DE767317C - Process for the production of cycloparaffins - Google Patents

Description

Process for the production of cycloparaffins Ers -, vurclo found that you can use cycloparaffins of the kind of cyclooctane and its '' higher homologues easily and with good can produce prey, 'if you have cyclooctote- traen or higher cycl (x @ lefine of the formula C. " " 14 " ", where n is a larger number <Lls .f, lx-.i ordinary or elevated temperature in the presence of catalysts whose active constituent of iron, K «I) old, Nickel or copper) with hydrogen treated: . Rlin'hm already cyclooctane by hy- dritrung% -one cyclooctotetraene in presence- is made of platinum, but this has proceed dtti disadvantage, <leave the catalyst is expensive and that hydrogenation is essential runs slower. The catalysts can be skeletal or Alloy catalysts or on carriers can be applied. As skeleton catalogers are particularly suitable by merging, of aluminum or silicon with iron, lobalt and \ icktl: received lxnieni @ ine @ i, from which the less noble I t lecnent removed, for example by treatment with alkali lye is dissolved out wordcta. : \ 1s Oil-in-use catalysts come in particular those made of nickel and chrome, cobalt and chrome or nickel, chromium and copper Alloys into consideration. Supported catalysts is obtained, for example, by precipitating iron, cobalt, nickel or copper salts or their mixtures on the usual carriers, e.g. B. active coliles, silica gel, fuller's earth, pumice stone, bentonite. active alumina, asbestos or barium sulfate, and reduction of the catalysts obtained before use in a hydrogen stream, optionally with the addition of diluents such as water, alcohols, ethers or hydrocarbons. The catalysts can, however, be hydrated only in the presence of the cyclopolvolefin or mixture of cyclopolyolefins to be hydrogenated. Furthermore, the 1letallkatalvsatoren the usual in hydrogenation activators are incorporated, z. B. Oxides and Hydraxes of the Metals of the First to Seventh Groups - of the Periodic Svsbecns.

You can either in the liquid phase or in the gas phase, if appropriate hydrogenate under elevated pressure, continuously or discontinuously can work. Used in continuous hydrogenation in the liquid phase one expediently a trickle process, called the liquid starting material Flows over the catalyst, while the hydrogen is conducted in cocurrent or countercurrent will.

You can also use solvents or diluents, e.g. B. water, alcohols; such as methanol, ethanol, butanol or cyclohexanoI, ethers such as tetrahydrofuran, di-n-butyl ether or diethyl ether, hydrocarbons such as cyclohexane or isooctane, and also chlorohydrocarbons. The hydrogen can also be diluted, for example by nitrogen or water vapor. The most suitable temperatures for the hydrogenation are between 0 and 300 °; it is advisable to work at temperatures between? o and 25o3.

It is known that Cvclooktan by catalytic hydrogenation of cyclooctadiene to manufacture. The starting material of this process differs from the analogue one of the present. Procedure due to a shortage of two double bonds. In view of the known fact that Cyclohexene and others partially hydrogenated aromatic hydrocarbons are much more easily hydrogenated to cycloparaffins than benzene, one could not expect that in the hydrogenation of the higher, The base N-Ieta11 catalysts are dissolved analogously to benzene enabled a particularly high hydrogenation rate. It is also owned - # corden, cyclooctotetraene behave like a conjugated system with an open Chain, but this does not correspond to the facts, so that this assertion also does not Aure-ung could go to hydrogenate cyclooctotetraene in kind of base metals. Present-It processes are already known, cycloparaffins from other starting materials to manufacture. So one already liat multiple cyclic ketones with amalgamated "Reduced zinc. Besides that a catalytic hydrogenation is technically easier is, this known method has the disadvantage that cyclic concretes are finite large number of chain links are difficult to access in large quantities. In contrast are the starting materials of the present process easily by self-condensation can be produced from acetylene.

The parts given in the following examples are parts by weight. Example i A solution of 6 parts of cyclooctotetraene in 440 parts of methanol is used add about 20 parts of a nickel skeleton catalyst. which by decomposition of a .NN nickel-aluminum alloy with 34% nickel content produced using caustic soda has been. Hydrogen is pressed into the mixture in a high-pressure vessel made of stainless steel below 15o atm. Press on at room temperature until the pressure no longer decreases. Since the resulting Cvclooktane is only partially dissolved in the ethanol, one can -first cut off the undissolved part. This is driven out of the methanolic layer Methanol and the residue is distilled off together with the rest of the cyclooctane (Kp7ii0 = 148.5 to 1: 19.5 °). The yield is 930/0, the cyclooctane obtained is very high pure.

If you treat a solution of 5z under otherwise identical conditions Parts of cyclooctotetraene in 91 parts of tetrahydrofuran give cyclooctane in # 92o / o yield. Example 2.

104 parts of cyclooctotetraene are present in the presence of 20 parts of the catalyst described in Example III with hydrogen below 150 = 1tm. Print treated at room temperature. When the reaction mixture is distilled, 100 parts of cycloactane are obtained, corresponding to a yield of 900/0. EXAMPLE 3 A mixture of 52 parts of cyclooctotetraene with 50 parts of methanol is mixed with 5 parts of a copper catalyst and the whole is traded at 100 ° and under a hydrogen pressure of 50 atm. until saturation. When calculating in the manner described in the example, matt receives .10 parts of cyclooctane. The catalyst is made, itl (lctti basic copper carbonate is used as a mixture with a little baritim carlx> tiat and zilil: carboii: tt precipitates on diatomaceous earth - and this then in aqueous suspension with hydrogen i5oAtm. Treated pressure at 20o °. Which he- paste is held before the addition to: \ tls- raw material through _, washing out with% letli: inol freed from water. example 5o parts of a mixture of Cychxlekap- taen and Cyölododekaliexaen (KP-, o = 17o to iSo °) is treated in: \ n @ \ - esenlieit of 5 parts of that described in example i Nickel catalyst with - hydrogen hot Room temperature below 50 atm. Pressure. When the hydrogen uptake decreases, ar- work at 4o to 5o 'and close Lich at 100 ° until the end of the hydraulic tion continues. The catalyst is filtered off and distill the filtrate. The distillate will diluted with the same amount of water, % resulting in two layers. The oily one Layer is separated from the aqueous layer separated and, this becomes exhaustive with Ligroin extracted. The ligroin extract one agrees with the oily layer and distilled loses the ligroin. The residue will fractionally distilled, with two main factions received: the first fraction tion (Kplg = ioo to i4o °) exists. in the essential from Cvclodekan. The second Fraction (KP, = T40 to 1801) appointed in essentially from cyclododecane. The yield of cyclodecane is 26 parts and of cyclo- dodecanese 9 parts. Example 5 5z parts_Cyclooktotetraen and io.4 parts Water with the addition of the in Example i described nickel catalyst with water fabric under 15o @tin. Pressure]> ei more common Temperature treated. llan receives 48 parts (. \ 't.'ll> (Jk11111, \\ 1t @ elnelll `@ ° al @ etl. V nisatz elite, praises. Ileispicl () Ztt e @ iiiei 'solution of tc) 4 @ Ceilen t @ \ - c1 (JC11 <- tf) tt`traetl 1n -oo l'elleti @ le.thal @@ T1 tll-t 111a11- lo parts of a Nid: el-Chrum-Lsatal \ 'sator (1o% Ni, 5o / oC1 '). which by = \ tlsf; Illegal v (-) li hieselsüuresol on pumice stone, zugeN i of nickel carbonate and Ciiromsütire and 48 hour reduction of the expired N ickelchroniats]> ei 320 to 400 'im \\ - as: er stoffstroin has been produced. The GE- it is mixed in a high pressure vessel Hydrogen under iSo Atin. Pressure up saturation hei treated 4o '. After loading the end of the reaction (read the product in the in Example i worked up manner described. The yield of cyclooctane is 80%.

Claims (1)

PATENT CLAIM: '' experienced in the production of cyclopa- refines by catalytic hydrogenation Cyclopolyolefnen, characterized in that that one Cvclooktotetraen or higher Cy- clopolyolefined formula C. = "H""\% - ol> ri ri a number greater than 4. and the number of Double bonds equal) a is, with ordinary lighter or higher temperature with water hydrogen in the presence of catalysts Treated that as an effective ingredient Iron, cobalt, nickel or hoppy keep. To limit the subject of the invention from the state of the art are in the granting consider the following publications drawn 7ror (len: Sabatier, "The Catalysis", German: \ us- gab> e, 1927, p. 139; Hückel, »Theoretical Foundations of organic clieniie ", l: d. 1. 3 .. \ titL 1 () 40. P. 501, .1bs. 2: TTrlvetica Chimica Acta, Vol. Il>. 5 .. () Sff.