SU493757A1 - The method of obtaining dicarbocyanin dyes - Google Patents

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(54) METHOD FOR OBTAINING DICARBOCYANINES. DYES 493 3 amines, for example, triethylamine at room temperature (15-2 ° C) or heated to 100 ° C. EXAMPLE 1: Preparation of 1, 1, 3, 3, 3, 3, 3-hexamethylene carbocyanine cytokine, a mixture of 1.5 g of yotsmetilate 2, 3, 3-trimethylinclolenine, 0.7 g of phenoxyacrolein, 5 ml of acetonitrile, and 0.35 ml of triethylamine is heated for 3 minutes in a flask with a reflux condenser on a boiling water bath, and a crispy precipitate is separated. After cooling, the dye is filtered off and successively washed in several steps with 1 5 ml of warmer, 10 ml of ethyl alcohol and 15 ml of ether. Exit; 14, -, 2%); m.p. 250 2510С. -l-i ...;.; After recrystallization from ethyl alcohol (1:25), blue crystals are obtained with a steel luster; m.p. 254-2. can be obtained similarly in acetic anhydride (5 ml). Yield 1, O5 g (82.3%);, - t. square 254255 ° C; recrystallization from ethanol. Example 2. Preparation of 1, 1 3, 3 3, 3, -hexametyl-4, 5, 4, 5 - cybenzoin picaparbocyanine cytokine. A mixture of 1.8 g of yotsmetilat 2, 3, 3-trimethyl-4, 5 benzoindolenin, 0.7 g of y8-phenoxyacrolecna, 15 ml of yi cycHoro angiitsritz. and 0.35 ml of triethylamine are thoroughly mixed and left for 72 hours in a bright place. The precipitate which separated was filtered and washed in several steps with 50 ml of water, 20 ml of ethyl alcohol and ether. Yield 1.3 g (81.2%); m.p. 279-2800С. After recrystallization from methyl alcohol, bronze crystals are formed with a metallic sheen; m.p. 270-271 ° C. Found,%:%: a 19.64; 19.61 5 "35 3 SNDON. Calculated,%: J 19.75. PRI me R 3. Obtaining 3,3-aetilo xycicarbrycyanone. A mixture of 1.45 g of 2-methylbenzoxazole iodoethyl, 0.7 g of α-phenoxyacrolein, 5 ml of acetonitrile and 0.7 ml of trietrlamine is heated for 15 minutes in a boiling water bath. After cooling, the solution is risen with ether, after 2 hours the ether is drained, the residue is washed 3-4 times with ether, treated at boiling with 5 ml of ethyl alcohol and the mixture is kept at room temperature. After 12-18 hours, the dye is filtered off, washed with water and ether. Output O, 5 g (41.6%); mp, 215-22P ° C. After recrystallization from methyl alcohol, dark-blue IgG1 with steel casting is obtained: mp. 23O-231 C. Example 4. Preparation of 3, -a-itil-5, -5-diphenyloxy-scarbocyanine iodide. A mixture of 1.7 g of ethylmethyl sulfate, Methyl-: -5-phenylbenzoxazole, 0.7 g of y9-phenoxy-acrolein, 5 ml of acetonitrile and 0.7 ml of triethylamine is heated for 30 minutes in a boiling water bath. After cooling, the solution is diluted with ether, after 2 hours the ether is poured, the residue is washed with ether, dissolved in 30 ml of ethyl alcohol and the dye is separated by adding an equal volume of 1 O% aqueous solution of potassium iodide. The precipitate is filtered off, washed in several stages with 4OO ml of water and 4OO ml of benzene, then treated at boiling with 1OO ml of benzene, filtered and washed on the filter with benzene. Yield 0.34 g (22%); m.p. 21 ° -22 ° C. After recrystallization from methyl alcohol, grayish-blue prisms are obtained, mp. 247-250 ° C. Found,%: 3 19.73; 19.63 5 313 2 2 Calculated,%: D 19.83., Example 5. Preparation of 3,3-diethyl-thiadicarbocyanine tiada. A mixture of 1.52 g of 2-methylbenzthiazole iodoethyl. About 7 g of A-phenoxyacrolein, 2.5 ml of acetonitrile and 0.35 of triethylamine are heated for 5 minutes at 7 ° C (in a bath). After cooling, the precipitated crystalline precipitate is filtered and washed with 7.5 ml of water, 5 ml of ethyl alcohol and 5 ml of ether. Yield 1.2 g (92.6%); m.p. 23 ° -233 ° C. Get green., Needles (from methyl alcohol, 1: 20O); m.p. 248-25 ° C. With a yield of 81%, the dye is formed by conducting the reaction in anhydrous ethyl alcohol 1 while heating for 1 minute in a boiling water bath. (Example. Preparation of 3,3-diethyl 5, 6, 5, 6-tetramethyl adicarbocyanine-p-toluenesulfonate. A mixture of 1.9 g of ethyl-p-toluenesulfonate 2,5,6-trimethylbenzthiazole, 0.7 g; and phenoxyacrolein, 5 ml of acetonitrile and 0.35 ml of triethylamine are allowed to stand for 24 hours at room temperature in a protected place; the precipitated crystalline precipitate is filtered and washed with 7.5 ml; water, 2.5 ml of ethanol and 15 ml of ether. (87.3%); mp 227–29 ° C. Green needles are formed (from ethyl alcohol, 1: 16O); mp 238–24 ° C. Example 7: Preparation 3,3- cyethyl selenacycarbocyanine oocytes A mixture of 1.75 g of 2-methylbeneselenazole yozetilate, 0.7 g of uB -phenoxyacrolein, 7.5 ml of ethyl-free alcohol and 0.35 ml of triethylamine are allowed to stand at room temperature for 2 hours. The dye is filtered and washed with 5 ml of water, 7, 5 ml of ethyl alcohol and 7.5 ml of ether. Yield 1D g (84.6%), mp 223-225 ° C. ... Green needles are obtained (from methyl alcohol, 1: 340); mp. 234-235 ° C. Example: Preparation of 1,1-aethyl-2, 2-quinodicarbocyanine iodide. A mixture of 1.5 g of quinaldine iodoethyl. 0.75 g of B -phenoxyacrolein, 5 ml of acetic anhydride and 0.35 ml of triethylamine are allowed to stand for 72 hours at room temperature in a dark place. The crystalline precipitate that separates is filtered, washed. With 10 ml of water, 10 ml of ethyl alcohol and 15 ml. the ether. Yield 0.75 g / 60%, t ; pl. 258-2 ° C °. Green needles (from methyl alcohol, 1: 7O) are formed, so pl. 265-267 ° C. 1.5 g of quinaldine iodoethyl, 0.7 g of y8-pheno-xacrolene, 4 ml of acetic anhydride and 0.35 ml of triethylamine are obtained by heating the mixture for 2 min in a boiling water bath. Output 1, O5 g (83.3%), so pl. .258260 ° С, Pr and 1 Ер 9. Preparation of 3,3-diatil-5, 5-di lelthia of diazolo (1,3,4) -dicarbocyanine iodide. A mixture of 1.35 g of iodoethyl 2,5-dimesh1 thiodiazole (1, 3, 4), O, 7 g of α-phenoxyacrolein, 5 ml of acetonitrile and 0.35 ml of triethylamine is incubated for 24 hours at room temperature, protected from light. The precipitated crystalline precipitate is filtered off, washed with 7.5 ml of water, 2.5 ml of ethyl alcohol and 5 ml of ether. Yield 0.9 g (8O, 3%); mp 1 96-1 97 ° C. Get blue needles (from ethyl alcohol, 1: 6O); m.p. 199-2OOOS. Example 1O. Preparation of 3,3-diethyl 5,5 -py41heshthiaaiazolo- (1,3,4) -cycarbo1 Shanin 11odide. A mixture of 1.65 g of 2-methyl-5-α-phenylthioaziazole (1,3,4) iodothylate, 0.7 g of α-phenoxyacrolein, 5 ml of apetonitrile and 0.35 ml of triethylamine is kept for 24 hours at room temperature and protected from light. The precipitated crystalline precipitate is filtered off, washed with 5 l of wax with 5 ml of ethyl alcohol and 10 ml of ether. Output 0.1 g (70%); m.p. 152-157. After crystallization from ethyl alcohol, green needles are obtained; m.p. 173-177 ° C. Found,%: S 1O, 93; 1O, 88 3 1.1.20. Calculated, Example 11. Obtaining 3,3-diethyl-4, 5,4, 5-tetraphenylthiazolodicarbocyanine iodide. Mixture 2, O g of 2-methyl-4,5-diphenylthiazole iodoethyl, 0.7 g-phenoxyacrolein, 5 ml pyridine, 5 ml acetonitrile and 0.35 ml triethylamine are incubated for 24 hours at room temperature and diluted with 15 ml ether. The residue is filtered, washed with 10 ml of water, 5 ml of ethyl alcohol and 15 ml of ether. Yield 1.5 g (83.3%); m.p. 18 ° -181 ° C. Get bronze needles (from ethyl alcohol, 1: 4O); m.p. 18 ° -181 ° C. The subject matter of the invention 1. The method of obtaining the dicarbocyanine dyes of the general structure and + r-cn-cf-c 4 -... where Y O, S, Ze, C (R) ,, Z "C - or (in the latter case, U is absent) ; II and C - or - 1x1 -, R is an unsubstituted or substituted hydrocarbon residue; f is a hydrocarbon residue; X is an acid residue (X is absent if R contains an acid group), by condensation of quaternary salts of heterocyclic bases containing a methyl active group with derivatives ak; olein, h and l and h so that, in order to simplify the process technology and determine the degree of cleanliness and the degree of purity of the pelevl-lh products, as a manufacturer. 1.

acrolein used with aaryloxynic solvents, for example, in acetoacroleins and the reaction is carried out at a temperature of nitrile, acetic anhydride,

IS-IOO C. lower aliphatic alcohols or pyritium,

2. The method according to p. 1, about tl and h and y and n-ne, in the presence of tertiary aliphatic

so that the process is carried out in the medium LH-- 5 .ov, national triethylamine.

493757