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Quinaldine based semisquaraines and squaraine dyes, process for preparation thereof and use thereof

A technology of squarylium and quinaldine, applied in the field of quinaldine-based semisquarine and squarylium dyes, their preparation and application, capable of solving problems such as the difficulty of destroying deep tumors

Inactive Publication Date: 2009-03-25
COUNCIL OF SCI & IND RES
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Porphyrins have satisfactory optical properties and biodistribution patterns, but their photodynamic applications require solubilizers or emulsifiers such as liposomes or lipoproteins
Chlorins have strong absorption in the red and infrared regions of the spectrum and are comparable to photoporphyrins, but skin photosensitivity is their major concern
Therefore it becomes difficult for these compounds to destroy deep tumors

Method used

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  • Quinaldine based semisquaraines and squaraine dyes, process for preparation thereof and use thereof
  • Quinaldine based semisquaraines and squaraine dyes, process for preparation thereof and use thereof
  • Quinaldine based semisquaraines and squaraine dyes, process for preparation thereof and use thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0063] General procedure for preparing the compound represented by Formula 1. The corresponding mixture of quinalidine salt (1mmol), square acid (1mmol) and quinoline (0.5mL) in a mixture of n-butanol and benzene (6-9mL each, 1:1) in azeotropic distillation with water Reflux for 24-36h under conditions. The solvent was distilled off under reduced pressure to obtain a residue, which was chromatographed on silica gel. The column was eluted with a mixture of methanol and chloroform (1:19) to obtain the hemisquaraine of general formula 1.

[0064] General formula 1 (where X=OH, Y=H and Z=H, R 2 =CH 3 , 90-95%) of the physical and chemical properties of the compound: mp 150-152℃, IR(KBr)v max 3412, 3042, 2963, 1761, 1606cm -1 . 1 H-NMR(CDCl 3 +DMSO-d 6 , 1:4) δ 10.06 (1H, OH), 9.29 (1H, d, J = 11.4 Hz), 7.89 (1H, d, J = 9.3 Hz), 7.73 (1H, d, J = 9.4 Hz), 7.34 (1H, d, J = 9.3 Hz), 7.17 (1H, s), 6.14 (1H, s), 4.64 (2H, t, J = 6.5 Hz), 4.11 (3H, s), 1.78 (2H, m) , 1.45 (2H, m), 0.93 (3H, ...

Embodiment 2

[0069] General procedure for preparing the compound represented by Formula 2. The mixture of the corresponding quinalidine salt (1mmol), squaric acid (0.5mmol) and quinoline (0.5mL) was azeotropically distilled with water in a mixture of n-butanol and benzene (6-9mL each, 1:1) Reflux for 24-36h under the same conditions. The solvent was distilled off under reduced pressure to obtain a residue, which was chromatographed on silica gel. The column was eluted with a mixture of methanol and chloroform (1:9) to obtain the corresponding squaraine dye of general formula 2.

[0070] General formula 2 (where X=Br, Y=H, R 2 =CH 3 , 90-95%) of the physical and chemical properties of the compound: mp 336-338℃, IR(KBr)v max 3056, 1613, 1580cm -1 . 1 H-NMR(DMSO-d 6 )δ 9.31 (1H, d, J=9.5 Hz), 9.28 (1H, d, J=9.3 Hz), 7.3-8.4 (8H, m, aromatic), 5.86 (1H, s, ethylene), 5.78 (1H, s, ethylene), 3.85 (3H, s); 3.78 (3H, s); FAB-MS: m / z=550.246 (C 26 H 18 Br 2 N 2 O 2 The calculated value is 550.248).

...

Embodiment 3

[0077] General procedure for preparing the compound represented by Formula 3. Mix the corresponding hemisquaraine (1mmol) and iodine or bromine substituted quinalidine salt (1mmol) and quinoline (0.5mL) in a mixture of n-butanol and benzene (6-9mL each, 1:1) Reflux for 18-24h under conditions of azeotropic distillation with water. The solvent was distilled off under reduced pressure to obtain a residue, which was chromatographed on silica gel. The column was eluted with a mixture of methanol and chloroform (1:9) to obtain the corresponding squaraine dye.

[0078] General formula 3 (where X=OH, Q=I, Y=H, Z=H, R 2 =CH 3 , 90%) of the physical and chemical properties of the compound: 325℃, IR(KBr)v max 3442, 3046, 1729, 1621, 1579, 1560cm -1 . 1 H-NMR(DMSO-d 6 )δ 10.2 (1H, OH), 9.29 (1H, d, J = 9.2 Hz), 9.01 (1H, d, J = 9.5 Hz), 7.86-7.01 (8H, m), 5.77 (1H, s, ethylene ), 5.44 (1H, s, ethylene), 3.9 (3H, s), 3.5 (3H, s); FAB-MS: m / z=534.040 (C 26 H 19 IN 2 O 3 The calculated value is...

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Abstract

The present invention provides quinaldine-based semisquaraines, symmetrical and unsymmetrical squaraine dyes represented by the general formulae 1, 2 and 3 and / or pharmaceutically acceptable derivatives thereof as sensitizers for photodynamic therapeutical and industrial applications. These symmetrical and unsymmetrical squaraine dyes posses absorption which extends well into the photodynamic window (650-800 nm) and hence are useful for the treatment of deep seated tumors. The absorption of these dyes can be tuned by changing the substituents on the quinaldine moiety thereby enabling the development of a library of dyes which have absorption ranging from 650 to 800 nm. They also exhibited fluorescence emission in the long wavelength region making them useful as near infrared fluorescence sensors for the detection of tumors. These dyes are non-toxic in the dark and exhibit good photocytotoxicity. Accordingly the quinaldine based semisquaraines, symmetrical and unsymmetrical squaraines are extremely useful as diagnostic and therapeutic agents for photodynamic therapeutical and industrial applications.

Description

Technical field [0001] The present invention relates to quinaldine based semisquaraine (quinaldine based semisquaraine) of general formula 1 and squaraine (squaraine) dyes of general formula 2 and 3 for photodynamic therapy, diagnosis and industrial applications and their pharmaceutical properties. The general formulas of the accepted derivatives are as follows: [0002] [0003] Formula 1 [0004] Among them, X = H, I, Br, NO 2 , CN, COOH, SO 3 H or OR 1 , Where R 1 =H, alkyl with 1-6 carbon atoms, diol with 2-4 ethylene, cholic acid, cholesterol, sugar, amino acid or peptide; Y=H, I or Br; Z=H, I, Br, NO 2 , CN, COOH, SO 3 H, SO 2 Cl or OR 1 ; R 2 = Alkyl groups with 1-6 carbon atoms, diols with 2-4 ethylene groups, alkyl sulfonic acids and acid chlorides with 1-6 carbon atoms; [0005] [0006] Formula 2 [0007] Among them, X = H, I, Br, NO 2 , CN, COOH, SO 3 H, SO 2 Cl or OR 1 , Where R 1 =H, alkyl with 1-6 carbon atoms, diol with 2-4 ethylene, chol...

Claims

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Application Information

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IPC IPC(8): C09B57/00A61K31/00A61K49/00A61P35/00
CPCC07D215/14C09B57/007A61P35/00
Inventor R·达纳博伊纳J·库哈纳皮利尔T·A·卡利阿特
Owner COUNCIL OF SCI & IND RES