DE666466C - Process for the preparation of monomeric condensation products - Google Patents

Description

Process for the preparation of monomeric condensation products It has been found that '.) kung of halogen-free aliphatic vinyl compounds based on aromatic 1 @ oillen «# water- substances in the presence condensing @@ irkender Medium valuable mononier l @ ondensationspro- products received. The condensation is useful in the Way done that you get the aromatic Hydrocarbon with the Vinvlverbindunz mixes and then the condensing agent added in small portions. One can also proceed in such a way that the l @ ondensations- medium in the aromatic hydrocarbon dissolves or suspends and thereby the valve compound vapor or llüssia, given at least by means of inert gases or lüsun, sinittel dilutes, introduces, or registers. The condensation occurs int all, in one already at room temperature and is usually strong etotlierm. In some halls it throws in however, the condensation by weak Initiate heating or accelerate it. Suitable vinyl compounds are e.g. B. the Viltvlesters of organic acids, such as 1'invlacetat, Vinvlpropionat, also the @ 'invlüther, «#ie met (Mäther, Vinyläthylüthcr, die @ 'iny @ a @ kvl- ketolie, like 'lethvlvinvlketon, = 1tht-lvinvll: eton, also the `` iiivlcarbons; iiii-eit, such as: 1crvic acid, lletllvlacrvläur, the @ -111 \ "I111Trlle, like: lcrvl- acid nitrile ti. like .. _11s condensation agents come e.g. B. the in the syntheses according to Hriedel-Crafts applied anhydrous metal halides, such as Aluminum chloride, aluminum bromide, boron fluo- rid, zinc chloride, ferric chloride, on its own or in Form of their reactive derivatives, such as Na- trium aluminum chloride, addition compounds from boron fluoride and: ethyl or methyl ether, also strong mineral acids, such as concentrated ones Sulfuric acid or phosphoric acid and the like, in Consideration. The amount of con- densification agent depends on the reaction ability of the vinvlconnection used applications and is available through a simple '"request easy to determine. Min general fill already small menzen, about r to 2 weight percent of vinyl compounds used, but in some cases it can be B. at the Application of inert vinyl compounds, it may be advantageous to use larger amounts of the condensate 5atlUnsinittelS apply. Although it is known to use benzene with Viitvlclilorid in the presence of full aluminum chloride but one cannot draw the conclusion from this draw, dab inan l:) eitzol and other aromatic lZolilenwasserstotie, search with halogen-free ali- phatic Viltvlverhiltduligen in the present can fully implement lZondensationsillmittel. Paint still has v @@ r @ escllla @ en, mixtures from aliphathclleIt @ -111 \ 'I1-el-lllil (IIIIteld and "-ztvrol to subject to a polymerisation, whereby mixed polymers are formed. In contrast, the reaction of aromatic hydrocarbons with halogen-free aliphatic vinyl compounds in the presence of condensing agents proceeds in a different direction; R-H + CH @ = CHR '-r R-CH.-C H ..- R' (R denotes the residue of an aromatic hydrocarbon and R ', for example, an alkoxy, Acvl, Carbotvl or nitrile group, etc.).

Example i In a solution of 100 parts of Vin @ -liithi-1-ether in 100 5 parts of anhydrous benzotene are concentrated with cooling and vigorous stirring Sulfuric acid slowly added dropwise. The condensation soon sets under weaker Yellow discoloration and temperature rise or fall. Man s (-. R-, t by suitable cooling that the temperature does not exceed 20 to 25 '. Once the condensation is finished, the reaction mixture is washed with water and then with \ atrnnlauae -, ewash, whereupon the residue remaining after the excess benzene has been displaced Vacuum is fractionally distilled. An oil with a boiling point of iSo to is obtained 22o`, which consists mainly of the ether of the phenolic alcohol.

EXAMPLE 2 5 parts of concentrated sulfuric acid are emulsified in 1,000 parts of benzene by vigorous stirring and then zoo parts of vinyl acetate diluted with nitrogen are introduced in vapor form. The reaction sets in with warming and yellowing and is over after a few hours. The processing takes place in the in ßi @ i @ piel 1 specified way. One obtains a (A. das boils between 2io and 2.43 ° and for the most part from the acetate of phenyl ether alcohol, 'i) (- @ teht. Example 3 To a mixture of '4.oo Teileii.; El @ eiizol and 13 parts of anhydrous aluminite chloride one gradually wears lilü li under ruffles and cooling 5 o parts acrvic acid. Na (-li ended a can be worn for about 13 hours, then pour the reaction mixture onto ice and works on as usual. 'You get a solid Body from which one isolates hydrocinite can. If you use the: \ cr @ -Iainrc instead of the equivalent amount: acrylic acid nitrile, #, 11 obtained one phenylpropionitrile. example 26o parts of \ aphtlialin are heated in one Pressure vessel with 150 parts @% inylmctlivlketon, io parts fuller's earth and i part H% - (1r (iciiinon At 16o ° for 10 hours. "After this. Obtain one dissolves the reaction mixture in ther and filtered from the bleaching earth. Scar that Evaporation of the ether is distilled in the Va- kuum and thus receives a jerk under 1i min i) Liell, yellow, boiling between 138 and 16o ° 01 that gradually increases when standing in the air turns brown. Acts on the basis of the analysis it is probably a y-oxobtitvlated -Naphthalene.

Claims (1)

PATENT 1NSPRLTCII: Process for the preparation of monomeric condensation products, characterized in that halogen-free aliphatic invlverl) indun.gen are allowed to act on aromatic hydrocarbons in the presence of agents having a condensing effect.