashova, I.A. Musaev, V.N. Novikova, P.I. Sanin. Petrochemistry, t. 15, 2, 1975, 190) exhaustive hydrogenation of dimethylnaphthalenes to dimethyldecalin in an autoclave at 180 ^o and a hydrogen pressure of 120 atm in the presence of Raney nickel.

The known method (I.S.Akhrem, S.V. Witt, I.M. Churilova, A.V. Orlikova. Izv. AN, Ser. Chem., 1999, 12, 2304) to obtain a mixture of hydrocarbons C ₁₀ H ₁₈ , C ₁₁ H ₂₀ and C ₁₂ H ₂₂ , related to trans decalins and its methyl and dimethyl substituted, along with methyl substituted derivatives of cyclohexane and adamantane, obtained from cyclopentane in the presence of super electrophilic complexes of the type CBr ₄ • 2AlBr ₃ at 20 ^o C for 0 , 5-2 hours. However, the total yield of all cycloalkanes is not more than 27%, and the decalin yield is not more than 13% relative to the initial cyclopentane.

 Thus, the literature methods for producing decalin have significant drawbacks. Isolation from oil requires the use of laborious methods for the separation of mixtures with close boiling points and the result is a product containing almost all isomers of dimethyldecalin. The method of hydrogenation of dimethylnaphthalene requires the use of high temperatures and pressure, as well as the use of scarce raw materials - dimethylnaphthalene. The method of obtaining the target product from cyclopentane has a low yield of the target product with low selectivity.

 A method for the joint production of E3, E8-dimethylbicyclo [4.4.0] decane (I) and E3, E9-dimethylbicyclo [4.4.0] decane (II) is proposed.

The essence of the method consists in the interaction of the starting cyclohexane with an organoaluminum compound (AOC) R ₃ Al, R ₂ AlH, R _n AlCl _3-n , where R is C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ ; n is 1; 1.5; 2 and polychloromethane (CCl ₄ or CHCl ₃ ) in the presence of a complex or transition metal salt (PdCl ₂ Pd (acac) ₂ , Ni (acac) ₂ , Co (acac) ₃ , Fe (acac) ₃ , Cp ₂ TiCl ₂ ) taken in a molar ratio of 100: (4-13): (27-50): (0.079-0.132), mainly 100: 9: 32: 0.1. In order to avoid a violent exothermic reaction between AOS and polychloromethane, the reagents are mixed at a slightly lower or room temperature of 10-20 ^o C, adding polychloromethane to the mixture slowly dropwise. A further reaction is carried out depending on the activity of the reaction system at room temperature or with slight heating to 60 ^{° C.} and atmospheric pressure. The reaction time is 1-4 hours. The starting reagent cyclohexane is used as a solvent. The conversion of cyclohexane is 71-94%. The yield of target products I, II is 32-58%.

In all experiments, along with the target products, the formation of a small amount of polychloromethane conversion products (in the case of CCl ₄ : CHCl ₃ , CH ₂ Cl ₂ , CCl ₃ -CCl ₃ , CCl ₂ = CCl ₂ ), a number of alkyl substituted cyclohexane (methyl and dimethylcyclohexane) is observed 2-10%, mainly 5-6%, and unidentified compounds with a molecular weight of M = 180, 194, 206, 208, 248, amounting to 2-16%, mainly 10-16% of the starting cyclohexane.

Проведение реакции в присутствии алюминийорганического соединения больше 10 мол. % и меньше 9% по отношению к циклогексану не приводит к увеличению выхода продуктов I и II, но приводит к уменьшению конверсии циклогексана. Уменьшение выхода целевых продуктов наблюдается при уменьшении исходного полихлорметана меньше 10 мол. %. Конверсия циклогексана уменьшается при увеличении содержания переходного металла более 0,3 мол.%.The reaction proceeds according to the scheme.

The reaction in the presence of an organoaluminum compound is greater than 10 mol. % and less than 9% with respect to cyclohexane does not lead to an increase in the yield of products I and II, but leads to a decrease in the conversion of cyclohexane. A decrease in the yield of the target products is observed with a decrease in the initial polychloromethane less than 10 mol. % The cyclohexane conversion decreases with an increase in the transition metal content of more than 0.3 mol%.

 Significant differences of the proposed method.

 The proposed method is based on the use of an organoaluminum compound and polychloromethane, during the interaction of which, in the presence of catalytic amounts of transition metal compounds, cyclohexane is involved in the formation of predominantly two isomers of dimethyldecalin - E3, E8-dimethylbicyclo [4.4.0] decane (I) and E3, E9- dimethylbicyclo [4.4.0] decane (II).

 In the proposed method for the joint preparation of compounds I and II, affordable and cheap starting reagents are used. For the reaction described in Example 1 below, in accordance with the prices of the reagents listed in the well-known catalog "Organic and Inorganic Reagents for Chemical Synthesis", ALDRICH, 2000, the cost of 1 g of the obtained product is not more than 10 DM. In the most well-known method for the preparation of dimethyldekalin by exhaustively hydrogenating dimethylnaphthalenes according to the ALDRICH catalog, only the price of the starting 2,6-dimethylnaphthalene and 2,7-dimethylnaphthalene is 60 DM and 286 DM per 1 g, respectively.

 The proposed method allows to selectively obtain predominantly stereoisomers I and II with a yield of 40-50 mol.% Relative to the initial cyclohexane in one stage at low temperatures and atmospheric pressure.

 The method is illustrated by the following examples.

Example 1. In a 150 ml glass reactor mounted on a magnetic stirrer, 26 ml (241 mmol) of cyclohexane, 78.5 mg (0.256 mmol) of Pd (acac) ₂ and 5 ml of a 91% Et ₃ solution are placed under argon atmosphere. Al (30 mmol), at 7 ^{° C.} slowly, dropwise, preventing the reaction mixture from heating above 10 ^{° C.} , 8 ml (83 mmol) of CCl ₄ are added with constant stirring. The addition of CCl _{4 is} accompanied by evolution of a gas consisting of ethane and ethylene. Stirring of the reaction mixture was continued at 10-12 ^{° C. for} another 3 hours. The reaction was accompanied by evolution of HC1. At the end of the reaction, two layers are formed: a transparent upper layer and a dark brown viscous layer containing residues of organoaluminum compounds, the lower layer. The top layer was selected, passed through Al ₂ O ₃ . GLC analysis of the resulting colorless transparent liquid (20.3 g) showed a dimethyl decalin content of 30% and unreacted cyclohexane 24%. Fractional distillation with a reflux condenser in the temperature range of 200-220 ^o With gives 4.5 g of a liquid containing 49% of isomer I, 38% of isomer II, 2-3% of 4 unidentified isomers of dimethyldecalin with M ⁺ = 166 and 5 isomers with M ⁺ = 166 0.2-0.3%.

¹³ C NMR spectrum of compound I (δ, ppm, literature data in parentheses): 43.05 (43.0, C ¹ ), 43.05 (43.05, C ² ), 33.10 (33 , 1, C ³ ), 35.64 (35.6, C ⁴ ), 34.34 (34.2, C ⁵ ), 43.05 (43.0, C ⁶ ), 43.05 (43.0 , C ⁷ ), 33.10 (33.1, C ⁸ ), 35.64 (35.6, C ⁹ ), 34.34 (34.2, C ¹⁰ ), 22.89 (22.8, CH ₃ ), 22.89 (22.8, CH ₃ ), M ⁺ = 166.

¹³ C NMR spectrum of compound II: 43.25 (43.3, C ¹ ), 43.25 (43.3, C ² ), 33.10 (33.1, C ³ ), 35.77 (35.7 , C ⁴ ), 34.08 (34.0, C ⁵ ), 42.92 (42.9, C ⁶ ), 34.08 (34.0 C ⁷ ), 35.77 (35.7, C ⁸ ), 33.10 (33.1, C ⁹ ), 43.25 (43.3, C ¹⁰ ), 22.89 (22.8, CH ₃ ), 23.09 (22.8, CH ₃ ), M ⁺ = 166.

From the ¹³ C NMR spectra it follows that 4 unidentified isomers also have a trans-junction of rings and the equatorial position of methyl groups and differ from products I and II only in the position of methyl groups.

Example 2. In a glass reactor with a volume of 50 ml mounted on a magnetic stirrer, in an argon atmosphere at 22-23 ^o C is placed 7 ml (65 mmol) of cyclohexane, 15.7 mg (0.05 mmol) of Pd (acac) ₂ , 6 mmol Et ₃ Al and 1.4 ml (17.5 mmol) CHCl ₃ , heated to 60 ^o C and stirred. After 1.5 hours, the reaction mixture is stratified into 2 layers. The top layer was selected, passed through Al ₂ O ₃ . The obtained colorless transparent liquid contains products I and II of 46.5%, unreacted cyclohexane 19%, products of the composition C ₁₂ H ₂₂ 53.4%, 87% of which are compounds I and II.

 Other examples confirming the method are given in the table.

Claims (1)

The method of co-production of E3, E8-dimethyltransbicyclo [4.4.0] decane and E3, E9-dimethyltransbicyclo [4.4.0] decane, characterized in that to the reaction mass consisting of cyclohexane C ₆ H ₁₂ and an organoaluminum compound (AOC) R ₃ Al, R ₂ AlH, R _n AlCl _3-n , where R is C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ ; n is 1; 1.5; 2, polychloromethane (CCl ₄ or CHCl ₃ ) is added dropwise, in a molar ratio of 100: (4-13): (27-50), respectively, and the reaction is carried out in the presence of a complex or a transition metal salt of PdCl ₂ , Pd (acac) ₂ , Ni (acac) ₂ , Fe (acac) ₃ , Co (acac) ₃ , Cp ₂ TiCl ₂ as a catalyst, taken in an amount of 0.079-0.132 mol. % relative to the original cyclohexane, in an argon atmosphere at atmospheric pressure and a temperature of 10-60 ^o C for 1-4 hours

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