RU1803415C - Method of @@@-di-@@@-sulfopropyl -9-ethylcarbocyanine betaine synthesis - Google Patents

Abstract

SUMMARY OF THE INVENTION: 3,3-di-y-sulfopropyl-9-ethylcarbocyanine betaines are prepared by reacting y-sulfopropyl 2- / 3-substituted benzthiazoles (benzoxazoles) cy-sulfopropyl betaine with 2-methyl substituted benzthiazole or benzoxazole of the general formula c + A CH C-OS2H5 I (CH2) 3S03 where Y-0 or S, B-5-phenyl, 5-methoxy group, in an organic solvent: phenol or a mixture of phenol with alcohol (1: 1), or phenol with dimethyl sulfoxide (1: 5) in the presence of trialkylamine at 20-110 ° C. (L C

Description

the method is the simplification of the process (2 stages less), a good yield of the target products, and also the elimination of the release of toxic environmental polluting alkyl mercaptans, which makes the process environmentally friendly

The distinctive features of the claimed technical solution is the use of 2-D-ethoxybutenyl-benzothiazoles (benzoxazoles) of formula II in the process of producing y-sulfopropyl betaines, the process in phenol, a mixture of phenol and alcohol (1: 1), phenol and dimethyl sulfoxide (1: 5).

The following examples illustrate the invention.

Example 1. Obtaining tributylammonium salt of 3,3-di-y-sulfopropyl-5-methoxy-4, 5-benzo-9-ethylthiacarbocyanine betaine (prototype), B 5-methoxy, W-4,5-ben zo, K + - (H-C4Hg) cNH.

A mixture of 2 t of γ-sulfopropylbetaine 2- / 3-methylmercaptobutenyl-5-methoxybenzothiazole (0.005 mol), 1.6 g of γ-sulfopropylbetaine 2-methyl-4,5-benzobenzothiazole (0.005 mol), 25.0 ml absolute alcohol. It is heated to boiling and boiled for 5-6 minutes, then 3.6 ml (2.78 g) of tributylamine (0.015 mol) are added to the reaction mass and boiled for 1 hour in a water bath with periodic stirring. The hot solution is filtered, washed with 4.0 ml of absolute alcohol, after cooling, diluted with 180 ml of dry ether, -

and left until the next day in the refrigerator. The ether is drained, and the gummy residue is washed with 60 ml of dry ether (2 times 30 ml). The residue after washing is dissolved in 12 ml of absolute alcohol with heating, stirred and poured into

, -

conical flask, rinse with 2 ml of absolute alcohol and attach to the basic alcohol solution, cool to room temperature, rubbing the walls and the bottom of the flask with a glass rod cause crystallization to begin and leave in a refrigerator until the next day. Get green needles with so pl. 215-225 ° C.

Yield 2.4 g (56.7%, assuming 2-dimethylmercaptobutenyl-5-methoxybenzothiazole for y-sulfopropyl betaine, and only 38% for 2-ethoxybutenyl-5-methoxybenzothiazole).

The maximum absorption in ethyl alcohol at 572 nm.

Found,%: C 59.70, 59.49; H, 7.31; 7.25; N5.00.4.95.

S42H59MzO 54.

Calculated,%: C 59.61; H 7.02; N, 4.97.

5

U 15

twenty

25 30 35

40

45

50 55

Example 2. Preparation of the tributylammonium salt of Z. Z1-di-y-sulfopropyl-5-methoxy-4, 5-benzo-9-ethylthiacarbocyanine 1-betaine.

A mixture of 3.85 g of γ-sulfopropyl betaine 2- / 3-ethoxybutenyl-5-methoxybenzothiazole (0.01 mol), 3.2 g of γ-sulfopropyl betaine 2-methyl-4,5-benzobenzothiazole (0.01 mol), 10 g of phenol and 7.2 ml of tributylamine (0.03 mol) are stirred into a homogeneous mass during heating for 1 h at 105-110 ° С (in a bath), then 10 ml of absolute alcohol are added to the reaction mass and the mixture is heated for another 1 h, then filtered, washed with 8 ml of absolute alcohol and cooled. After cooling, dilute with 100 ml of dry ether and leave until the next day. The ether was drained, the residue was washed twice with 20 ml of dry ether and dissolved in 10 ml of absolute alcohol and left overnight in a refrigerator. The precipitate is filtered off, washed with 8 ml of absolute alcohol in 2 divided doses, with dry acetone (16 ml) in 2 divided doses, with ether (15 ml). Green needles are obtained with mp. 220-225 ° C (within 1-2 ° C). Yield 4.1 g (48.6%). The maximum absorption in ethyl alcohol is 572 nm.

Found,%: C 58.29, 58.37; H, 6.92; 7.10; N 4.51.4.66.

C42H5gN307S4 H20.

Calculated,%: C 58.37; H, 7.11; N 4.86.

Example 3. Preparation of the triethylammonium salt of 3,3-di-y-sulfopropyl-5-chloro-51-methoxy-9-ethylthiacarbocyanin betaine.

A mixture of 0.62 g-γ-sulfopropyl betaine 2-methyl-5-chlorobenzothiazole (0.002 mol), 0.78 g-γ-sulfopropyl betaine 2- / -ethoxybutenyl-5-methoxybenzothiazole (0.002 mol), 1.5 g of phenol , 0.84 ml of triethylamine. Heated in a boiling water bath for 1 hour. After cooling, the reaction mass was diluted with 20 ml of dry ether and left for 2 days. in fridge. The ether was drained, and the residue was diluted again 2 times with 10 ml of dry ether, then the ether was drained and the residue was dissolved in 6 ml of absolute alcohol and left in the refrigerator overnight. The precipitate is filtered off, washed on the filter with 3 ml of absolute alcohol, 5 ml of ether. Yield 1.1 g (70.50%), mp. 233-234 ° C. Green crystals with a metallic sheen. The maximum absorption in ethyl alcohol at 558 nm.

Found,%: C 49.21, 49.31; H, 6.05; 6.21; N, 5.35, 5.47; CI 4.48, 4.50; S 16.53, 16.7. C32H44CIN307S4 2H20.

Calculated,%: C 49.11; H, 6.18; N, 5.37; C 4.53; S 16.39.

Water confirmed by GLC.

Example 4. Obtaining the triethylammonium salt Z. Z1-e, l-y-sulfopropyl-5-phenyl-4, 5-benzo-9-ethyloxathiocarbocyanine is a secret.

A mixture of 0.52 g of γ-sulfopropylbetaine 2- / ethoxybutenyl-5-phenylbenzoxazole (0.00125 mol), 0.32 g of γ-sulfopropylbetaine 2-methyl-4,5-benzobenzothiazole (0.001 mol), 0.5 g phenol, 2.5 ml of dimethyl sulfoxide (DMSO) and 0.21 ml of triethylamine (0.003 mol) were dissolved at room temperature and incubated for 24 hours at room temperature, then filtered off from a slight precipitate and 25 volumes of acetone were added. The precipitate is filtered off, washed on the filter with dry acetone (25 ml), dry ether. Weight 0.35 g (24%). Dark cherry crystals with so pl. 222-225 ° C (within 1-2 ° C). The maximum absorption in ethyl alcohol at 538 nm.

Found,%: C 57.99.58.30; H, 6.12; 6.18; N, 4.58, 4.78.

C41H49N307S3 ZN20.

Calculated,%: C 58.20; H 6.55; N, 4.96.

Water confirmed by GLC.

Example 5. Preparation of the triethylammonium salt of Z. Z1 -di-y-sulfopropyl-5-phenyl-5-chloro-9-ethyloxathiocarbocyanine betaine.

A mixture of 1.04 g of γ-sulfopropyl betaine of 2- / 3-ethoxybutenyl-5-phenylbenzoxazole (0.0023 mol), 0.62 of γ-sulfopropyl betaine of 2-methyl-5-chlorobenzothiazole (0.0002 gm), 1 g of phenol, 5 ml of dimethyl sulfoxide (DMSO) and 0.42 ml of triethylamine (TEA) were incubated for 24 hours at room temperature, then diluted with 15 volumes of ether, the ether was drained, and the residue was dissolved in 15 ml of ethyl alcohol, the solution was filtered and diluted to 200 ml dry acetone. It is left in the refrigerator for one day. The precipitate is filtered off, washed on the filter with dry acetone (50 ml), dry ether (10 ml). Weight 0.66 g (38%). Red crystals or cherry with so pl. 189-190 ° C. I max - 528 nm (in ethanol).

Found,%: C 51.31, 51.07; H, 6.42; 6.21; N 4.68, 4.60.

Sz7N4bS1M3075z 5N20.

Calculated,%: C 51.28; P 6.51; N 4.84.

Water confirmed by GLC.

Example 6. Preparation of the tributylammonium salt of 3,3-di-y-sulfopropyl-9-ethyl-5,5-diphenyloxacarbocyanin betaine.

A mixture of 0.6 g of γ-sulfopropyl betaine of 2-methyl-5-phenylbenzoxazole (0.02 mol), 9.6 g of γ-sulfopropyl betaine of 2-uz-ethoxybutenyl-5-phenylbenzoxazole (0.023 mol), 12 g of phenol are heated at 105 -110 ° C (in

bath) for 5-10 minutes until the starting materials are completely dissolved, then 7.2 ml (0.03 mol) of tributylamine are added and the mixture is heated for 2.5 hours at 105-110 ° C (in

bathhouse).

After cooling, the reaction mixture was diluted with 100 ml of dry ether and allowed to stand for 2-3 hours, after which the ether was drained and refilled with a fresh portion (100 ml) and left until the next day. The ether solution is drained the next day, and the gummy residue is boiled for 3-5 minutes, with dry acetone (50 ml), after cooling, diluted with dry ether (150 ml) and left until the next

days

The ether-acetone wash was drained and the residue was triturated with (20 ml) dry acetone.

Weight 8.35 g (46.4%) with mp 264-265 ° C. After crystallization from absolute alcohol, orange or red crystals are obtained with mp. 280-285 ° C. Yamax 506 nm (in ethanol).

Found,%: C 65.58, 65.98; H, 7.14; 7.22; N, 4.49, 4.59.

С49НбзМз0852 0.5 Н20. Calculated,%: C 65.74; H, 7.20; N 4.69. Water confirmed by GLC.

Claims (1)

The claims Method for producing 3,3-di-y-sulfopropyl-9-ethylcarbocyanine betaines by reacting y-sulfopropyl 2- / -substituted benzene-condensed five-membered heterocyclic compound with y-sulfopropylbetaine 2-methyl-substituted condensed with with benzene of the five-membered heterocyclic compound in an organic solvent in the presence of trialkylamine, which, in order to simplify the process and improve environmental conditions, as the γ-sulfopropyl betaine of the 2- / 3-substituted benzene-condensed five-membered heterocyclic compound, use the compound general formula g m B fJ-CH c-oc2H N 55 (sn2) 3zo; where Y is 0 or S, B is 5-phenyl or 5-methoxy group, phenol or a mixture of phenol with alcohol as an organic solvent with a mass ratio of 1: 1, or a mixed ratio of 1: 5, and the process is carried out with phenol with dimethyl sulfoxide at a mass of 20-110 ° C.