DE1298525B - Process for the preparation of cyclooctadiene (1, 5) from butadiene in the presence of a complex nickel catalyst - Google Patents

Description

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It is from the German patent specification 951213,, As an ester of phosphorous acid is used knows that you can butadiene in the presence of nickel, the lower aliphatic alcohols or the catalysts of the composition phenols. You can also use mixed aliphatic-aromatic

IYR (T> Pl ΝιΎΓΩΊ matic esters. For example, one can use

w ^ js j * uuvv ^ 4- * ₅ triethyl phosphite, tri-isobutyl phosphite, triphenyl

where R is an alkyl or aryl radical and jc is at least phosphite or tricresyl phosphite. One means 1, at an elevated temperature and an elevated temperature, phosphorous acid esters can also be used, which can dimerize under pressure to give cyclooctadiene (1,5). There- fore polyhydric phenols and substituting phenols are formed in considerable amounts. B. of catechol, resorcinol, hyhexene (l) as a by-product. The yield is io drochinon, chlorophenol, p-chlorophenol, the nitro About 18 ° / _0th . phenols, guaiacol or thymol.

It is also in the German patent specification 881511. The dimerization of the butadiene is carried out in acidic, that cycloolefins with at least 8 substance-free and anhydrous, inert diluents and solvents and more carbon atoms in the ring of butadiene are solvents. These can be of various types, and acetylene can be obtained at elevated temperature, e.g. B. are aliphatic, cycloaliphatic and if, starting from Ni (CO) ₄ , a catalyzed aromatic hydrocarbons, such as η-hexane, n-Ocsator, in which at least one of the CO groups, their isomers and higher homologous, as ₄ groups of Ni (CO) by a compound of the 3wertigen gasoline fractions, preferably with a Siedebe phosphor, for example a phosphine or phosphite, ranging from 60 to 25O ⁰ C, is substituted further benzene, toluene, xylene. In this procedure, in addition to 20 cyclohexane, decahydronaphthalene are formed; you can also use about 45 ° / ₀ cyclooctadiene (1.5) or a considerable excess of liquid butadiene or cyclo amounts of compounds with a higher molecular octadiene (1.5) as a solvent. Also weighted as that of cyclooctadiene (1.5). The waste is liquid carboxamides, such as formamide, separation of cyclooctadiene (1,5) from such methylformamide, Ν, Ν-dimethylacetamide, N-methyl bonds in pure form is with great difficulty- 25 pyrrolidone, N-butylpyrrolidone or higher boiling points connected. aliphatic open _; or ring-shaped ethers, such as di-

It is the subject of the older German patent butyl ether, tetrahydrofuran, dioxane and ketones, 1140 569, by catalytic dimerization of 1,3 z. B. acetone, cyclohexanone, can be used. Based on diolefins to produce cyclooctadienes, using the solvent both the catalysts described, which are used by mixing 30 organic nickel compounds with Ovalent nickel, carbon monoxide-free compounds of nickel with and the phosphites in amounts of 1 to halogen-free organometallic compounds such as 10 percent by weight. However, the reaction takes place metal allyls, metal aryls or, like metal hydrides, also with smaller amounts of the cited catalyst or with metal hydride complex compounds and elec- tronic components,
tron donors arise. 35 The Dimerization of Butadiene to Cycloocta-

It is also the subject of the older German Pa- (l, 5) generally takes place in a tents 1144268, at the catalytic Cyclodimerisa- temperature range from room temperature to 250 ⁰ C, butadiene to cyclooctadiene- (1.5) as Kataly- preferably at 60 to 150 ⁰ C. You carry out a nickel complex compound with a sator with less than pressure, which is derived from the vapor pressure of the buta-4 ligand to use, the reaction of 40 diene and the solvent used in the ge-Nickel-bis- (acrolein),, Nickel-bis-tetracyanoethylene). given temperature results as total pressure, with- or nickel-bis-Cacrylsäurenitril) with esters of phosphos for example in the range from 10 to 20 atm. Phosphorous acid can be obtained and, however, higher pressures can also be selected before using it, in that inert ones have been isolated. Gases such as nitrogen, noble gases, saturated carbon

It has now been found that cycloocta 45 water or carbon dioxide is injected.
diene- (l, 5) in good yield and simpler manner from It is advantageous to carry out the dimerization in the presence of

Carry out butadiene in the presence of a diluent in the case of polymerization retarders in order to avoid the increased temperature and pressure in the presence of moisture and to prevent the formation of straight-chain polymers from butadiene. As such a retarder are particularly complex nickel catalyst, which is composed of a carbon 50 phenolic compounds, z. B. hydroquinone or monoxide-free organic Ovalent Nickelverbin- amines, such as Ν, Ν'-diisopropylphenylenediamine.
The dimerization can be discontinuous

has been made, if one is carried out as Nickelver as well as continuously. A disconnection Nickel-bis (tetracyanoethylene), nickel-bis-continuous implementation of the invention (acrylonitrile) or nickel-bis- (acrolein) used 55 Process can be carried out in such a way and the starting materials for the formation of the catalyst that the catalyst under air and moisture at the same time with butadiene exposes the reaction conditions to the exclusion of the solvent in a car, klav brings in and adds the liquid butadiene.

The Ower- The autoclave used as the catalyst components is heated to the reaction temperature ertigen nickel compounds and phosphorous acid ester 60, for example 60 to 150 ⁰ C. provides this case, in an inert diluent are mixed in a pressure in a pressure vessel, depending on the solvent used optionally. Then butadiene is added, which is between 10 and 20 atmospheres. After pressing and the mixture is heated. In the process, the coolant is formed, an effective catalyst system which is liquid at room temperature is obtained, and at the same time the reaction product, which may be used after the butadiene has been dimerized, is used. 65 tration is fractionated. The main

Of the carbon monoxide-free organic compound fractions cyclooctadiene (1,5) in addition to 4-vinylcyclodungen with Ovalent nickel, the easily accessible hexene (1).
borrowed nickel bis (acrylonitrile) are preferred. The process can also be carried out continuously

shape by running the butadiene dimerization in a so-called sump or trickle process leaves. In one case, the butadiene is kept at the reaction temperature and pressure Injected reaction mixture of the catalyst components and the solvent. in the otherwise the butadiene is used together with the catalyst components and the solvent passed under given temperature and pressure conditions over large-area moldings.

Both pure butadiene and butadiene mixtures can be used with the catalyst system described with other unsaturated hydrocarbons, such as those obtained from cracking, to form cyclooctadiene- (1.5) dimerize.

An advantage of the procedure described is that the dimerization of butadiene is less extensive The formation of high-boiling and resinous by-products is suppressed. Another The advantage is the very favorable ratio of cyclooctadiene (1.5) to 4-vinyl-1-cyclohexene, which is above 5: 1, to see. Finally, the method of operation according to the invention is also much easier to carry out than that previously known method.

example 1

A mixture of 1.5 g of nickel bis (acrylonitrile) and 3 g of tri-p-cresyl phosphite in 40 ml (= 31.2 g) of oxygen-free and anhydrous cyclohexane containing 200 mg is poured into a 250 ml pressure vessel under nitrogen Filled with hydroquinone. 29 g of liquid butadiene are injected into the closed pressure vessel. The pressure vessel is ^{heated to HO 0} C for 12 hours with shaking. The reaction mixture is then distilled under reduced pressure. 54 g of distillate pass over in the range from 75 to 125 ° C. at 25 torr, the distillation residue is 4.5 g. Gas chromatographic analysis shows that 19.4 g of cyclooctadiene and 3.9 g of 4-vinylcyclohexene (l) are contained in the distillate.

Example 2

However, the procedure is as in Example 1, the reaction mixture is heated only to 8O ⁰ C, is obtained in the distillation of 46.5 g of distillate (boiling range 75 to 125 ° C / 25 torr) and a distillation residue of 4.5 g. In the distillate, 14.9 g of cyclooctadiene (1.5) and 1.3 g of 4-vinylcyclohexene (l) are determined by gas chromatographic analysis.

Example 3

A mixture of 1.5 g of nickel bis (acrolein), 5 g of tri-p-cresyl phosphite and 30 g of liquid butadiene in 40 ml (= 31.2 g) of cyclohexane with 200 mg hydroquinone filled. The pressure vessel is ^{heated to 135 °} C. for 12 hours while shaking. Working up as in Example 1 gives 45.5 g of distillate (boiling range 75 to 125 ° C./25 Torr) and 9 g of residue. In the distillate, 14.3 g of cyclooctadiene (1.5) and 3 g of 4-vinylcyclohexene (l) are determined by gas chromatography.

Example 4

A mixture of 1.5 g of nickel bis (acrylonitrile) and 5 g of tri-p-chlorophenyl phosphite in 31.2 g of cyclohexane and 200 mg of hydroquinone is poured into a 250 ml pressure vessel. After 21 g of liquid butadiene have been injected, the mixture is ^{heated to 120 °} C. for 12 hours. If the reaction mixture is worked up as in Example 1, 46.5 g of distillate and 1 g of non-volatile resin are obtained. The distillate contains 12.6 g of cyclooctadiene (1.5) and 2.2 g of 4-vinyl-cyclohexene (l). Based on the total amount of butadiene reacted, the following yields result:

Cyclooctadiene (1.5) = 80%
Vinylcyclohexene = 13.7%
Resin = 6.3%

Example 5

A catalyst mixture of 15.5 g of nickel bis (acrylonitrile) and 20 g of tri-p-cresyl phosphite is introduced into a 3 l stirred autoclave under nitrogen. 700 ml of oxygen-free and water-free cyclohexane are used as the solvent. The main amount of nitrogen is removed from the autoclave by brief evacuation and the butadiene is continuously injected from a steel bottle under a vapor pressure of about 2 to 3 atmospheres. The autoclave is heated to 70 ° C. with rapid stirring and held at this temperature for about 8 hours. 1959 g of a red-brown liquid are obtained as the reaction mixture. From 1847 g of this mixture, after distilling off the unreacted, dissolved butadiene and the cyclohexane used as solvent, 1150 g of residue are obtained which, in addition to the catalyst (33 g), contains the reaction products of butadiene. Fractional distillation through an effective column gives 785 g of cyclooctadiene (1.5), n% ⁵ 1.4919, and 104 g of 4-vinylcyclohexene) and 242 g of residue at 150 to 151 ° C / 760 torr. The cyclooctadiene yield is 70%, based on converted butadiene.

Claims (1)

Claim: Process for the preparation of cyclooctadiene (l, 5) from butadiene in the presence of a diluent at elevated temperature and pressure with exclusion of moisture and oxygen in the presence of a complex nickel catalyst consisting of a carbon monoxide-free organic nickel compound and an ester of phosphorous acid is characterized in that the nickel compound used is nickel bis (tetracyanoethylene) or nickel-bis (acrylonitrile) or nickel-bis (acrolein) used and the starting materials for Formation of the catalyst simultaneously with butadiene exposing the reaction conditions.