DE693862C - Process for the production of decacycles - Google Patents

Description

Process for the production of decacycles It is known from the literature that when a mixture of acenaphthene and sulfur is heated, the hydrocarbon decacycles formed from 3 molecules of acenaphthene and the sulfur-containing dinaphthylenethiophene are formed. According to K. ID zi ew onsky (Ber. 36, 965, 1903) a mixture of acenaplhthene and sulfur is first heated to 2o5 °, during which vigorous evolution of hydrogen sulfide occurs. After this has subsided, D ziewonsky heated the reaction mixture further to 29o to 294 °. After P '. Rehländer (Ber. 36, 1584, 1903) a mixture of aoenaphthene and sulfur is also heated to 19o to 200 °. In both cases, some decacycle is formed in addition to copious amounts of dinaphthylenethiophene, from which it is separated by successive extraction with alcohol, benzene, toluene and xylene, which, given the almost identical solubility ratios of the two compounds, creates considerable difficulties. Dziewonsky gives the yield as 20%, while O stro-my ss 1 ensky (Journ. Pr. Chem. 76, 269, 1907) found that, from zoo g acenaphthene, only 4 to 5 g pure Deka! -cyclen are available.

It has now been found that the formation of dinaphthylenethiophene can strongly suppress and obtain decacycles in technically good yields, if one does not heat the Acenaphthen-Schwefel-Gemis.ch, but the sulfur at temperatures above 23o °, expediently in the vicinity of the boiling point of acenaphthene, after and after entering into molten acenaphthene in small portions, so that one at a time the lowest possible sulfur concentration is present.

It was also found that. the processing of the, melt through the use of chlorinated hydrocarbons resistant to decacycles, preferably Tetrachlorätha, much simplified and a complete separation of the thiophene derivative is made possible.

For better handling of the reaction mass, it is advantageous from the outset worked in the presence of solvents with suitable boiling points. Therefor for example i-chloronaphthahn, trikresyl phosphate, diphenyl ether and diethylene glycol in question. You can also submit the Dekacyclen yourself.

Under certain circumstances it may be advisable to add hydrogen sulfide to the reaction mass to add separating agents and agents which prevent resin formation; of the former become copper, nickel, mercury oxide and lead oxide, of the latter the compounds known as antioxidants, such as hydroquinone, hydroquinone dimethyl ether and a-naphthol. Working in the absence of air can also be advantageous. The process allows the industrial production of the decacycle.

EXAMPLE i In 100 parts of acenaphthene heated to 265 °, 36 parts of sulfur are gradually added in small portions, the end of the evolution of hydrogen sulphide having to be awaited before each new addition. After cooling, the melt is ground and stirred with tetrachloroethane, suction filtered and washed so long, are removed to dark accompanying substances and yellow to orrangegelbes crystalline powder remains. This residue is heated to the boil with five times the amount of tetrachloroethane, no solution taking place, and, after cooling to about 60 °, suctioned off. The residue is pure decacycle in a yield of 420/0. Example 2 36 parts of sulfur according to Example i are introduced into a mixture of 100 parts acenaphthene and 100 parts tricresyl phosphate, heated to about 270 °. After the reaction has ended, the mixture is allowed to cool to 120 °, 300 parts of tetrachloroethane are stirred in and, after cooling, is filtered off with suction. The residue is treated further as above; decacycles are obtained in a yield of 41%.

Example 3 100 parts of acenaphthene heated to 275 ° produce 36 parts Entered sulfur according to Example i. Then it is cooled to about 180 ° Melt with 1 ¢ o parts of tetrachloroethane, which is preheated to 85 °, mashed. After cooling to 70 °, the mash is sucked off. The backlog is already after single washing according to example i pure decacycle. The yield is 42 %.

Claims (1)

PATENT CLAIM: Process for the production of decacycles by fusing of Aeenaphthen and sulfur at temperatures above 23o °, preferably at about 265 to 27o °, characterized in that the sulfur is in molten acenaphthene is entered in small proportions one after the other, where appropriate in presence is worked by solvents.