SU95949A1 - The method of obtaining symmetric and asymmetric dicarbocyanine dyes with a methyl or phenyl group in the beta position of the polymethine chain - Google Patents

Description

where: R and R2 are the same or different alkyl residues,

RI is methyl or phenyl,

Y - S, Se, С (СНз) 2,

X is the acid residue,

They are used as optical sensitizers for galoid-silver emulsions to the dark red and near infrared spectral regions.

The known methods for the synthesis of these compounds have significant drawbacks, of which the main one is L1a, the availability of the starting products and the low yields of the dyes obtained.

It was found that symmetric and asymmetrical dicarbocyanine dyes with a methyl or phenyl group in the (3-position of the polymethine chain of the general structure (I)) can be easily and with sufficiently high yields obtained by condensation of quaternary salts 2-р-м№ 95949

thyl- or 2- (3-phenylpropenylbenzthiazole with formylmethylene derivatives of N-substituted heterocyclic bases according to scheme (II):

nA

, + O CH-CH i

-Sh

Afi

CH C-CH CH-CH 1

  .

The reaction proceeds with a brief interaction of an equimolecular mixture of the starting materials in a solution of pyridine in the presence of acetic anhydride upon heating or at a normal temperature.

Example 1. 3,9-dimstil-3-ethylthiadicarbocyanine aniodide.

0.85 g of 2-p-methylpropenylbenzthiazole iodomethyl and 0.5 g of 3-ethyl-2 formylmethylenebenzthiazoline is dissolved by heating in 5 ml of pyridine. After adding 0.5 ml of acetic anhydride, the mixture is heated for 3-4 minutes. in a water bath, and a crystalline precipitate falls out. After an hour, the dye is filtered and washed on the filter in several stages with ethyl alcohol.

Yield 0.5 g (38.6% of theoretical). T. pl. 190-192 °. It crystallizes from 85 ml of methyl alcohol in the form of rectangular green prisms with m.p. 201-202 ° (with splitting). Maximum absorption (in ethyl alcohol) at 663 m / s. Sensitizes up to 760 MMK with a maximum at 710 MMK. With a slightly lower yield, the dye can be obtained by carrying out condensation at ordinary temperature for 12 hours.

Example 2. 3,3-Diethyl-9-methylthiadicarbocyanine iodide.

0.86 g of 2- | 3-methylpropeylbenzthiazole iodoethyl and 0.5 g of 3-ethyl-2 formylmethylenebenzthiazoline dissolve when heated in 5 ml of pyridine. After adding 0.5 ml of acetic anhydride, the mixture is heated for 4-5 minutes. in a boiling water bath, a blue-violet color appears and a fine crystalline precipitate forms. After cooling, the mixture is diluted with 10 ml of ethyl alcohol, the dye is filtered and washed on the filter in several stages with ethyl alcohol.

Output 0.9 g (33.8Vo from theoretical). T. pl. 192--193 °. After crystallization from 60 ml of methyl alcohol, rectangular green prisms are obtained with a m.p. 210-211 °. Maximum absorption at 664 m / s (in ethanol). Sensitizes up to 760 MMK with a maximum at 710 MMK.

Example 3. 3-methyl-3-ethyl-9-feiylthiadicarbocyanine iodide.

1.0 g of 2-p-phenylpropenylbepzthiazole iodomethyl and 0.5 g of 3-ethyl-2-formylmethyl-benthiazoline iodomethyl are dissolved by heating in 5 ml of pyridine. After adding 0.5 ml of acetic anhydride, the mixture is heated for 1-2 minutes. in a boiling water bath, where syn. .l gchpo .nov „, ...-, s. V nouOt 9.03- .., r -.;, Md -tp tserez n pta -;,; - eTCft .. 0 4vv: -vo; ;; tsea oug ;. . ,% / i 35 o.,; W:; ctb ;; 3auv; .c. srJs. 3 ,, pa 0-, from - ix "a v ssuSsSsSb-bSSS-SJiS ОRPG5 OCH l) l". Y “a,.; B. .e 0,5., - p «. r, L.,. s. lr.ftO "i ,," "-Gb o"; -, b .- "G..ppr ,, obra ,,, .. Q ,, .-- XoD nr. , , V8 rrrri 0. . «« Lg, na-va. 6., ". -LSr ° YH. tv pc | f:;:. :,. "T), geL. veop.u, uot l „th“ and “°° 0“ .. “V“ -ve .n .., °. Je t. ,,. V „,. s., “ac“ t. M. “I. ::, o. ° s:;, “;, s.; V ;; b. «.6, SS« «° i J g 0.85 g W c..ee,; ; r..7.u, S. a to-e;, 3 exs., segs. ";; f. en - O; Gp; from m rt ,,, - egl1 ° yu / y.G - ts 5 oSr2l: .Т okf5 97, 04; i iloojjj z °: er. H. , 2.u ssa 5S ||: -.- ... .SSfMe Pac .. J J-Vac: ,, - / 5 2; -SiS7% S ow: ™ - .., 4rt: .e ,,. ,, P..Ven n. ., L ,,,: 2.- 3.3. S: s - ;: t - «- :::: I - jir. -.ae.r About .- “a - - ,, -; | 1 "5r- ° -IS o ..,, 1 °. Chvd: 52; i t4f-. . . . .oa „;„ - o, o / - - - / -S P. 660. ,, fS ..- Г ° „P4„ / 85,,. . 191 en, Z er ..... ., "5 - ..,., .--. OG OA, V. fftfJI.r In,: - fwr "s. . / ToS CS e .... from 5 ::. r D 4,3 / TH „PifL 4l-ei ° -: BO.O .o ;. j, 3o.o. Onj 7. four -. 50 :,. . with. 198 °,: .... ,, oh,. Ssj oZrlf -0; .: OBoff r.l.r dsl-jojc. “B g, Pab .-- - l - b, Me

absorption maximum at 662 mcf (to ethanol). Septicilization up to 750 MMK s; Max. at 705 mm to.

Pr iM er and. 3-methyl-3-ztil-9-phenyl-thithiazolinone dicarbocyanine iodide.

, 0 g of 2-p-phenylpropennylbenzthiazole iodomethyl and 0.4 g of 3-ethyl-2-formylmethylene thiazolidine are dissolved by heating in 5 ml of pyridine. After cooling to normal temperature, 0.5 ml of acetic anhydride is added to the solution and the liquid is charged for 2-3 minutes. in a boiling water bath. The solution is diluted with ether 01M, the separated gummy precipitate is washed two or three times with ether and then processed by heating with JO ml of ethyl alcohol. Upon cooling and rubbing the walls of the flask with a glass rod, crystallization starts. After 2-3 hours. the dye is filtered and washed on the filter with ethyl alcohol until a pure blue-violet color of the filtrate is obtained.

Output 0.5 g of f37,5Vo from theoretical). T. pl. 174-175 °. It crystallizes from 1 ml of methyl alcohol in the form of shallow dark green prisms with m.p. 184-185 °. Maximum of glogpepea at 609 MMK (ethyl alcohol).

Example J2. G, 3,3, 3, 9-pentamethylthiaindodicarbocyanine perechlorate.

A mixture of 0.85 g of 2-) 3-methylpropionylbenzthiazole iodomethyl and 0.5 g of I, 3, 3-trimethyl-2-formylmethyleneindolinine is dissolved by heating in 3.75 ml of pyridine. After adding 0.37 ml of acetic anhydride, the liquid that has stained with an intense blue-orange color heats up for 2-3 minutes. in a boiling water bath. After cooling, the solution is diluted with ether, the separated gummy precipitate is washed two or three times with ether and dissolved in a small amount of ethanol. When an equal volume of lOVo-Horo is added to a solution of an aqueous solution of sodium perchloric acid, the dye perchlorate is formed as a rapidly crystallizing saliva. The precipitate is filtered and washed on the filter with a small amount of ethyl alcohol to a pure blue-violet color of the filtrate.

Yield 0.75 g (58.3Vo from theoretical). T. pl. 161-162 °. Dark green indefinite crystals (of methyl alcohol). T. pl. J80-181 °. A1 maximum absorption at 643 m / ik (in ethyl alcohol). Sensitizes up to 730 MMK with a maximum at 685 MMK.

Example 13. 3-methyl-3-ethyl-9-feiil-6, 7-tetramethylenediadicarbocyanine iodide.

, 0 g of 2-p-phenyl-propenylbenztpazole iodomethyl and 0.65 g of 3-ethyl-6,7-tetramethylene-2-formylmethylenebenzthiazoline dissolved in 5 ml of pyridine. After cooling, 0.5 ml of acetic anhydride is added to the liquid and the mixture is heated for 3-4 minutes. in a boiling water bath. The blue-violet solution is diluted with ether, the separated resin is washed two or three times with ether and treated at boiling with 10 ml of ethyl alcohol, and crystallization occurs. In 2 hours the dye precipitate is filtered off and washed on the filter in several stages with 25 ml of alcohol and ether.

Output 0.5 g (31.5Vo from theoretical). T. pl. 182-183 ° (with decomposition). After crystallization from 25 ml of methyl alcohol, small green prisms are obtained with a gold-colored finish. T. pl. (with decomposition m.) Maximum absorption at 676 m / y (in ethyl alcohol).

PRI and m.m 14. 3,9-dimethyl-3-ethnl-6-diethylampnoadnocarbocyaniniodide.

- about - -AO 95949

A mixture of 0.85 g of 1-lata 2-p-methylpropenylbenzthiazole iodome and 0.7 g of 3-ethyl-6-diethylamino-2-formylmethylenebenzthiazoline is dissolved in 5 ml of pyridine when heated. After adding 0.5 ml of acetic anhydride, the liquid is heated for 1-2 minutes. on a boiling water bath, where an intense greenish-blue color appears and a crystalline precipitate appears. After cooling, the dye is filtered and washed on the filter in several stages with 25 ml of ethyl alcohol to a pure greenish-blue color of the filtrate.

Output 0.25 3 (16.9Vo from the theoretical). T. pl. 165-166 °. Crystallizes; from 40 ml of methyl alcohol in the form of dark green prisms with a golden sheen. T. pl. 190-19G. Maximum absorption at 697 mk. (in ethanol). Sensitizes up to 800 MMK, with a maximum at 745 MMK.

The method of obtaining symmetric and asymmetric dicarbocyanine dyes with a methyl or phenyl group in (5-position polymethine depy of the general structure

where: R and Ra are the same or different alkyl residues.

RI is methyl or phenyl,

At S, Se, С (СНз) 2,

X - acid residue,

characterized in that quaternary salts of 2-p-methyl- or 2-p-phenylpropenylbenzothiazoles are condensed with formylmethylene derivatives of N-substituted heterocyclic bases in a solution of pyridine in the presence of acetic anhydride at ordinary temperature or moderate heating.

Subject invention

cn cn cn-CH k.k

H- "p N

RR,