DE1043329B - Process for the production of cyclododecatrienes (1, 5, 9) among other ring-shaped hydrocarbons - Google Patents

Description

Process for the preparation of cyclododecatrienes (1, 5, 9) besides other annular hydrocarbons The invention relates to manufacture of cyclododecatrienes (1, 5, 9) along with other cyclic organic hydrocarbons with at least 8 carbon atoms and at least two double bonds in the ring, e.g. B. Cyclooctadiene and cyclohexadeca: tetraene (1, 5, 9, 13).

It has already been suggested that isoprene, piperylene and preferably butadiene from the action of Titanium halides and alkyl aluminum halides at temperatures up to 150 ° C are useful in the presence of solvents, to submit. Receives such a procedure one compounds with a 3-times unsaturated 12 ring with yields of over 80%. Study of the infrared spectrum of the compounds obtained by this method has shown that the compounds of the cyclododecane series formed are essentially compounds in which two double bonds in the ring are to be assigned to the trans conguration, while the third double bond is to be assigned to the ciiS conguration listened to.

It has now been found that cyclododecatriene- (1, 5, 9) of the general Formula C12X18, in which X is hydrogen or methyl, among others ring-shaped Hydrocarbons also through the reaction of butadiene, isoprene or piperylene in the presence of catalysts made from chromium halides and aluminum hydrocarbons can. Instead of the starting materials mentioned, gas mixtures can also be used as starting materials. Use materials that contain the dioloefins. The technical ones are particularly suitable easily prepared dehydrogenation products of butane or butylene.

The catalysts can be aliphatic or aromatic aluminum hydrocarbons, preferably Aluminum trialkyls or aluminum alkyl hydrides, optionally also aluminum dialkyl monohalides, together with ear halides or oxyhalides or with mixtures of halides des s chromium included. Chromium is a particularly inexpensive catalyst (III) -chloride and aluminum trialkylene or aluminum dialkyl hydrides. The aluminum compounds reduce the heavy metal salt extremely easy. When working with catalysts made from chromyl chloride and aluminum triethyl, preferably in the ratio Cr: A1 = 1: 5, the reaction product essentially consists from trans-transtrans-cyclododecatriene- (1,5,9).

The diols can be reacted directly in the catalyst mixture or else work in the presence of solvents, expediently in the presence of aliphatic or aromatic hydrocarbons or halogenated hydrocarbons, e.g. B.

Benzene, toluene, chlorobenzene, dichlorobenzene or hexane.

The reaction proceeds already at ordinary temperature with good yields of over 50% and can be favored by increasing the temperature up to 150 ° C if necessary. It is also possible to operate at temperatures below -0 ° C, e.g. B. to -20 ° C to work. Man generally works at normal pressure, but can also work at reduced pressure or at Work at increased pressure. The process can be carried out continuously without further difficulty will.

In many cases, isomeric reaction products are formed, which can be fractionated by known methods Distillatino, or crystallization, can separate.

The ring-shaped compounds obtained are valuable starting materials for organic synthesis The ring-shaped organic compounds can thus be hydrogenated in a known manner, z. B. the cyclododacatriene- (l, 5, 9) to cyclododecene or cyclododecane. These hydrogenated products in turn can be in a known manner to the corresponding dicarboxylic acids, for. B. dodecane-1, 12-diacid, oxidize.

On the other hand, the cyclododeca.trien- (1, 5, 9) can be directly assigned Succinic acid oxidize.

These dicarboxylic acids are known to be valuable starting materials for plastics, z. B. polyamides and polyesters dissolved under nitrogen. After adding 1 g of finely powdered anhydrous chromium (III) chloride the mixture is stirred for 15 hours at room temperature. The solution turns dark due to the extremely finely divided catalyst. A part of the chromium (III) chloride is not converted under these conditions. One saturates mix with pure butadiene and stir for 48 hours at room temperature. Thereafter the catalyst is decomposed with a little methanol and the solution with dilute sulfuric acid and water washed. The solution is dried with calcium chloride. Is out of solution Can be precipitated in a polymer with acetone. Distilled after removing the solvent the residue in vacuo. 5 g of trans-trans-trans-cyclododecatriene (1, 5, 9) b.p. 13 = 95 ° C, which was already in the Claisen flask during the vacuum distillation Crystallized into beautiful long needles. Melting point 34 ° C. Yield 50%. The infrared analysis clearly showed that it is the trans-trans-trans compound because in the spectrum are the absorption bands characteristic of middle cis double bonds no longer detectable.

The hydrogenation of the crystalline product gives perfect results Cyclododecane.

Example 2 In 100 cc of absolute benzene, 0.5 cc of chromyl chloride becomes dissolved and under argon with 3.1 cc of diethylaluminum hydride (molar ratio Cr: Al = 1: 4, 7) offset. The mixture warms up slightly; it is stirred for 15 minutes, during which a dark brown catalyst suspension forms.

Pure butadiene is introduced with vigorous stirring, the temperature rises to 40 ° C. The solution is kept saturated in butadiene by introducing further gas. In the course of 2 hours the temperature drops to 30 ° C. The butadifene stream is turned on and the mixture is stirred for a further 15 to 16 hours at room temperature. After this After a while, the solution no longer contains any unreacted butadiene. 24 g of butadiene were taken up. The approach is worked out as described in Example 1. During the distillation 17 g of trans-trans-trans-cyclododecatriene (1,5,9) are obtained, which crystallizes immediately. Yield 71 (t. After recrystallization from ethanol the melting point is; t 34'C.

Example 3 In 100 ccm of absolute benzene, 0, 48 ccm = 6 mmol of dissolved bromyl chloride. Slowly drop 3, 3 into this solution cc = 24 mmoles of aluminum triethyl. The mixture warms up.

Pure butadiene is now introduced, the temperature slowly increasing increases. Keep the temperature at 50 ° C by carefully cooling with compressed air. at using this procedure, 60 to 65 g of butadiene are absorbed in the course of 3 hours. The flow of butadiene is then turned off while the mixture is left on for a further 2 hours Keep stirring vigorously so that the dissolved butadiene reacts completely. One decomposes the catalyst with a little methanol and the solution was washed with dilute sulfuric acid and water. From the solution, dried with calcium chloride, one can et-, Precipitate 1 g of butadiene polymer. The solution is worked up by distillation. 53 g of cyclododecatriene (l, 5, 9) are obtained, about 65 "/ oa, usdertrans-trans-trans-Ven bond exists next to the trans-trans-cis connection. The distillation residue is 10 g, yield 83% the theory.

Example 4 The procedure is as in Example 2, but an absolute value is used Toluene as a solvent. The reaction proceeds in the same way. Yield of cyclododecatriene- (1, 5, 9) 71% of theory.

Example 5 The procedure is as in Example 2, but an absolute value is used Chlorobenzene as a solvent. The reaction proceeds in the same way. yield in cyelododecatriene- (1,5,9) 71% of theory.

Example 6 The procedure is as in Example 3, but hexane is used as the Solvent undergoes the cyclododecatriene (1, 5, 9) in 60 "/ Mg yield.

EXAMPLE 7 In 11 absolute benzene, 4.8 cc of chromyl chloride are converted dissolved and treated with 33 cc of aluminum triethyl under argon. The mixture heats up easily, you stir them for 15 minutes, whereby a dark brown catalyst suspension forms. 400 g of isoprene are added dropwise at 50 ° C. over the course of 3 hours. Included there is a germ temperature increase.

The reaction mixture is stirred for a further 18 hours held at 40 ° C. The approach is then carried out in the manner described in the example worked up. The dried solution is distilled.

In addition to unchanged isoprene and benzene, a b.p. g = is obtained 50 to. Fraction boiling at 130 ° C, 160g. The amount of residue is 110g. He exists from tetrameric and higher molecular substances. The fraction boiling up to 130 ° C is subjected to a fine fractionation, the 90 g of a at bp 12 = 135 ° C, nD20 = 1, 5125 gives a substance passing over, which corresponds to a trimethylcyclododecatrium- (l, 5, 9) corresponds to what is confirmed by infrared spectrum and catalytic hydrogenation'.DisMethylgruppen are at the double termination carbon collision atoms.

Example 8 Proceed as indicated in Example 7 and set the catalyst of 0.5 cc of chcomyl chloride and 3.3 cc of aluminum triethyl in 100 cc of absolute benzene. 45 g of piperylene are obtained with this catalyst suspension Vigorously stirred for 24 hours at 50 ° C.

With analog processing and subsequent fine fractionation a trimethylcyclododecatriene (1, 5, 9) of b.p. 25 = 92 to 94 ° C, nD20-1, 4910 to 1,4930, which is confirmed by catalytic hydrogenation and infrared analysis. The methyl groups are located on the carbon atoms adjacent to the double bonds.

Claims (5)

PATENT CLAIMS: 1. Process for the production of cyclododecatriene (1, 5, 9) along with other ring-shaped hydrocarbons with at least 8 carbon atoms and at least two double bonds in the ring, characterized in that butadiene, Isoprene or piperylene in the presence of catalysts made from chromium halides and aluminum hydrocarbons, expedient in the present of solvents such as aliphatic, aromatic or halogenated hydrocarbons, at temperatures between -20 and + 150 ° C, preferably at about 40 ° C, can react. 2. The method according to claiml, da'durdh characterized in that the catalysts Contain aluminum trialkyls or aluminum alkyl hydrides. 3. The method according to claim 1 and 2, thereby geken. nzeictmet that the catalytic converters mixes various chromium halogen dl e included. 4. The method according to claim 1, characterized in that Ka. talysaiofen made of chromyl chloride and aluminum triethyl, preferably in proportion Cr: A1 = 1: 5, used. 5. The method nach'Anspruchlbis4, characterized in that as Benzene solvent used. Documents considered: British Patent No. 701 106.