DE955496C - Process for the production of polynuclear saturated and unsaturated hydrocarbons by polymerizing cycloocts - Google Patents

Description

Process for the production of polynuclear saturated and unsaturated Hydrocarbons by polymerizing cyclooctes It is known that one cyclooctene by treatment with concentrated sulfuric acid, in part to give A t 2-cyclooctenylcyclooctane can dimerize, but about 306 / o resinous, brown by-products are formed.

It has now been found that valuable polynuclear, colorless hydrocarbons can be obtained obtained when boron trifluoride is used on cyclooctene, expediently in the form of its complex compounds with water, alcohols, ethers or carboxylic acids, can act and the obtained unsaturated products, if desired, catalytically hydrogenated.

The conversion already takes place at ordinary temperature; one leads However, it is useful at about 70 to 1400, with one through if necessary Cooling ensures that the most favorable temperature is not determined is exceeded.

The amount of used - boron fluoride or its complex compounds as well as the nature of the latter can also influence the reaction be. In general, about 5 to 70% boron trifluoride is used, calculated on the basis of the increment the amount of cyclooctene to be converted, or the corresponding amount of its hydrate, alcoholate or atherats.

Indifferent diluents such as hexane, Use cyclohexane or cyclooctane.

The result is the action of boron fluoride or its complex compounds on the cyclooctene next to each other the z21 2-cyclooctenylcyclooctane of the empirical formula C16 H28 and a trimer Hydrocarbon with the molecular formula C24 H42. The proportion of the two hydrocarbons depends on the working conditions different; at lower temperatures, the yield of dimeric is generally Hydrocarbon higher. In any case, at most small amounts of not arise distillable resins.

The process can advantageously be carried out continuously, by the cyclooctene z. B. via a preheating zone qn an upright pipe lets in, in which a tightly fitting, second tube rotates, so that the Cyclookten in a thin layer between the inner wall of the outer and the outer wall of the inner Pipe flows downwards, whereby it is with the laterally supplied boron trifluoride or a boron trifluoride complex compound. The length of the tubes is selected and the feed rates are preferably such that the reaction occurs during the flow through is finished.

The polynuclear ones which are easily accessible in this way and in good yields Unsaturated hydrocarbons are valuable intermediates, especially for Manufacture of plastics and pharmaceutical preparations. The resulting in more usual Saturated hydrocarbons obtainable by catalytic hydrogenation have valuable lubricating oil properties because of their high boiling point and low pour point.

It was surprising that the cyclic olefin cyclooctene under the Effect of boron trifluoride or its complex compounds practically exclusively Di- and trimers supplies, while it is through concentrated sulfuric acid, which is common has the same effect on olefins as boron trifluoride, to a significant extent is converted into dark resins and does not provide any trimer.

The cyclooctene behaves towards boron trifluoride and its complex compounds different than other olefins. So z. B. the propylene by a boron trifluoride - Alcohol complex compound converted into isopropyl ether and polymerisation products (See H. Meerwein, Journ. Prakt. Chemie N. F., Vol. I4I, 1934, p.139), and the dem According to our own experiments, cyclohexene correspondingly built cyclohexene supplies below the conditions of the present process with boron trifluoride hydrate cyclohexanol and higher-boiling, also oxygen-containing products; on the other hand, one obtains unexpectedly from cycloocts both with boron trifluoride hydrate and with boron trifluoride alcoholates exclusively oxygen-free dimers and trimers in addition to only very small amounts of higher-boiling ones Shares.

The parts mentioned in the following examples are parts by weight.

EXAMPLE I 110 parts of cyclooctene are gradually stirred at from 5 to 100 parts 104 parts of boron trifluoride dihydrate and stir the mixture for about an hour at this Temperature. Then the cold bath is removed; at the same time the mixture begins to subside Warm brown color. Once the temperature has risen to 800 after about 2 hours is, you ensure by cooling that it does not rise higher. After another 20 up to 30 minutes the temperature begins to drop again. The mixture is stirred for a few times Time without cooling or heating and then neutralizes it with external cooling by adding ice and dilute sodium hydroxide solution. The organic layer is separated, washed with water, dried over calcium chloride and under reduced pressure fractionally distilled.

At first I5.5 parts of unreacted cyclooctene and a flow boiling at bp I to about 100 ° over. Then distilled as the main fraction in an amount of 58 parts the zlt2-Cyclooctenylcyclooktan as a colorless, viscous Oil from Kr.5 1280 about. 32 parts of a trimeric hydrocarbon are obtained from the residue the empirical formula C24 H42 as a very viscous O1, which at Kr.0.5 at an air bath temperature can be distilled from I79 to I820.

The 3t 2-cyclooktenylcyclooctane shows the expected molecular weight (found: 222, calculated: 220), the hydrogenation number found is 107 (calculated In5) 1 the refractive index etD ° = 1.4957, the solidification point - 560 and the viscosity of 15.53 cSt (= Centistokes) at 200 resp.

2.35 cSt at go0. By catalytic hydrogenation with Raney nickel and Hydrogen at 20 to 100 at, and at 100 to 2000 it provides the cyclooctylcyclooctane, a colorless oil of bp 1 = 100 °; by reacting with carbon oxide and hydrogen 100 to 1400 and 200 at in the presence of Raney cobalt it goes into the I-cyclooctyl-2-methylolcydooctane about that as colorless, .highly viscous, odorless 01 with bp 0.4 = 148 to 1500 boils.

The trimeric hydrocarbon with the empirical formula C24H42 shows the hydrogenation number 78 (calculated: 77), the molecular weight 333 (calculated: 330), the refractive index n20 = 1.5289, the viscosity Io380CSt at 400 or 79.32cSt at go0. By catalytic Hydrogenation provides the saturated hydrocarbon with the empirical formula C24H44, a viscous oil of KP 1 = 206 to 214 °.

Example 2 - To 110 parts of cyclooctene are left with stirring at 800 gradually flow in 10.5 parts of boron trifluoride dihydrate, cooling for this ensures that the temperature does not rise above 95. As soon as the mixture after about 20 Minutes no more heat of reaction developed, the cooling bath is removed and the mixture is stirred continue until it has reached room temperature. When working up, as in the example I can take place, 38.5 parts of unchanged cyclooctene and 46.5 parts of d12-cyclooctylcyclooctane are obtained and 25 parts of the trimeric hydrocarbon of the empirical formula C24 H42.

Example 3 110 parts of cyclooctene are used as in Example I with 160 parts Boron trifluoride dialcoholate, where one the initially cooled mixture can be heated up to II5 ". In the work-up, 10 parts are obtained unchanged cyclooctene and 5.5 parts first run 45 parts zli2-Cyclooktenylcyclooctan and 49 parts of the trimeric hydrocarbon of empirical formula C24H42.

If, under otherwise identical conditions, only parts of boron trifluoride dialcoholate are used to 110 parts of cyclooctene, 15.5 parts of unchanged cyclooctene are obtained, 7.5 Parts first run, 54 parts of 2-cyclooctenylcyclooctane and 33 parts of the trimeric hydrocarbon the molecular formula C24 H42.

Example 4 To a boiling mixture of 110 parts of cyclooctene and 140 parts of cyclohexane are left without further external heating within 20 to 30 minutes 16 parts of boron trifluoride dialcoholate flow in at such a rate that the Mixture remains at the boil. Then the mixture, which has turned dark brown, is stirred further, until it has reached room temperature and works it up as in Example I. Man receives 26 parts of unchanged cyclooctene, 7 parts of first run, 47 parts of d12-cyclooctenylcyclooctane and 30 parts of the trimeric hydrocarbon of the empirical formula C24 H42.

Example 5 110 parts of cyclooctene are heated to 800 and left under Stir slowly adding dropwise 25 parts of boron trifluoride ether, while cooling ensures that the temperature does not rise above 11 0.

As soon as the reaction mixture no longer develops any heat of reaction, the cold bath is removed and stirring is continued until it has reached room temperature. In the work-up, which can be carried out as in Example I, 31 parts are obtained unchanged cyclooctene 49 parts of ifl2-cyclooktenylcyclooctane, 24 parts of the trimer Hydrocarbon of the empirical formula C24 H42 and 6 parts of a higher-boiling residue.

If the boron trifluoride-glacial acetic acid complex compound is used instead of boron trifluoride etherate, in this way, under the conditions described above, one obtains in addition to unchanged cyclooctene as the main fraction 51 parts of At 2-Cyclooctenylcyclooktan and from the residue 25 Parts of the trimeric hydrocarbon with the empirical formula C24 H42.

Claims (1)

PATENT CLAIM: Process for the production of polynuclear saturated and unsaturated hydrocarbons by polymerizing cycloocts with acidic ones Agents, characterized in that boron trifluoride, expediently in the form of its complex compounds with water, alcohols, carboxylic acids or ether, allowed to act and the resulting cyclooktenylcyclooctane of the empirical formula C16 H28 and the unsaturated trimeric hydrocarbon with the empirical formula C24H42 if desired, catalytically hydrogenated. Publications considered: W. R e p p e, New developments in the field of acetylene and carbon dioxide, 1949, p.76; H. S. B o 0 th, boron trifluoride and its Derivatives, 1949, pp. 214 and 2I8.