SU394358A1 - METHOD OF OBTAINING SALTS, DIANYLOV-p-ZA. YESHANCHA a, a'-POLYMETHYLENE-GLUTACON D AND ALDEHYDES - Google Patents

Description

The invention relates to a process for the preparation of new compounds, salts of glutaconium dialdehyde dianyls, which can be used as intermediates in the synthesis of polymethine dyes. A method is described for the preparation of salts of dianyl a, a-: polymethyleneglutaconic dialdehydes that do not contain substituents in p-poslopeni. However, there are no references in the literature about the preparation of compounds of the following structure: C6a5NHCH-Cc-CH-NiC, ii, cr with an alkoxy or arylamino group or a chlorine atom in the p-position. At the same time, the introduction of these groups makes it possible to obtain dyes inaccessible by other means, which are good sensitizers of film and photo emulsions. A method for the preparation of p-substituted-a, a-a-polymethylene glutaconic dialdehyde dianyl salts is described. or aniline. The desired product is isolated in a known manner. Examples 1-about. Preparation of p-substituted-a, -polymethyleneglutaconic dialdehyde salts of dianyls. The synthesis is carried out according to the following scheme: to 45 g (0.3 g mol) of ethylformanilide in 50 ml of chloroform at 0th C, 46 g (0.3 g mol) of phosphorus oxychloride in 10 ml of chloroform are added. After 30 minutes, 0.1 g of a cyclic ketone or (when X is OAlk) ether of its enol form is added dropwise to the solution to be transferred at room temperature in 15 minutes. Transferring is continued for another 30 minutes at room temperature, and then for 3 hours at 45–50 ° C: If X-C1 or OAlk. 32 g (0.25 g mol) of aniline hydrochloride are then added to the reaction mass, and then 75 ml of methyl alcohol is added dropwise. Kip t 2 hours and evaporated to one third. If X is C1, 50 ml of acetone is added to the residue after 12 hours, the sediment is filtered, washed on the filter with 5; -th hydrochloric acid and acetone. Crystallized from nitromethane. If X is OAlk, 200 ml of 5% hydrochloric acid is added to the residue, the precipitate is well triturated, filtered and washed with water. Crystallized from nitromethane. If X is NHCeHs, then 32.6 g (0.35 g mol) of aniline is added to the reaction mass, and after thirty minutes of boiling, the dianiline salt is precipitated with ether and washed with methanol. Crystallized from a mixture of alcohol - nitromethane. Compound 1 is obtained, where: 1) X is C1, n 2 is 35% yield, that is, decomp. 236 ° C, maximum absorption at 555 nm (in acetic acid). Found,%: C1 20.05; 20.22. CigHjsCbHa. Calculated,%: C1 20.58. 2) X-C1, l 3; yield 78%, so decomp. 214 ° C, maximum absorption at 526 nm (in acetic acid). Found,%: C1 19.74; 19.77. C2oH2oCl2N2. Calculated,%: C1 19.77. 3) X - C1, p 4; yield 37%, so decomp. 220 ° C, maximum absorption at 533 nm (in acetic acid). Found,%: C1 18.86; 19.00 C2lH22Cl2N2. Calculated,%: C1 19.05. 4) X-ОСНз, yield 25%, t. 152 ° C, maximum absorption at 507 nm (in acetic acid). Found,%: C1 10.11, 10.04. C2lH23ClN20. Calculated,%: C1 10.01. 5) X —NHCeHs, ft 2; yield 40%, so decomp. 269 ° C, maximum absorption at 482 nm (in acetic acid). Found,%: C1 8.97, 8.88. C25H24C1N3. Calculated,%; C1 8.81. The subject of the invention is a method for producing p-substituted-a, a-a-polymethylene glutaconic dialdehyde dianyl salts of the general formula C CH-MNecH5, where X is C1, OAlk, NHCeHs, and 2-4, characterized in that alicyclic ketones or esters of their enol forms are treated complexly. m of phosphorus oxychloride with ethylformanilido or m-N-formyl tetrahydroquinoline, followed by treatment of the reaction mixture with aniline hydrochloride and methyl alcohol or aniline and isolation of the target product in a known manner.