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US 11,214,687 B2Granted
Small-molecule organic dyes
AssigneeUniversitäT Basel
InventorsChristof Sparr, Christian Fischer
Life of this patent
Estimating the term…
Abstract
The present invention relates to compounds of formula (A), wherein Z is NR10 or O. These compounds represent novel acridinium and xanthylium salts having an unprecedented substituted heterocyclic core. They are useful as fluorescent dyes or precursors thereof in different applications including various imaging and sensing techniques, and, in particular, as photosensitizers and hereby preferably as photocatalysts. The present invention further relates to processes for preparing the inventive compounds via 1,5-organodimetallic reagents from double directed ortho-metalation reactions or combined halogen-metal exchange/directed ortho-metalation reactions.
Claims14
A compound of formula (A)
- wherein
- Z is NR10 or O;
- R1 is selected from C1-C6-alkoxy, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14, OCNR2, CONHR14, CON(R14)2, C═NR14, CO2H, [CO2−], CO2R14, SO3R14, SO3H, SO2NC(CH3)3, [SO3−], SO2N(R14)2;
- R2 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, C1-C12-alkyl, SO3H, [SO3−, SO3R14, CO2H, [CO2−l ], CO2R14;
- R3 is selected from H, halogen, NO2, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2 and CN;
- R4 is selected from H, C1-C12-alkyl, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, SO3H, [S03−], SO3R14;
- R5 is selected from H, C1-C12-alkyl, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, SO3H, [S03−], SO3R14;
- R6 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, C1-C6-hydroxyalkyl;
- R7 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, C1-C12-alkyl, SO3H, [SO3−], SO3R14, CO2H, [CO2−], CO2R14;
- R8 is selected from H, halogen, C1-C6-alkoxy, OH, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14 , OCN(R14)2, CONHR14, CON(R14)2, C═NR14, CO2H , [CO2−], NO2, SO3R14, SO3H, SO2NC(CH3)3 and SO2N(R14)2;
- R9 is selected from aryl, heteroaryl, C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkyl, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl), C1-C12-alkoxy, C1-C12-hydroxyalkyl, C1-C4-alkyl-CO2H, C1-C4-alkyl-CO2-C1-C6-alkyl, C(═O)H, C(═O)-C1-C6-alkyl and C1-C12-alkylthio;
- and wherein said aryl and heteroaryl are optionally substituted by one or more groups independently selected from halogen atoms, CN, N3, C1-C6-alkyl, [SO3]−, SO3H, SO2Cl, OH, C1-C6-alkoxy, CO2−, C(═O)OH and C1-C6-alkoxycarbonyl, C1-C12-hydroxyalkyl, C1-C12-thioalkyl;
- R10 is selected from aryl, heteroaryl, C1-C4-alkyl-aryl, C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkyl, H, C1-C12-hydroxyalkyl, C(═O)H, C(═O)-C1-C6-alkyl, C1-C12-alkylthio, C1-C12-alkyl-CO2H, C1-C12-alkyl-CO2-C1-C12-alkyl, C1-C12-alkyl-CO2-C1-C4-alkyl-aryl, O−, S(═O)-C1-C6-alkyl, S(═O)aryl, S(═O)-heteroaryl, S(O2)-C1-C6-alkyl, S(O2)-aryl, S(O2)-heteroaryl;
- wherein said aryl and heteroaryl are optionally substituted by one or more groups independently selected from halogen atoms, CN, N3, C1-C6-alkyl, [SO3]−, SO3H, SO2Cl, OH, C1-C6-alkoxy, C(═O)OH and C1-C6-alkoxycarbonyl;
- R14 is selected from C1-C12-alkyl;
- and
- A−is a suitable anion preferably selected from halide ions, [BF4]31 , [PF6]−, [ClO4]−, [(C1-C5-alkyl)C(═O)O]−, [aryl-CH2-C(═O)O]−, [aryl-C(═O)O]−, [H2PO4]−[HSO4]−[SO4]2−, [(C1-C6-alkyl)SO3]−, [CF3SO3]−, aryl-CH2-SO3]−and [aryl-SO3]−, and wherein
- when R3 and R6 are independently selected from NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, then R9 is C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, C(═O)H, C(═O)-C1-C6-alkyl, C1-C12-alkylthio or aryl, wherein said aryl is substituted by one or more groups independently selected from C1-C6-alkyl, C1-C12-hydroxyalkyl, C1-C12-thioalkyl or N3;
- and wherein
- when Z is NR10, R1 and R8 is OMe, then R9 is not 2,6-dimethoxyphenyl or 4-( N(R15)2)-2,6-dimethoxyphenyl, wherein R15 is CH3, C2H5 or C6H13;
- and wherein
- when Z is O, R1 or R8 is OMe, then R9 is not 2,6-dimethoxyphenyl;
- and wherein
- when Z is O, R1 or R8 is OMe, then R9 is not phenyl.
21 more elements
A compound of formula (A′)
- wherein
- Z is NR10;
- R1 is selected from C1-C6-alkoxy, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14, OCNR2, CONHR14, CON(R14)2, C═NR14, CO2H, [CO2−], CO2R14, [SO3−], SO3R14, SO3H, SO2NC(CH3)3, SO2N(R14)2;
- R2 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, [SO3−], SO3H, SO3R14, CO2H, [CO2−], CO2R14, C1-C12-alkyl;
- R3 is selected from H, halogen, NO2, and CN;
- R4 is selected from H, C1-C12-alkyl, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, SO3R14, [S03−], SO3H;
- R5 is selected from H, C1-C12-alkyl, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, SO3R14, SO3H, [SO3−];
- R6 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, C1-C6-hydroxyalkyl;
- R7 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy and C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, C1-C12-alkyl, SO3R14, SO3H, [SO3−], CO2H, [CO2−], CO2R14;
- R8 is selected from H, halogen, C1-C6-alkoxy, OH, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14, OCNR2, CONHR14, CON(R14)2, C═NR14, CO2H, [CO2−], NO2, SO3R14, SO3H, SO2NC(CH3)3 and SO2N(R14)2;
- R9 is selected from aryl, heteroaryl, C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkyl, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, C1-C12-alkoxy, C1-C12-hydroxyalkyl, halogen, N3, C1-C4-alkyl-CO2H, C1-C4-alkyl-CO2-C1-C6-alkyl, C(═O)H, C(═O)-C1-C6-alkyl and C1-C12-alkylthio;
- and wherein said aryl and heteroaryl are optionally substituted by one or more groups independently selected from halogen atoms, CN, N3, C1-C6-alkyl, [S03]−, SO3H, SO2Cl, OH, C1-C6-alkoxy, C(═O)OH and C1-C6-alkoxycarbonyl, C1-C12-hydroxyalkyl, C1-C12-thioalkyl;
- R10 is selected from aryl, heteroaryl, C1-C4-alkyl-aryl, C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkyl, H, C1-C12-hydroxyalkyl, C(═O)H, C(═O)-C1-C6-alkyl, C1-C12-alkylthio, C1-C12-alkyl-CO2H;
- C1-C12-alkyl-CO2-C1-C12-alkyl, C1-C12-alkyl-CO2-C1-C4-alkyl-aryl, [O−];
- S(═O)-C1-C6-alkyl, S(═O)aryl, S(═O)-heteroaryl, S(O2)-C1-C6-alkyl, S(O2)-aryl, S(O2)-heteroaryl;
- wherein said aryl and heteroaryl are optionally substituted by one or more groups independently selected from halogen atoms, CN, N3, C1-C6-alkyl, [SO3]−, SO3H, SO2Cl, OH, C1-C6-alkoxy, C(═O)OH and C1-C6-alkoxycarbonyl;
- R14 is selected from C1-C12-alkyl.
14 more elements
A process for the preparation of the compound of formula (A)
- wherein
- Z is selected from NR10 and O;
- R1 is selected from C1-C6-alkoxy, OH, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14, OCNR2, CONHR14, CON(R14)2, C═NR14, CO2H, [CO2−], CO2R14, SO3R14, SO3H, [SO3−], SO2NC(CH3)3, SO2N(R14)2;
- R2 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, C1-C12-alkyl, SO3H, [SO3−], SO3R14, CO2H, [CO2−], CO2R14;
- R3 is selected from H, halogen, NO2, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, SH, C1-C6-alkylthio and CN;
- R4 is selected from H, C1-C12-alkyl, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, SO3H, [SO3−], SO3R14;
- R5 is selected from H, C1-C12-alkyl, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, SO3H, [SO3−], SO3R14;
- R6 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, aryloxy, O-alkyl-aryl, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio;
- R7 is selected from H, halogen, NO2, CN, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, OH, C1-C6-alkoxy, C1-C6-hydroxyalkyl, SH, C1-C6-alkylthio, C1-C12-alkyl, SO3H, [SO3−], SO3R14, CO2H, [CO2−], CO2R14;
- R8 is selected from H, halogen, C1-C6-alkoxy, OH, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14, OCN(R14)2, CONHR14, CON(R14)2, C═NR14, CO2H, [CO2−], NO2, SO3R14, SO3H, SO2NC(CH3)3 and SO2N(R14)2;
- R9 is selected from aryl, heteroaryl, C1-C4-alkyl-aryl, C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkyl, H, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, C1-C12-alkoxy, C1-C12-hydroxyalkyl, C(═O)H, C( O)-C1-C6-alkyl and C1-C12-alkylthio;
- and wherein said aryl and heteroaryl are optionally substituted by one or more groups independently selected from halogen atoms, CN, N3, C1-C6-alkyl, [SO3]−, SO3H, SO2C1, OH, C1-C6-alkoxy, C1-C4-alkyl-CO2H, C1-C4-alkyl-CO2-C1-C6-alkyl, C(═O)OH and C1-C6-alkoxycarbonyl, C1-C12-hydroxyalkyl, C1-C12-thioalkyl;
- R10 is selected from aryl, heteroaryl, C1-C4-alkyl-aryl, C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkyl, H, C1-C12-hydroxyalkyl, C(═O)H, C(═O)-C1-C6-alkyl, C1-C12-alkylthio, C1-C12-alkyl-CO2H;
- C1-C12-alkyl-CO2-C1-C12-alkyl, C1-C12-alkyl-CO2-C1-C4-alkyl-aryl, O−;
- S(═O)-C1-C6-alkyl, S(═O)aryl, S(═O)-heteroaryl, S(O2) -C1-C6-alkyl, S(O2)-aryl, S(O2)-heteroaryl;
- wherein said aryl and heteroaryl are optionally substituted by one or more groups independently selected from halogen atoms, CN, N3, C1-C6-alkyl, [SO3]−, SO3H, SO2Cl, OH, C1-C6-alkoxy, C(═O)OH and C1-C6-alkoxycarbonyl;
- R14 is selected from C1-C12-alkyl;
- and
- A−is a suitable anion preferably selected from halide ions, [BF4]−, [PF6]−, [ClO4]−, [(C1-C5-alkyl)C(═O)O]−, [aryl-CH2-C(═O)]−, [aryl-C(═O)O]−, [H2PO4]− [HSO4]−[SO4]2−, [(C1-C6-alkyl)SO3]−, [CF3SO3]−, aryl-CH2-SO3]−and [aryl-SO3]−;
- comprising
- (i) reacting a compound of formula (A″') with an organometallic reagent (R12M) selected from aryl-MgX, C1-C6-alkyl-MgX, aryl-Li and C1-C6-alkyl-Li;
- to form a compound of formula (A″)
- wherein when R11 is H, then R8 is selected from C1-C6-alkoxy, OH, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14, OCN(R14)2, CONHR14, CON(R14)2, C=NR14, CO2H, [CO2−], SO3R14, SO3H, [SO3−], SO2NC(CH3)3, SO2N(R14)2;
- and
- wherein when R11 is halogen, then R8 is selected from C1-C6-alkoxy, OH, C1-C6-hydroxyalkyl, O(CH2)O(CH3), O(CH2)O(CH2)2OCH3, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, SH, F, CF3, C1-C6-alkylthio, 4,4-dimethyl-4,5-dihydrooxazole, NHCOR14, NHCO2R14, OCN(R14)2, CONHR14, CON(R14)2, C═NR14, CO2H, [CO2−], SO3R14, SO3H, [S03−], SO2NC(CH3)3, SO2N(R14)2 and H;
- and
- wherein M is Li when the organometallic reagent (R12M) is aryl-Li or C1-C6-alkyl-Li;
- and wherein M is MgX when the organometallic reagent (R12M) is aryl-MgX or C1-C6-alkyl-MgX or MgX2 or alkyl2Mg or aryl2Mg;
- and wherein X is a halogen;
- (ii) followed by reacting said compound of formula (A″) with a compound of formula (B)
- or (C)
- R9CO2R13 (B)
- R9COCl (C)
- to form a compound of formula (A′),
- wherein R13 is C1-C6-alkyl, C1-C6-alkanoyl;
- or
- wherein R9 and R13 together with the atoms to which they are attached form a 4 to 6-membered ring optionally substituted by C2-C6-alkenyl-aryl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-alkyl, NH2, N(H)(C1-C6-alkyl), N(C1-C6-alkyl)2, C1-C12-alkoxy, C1-C12-hydroxyalkyl, halogen, CN, N3, C1-C4-alkyl-CO2H, C1-C4-alkyl -CO2-C1-C6-alkyl, C(═O)H, C(═O)-C1-C6-alkyl and C1-C12-alkylthio;
- or wherein R9 and R13 together with the atoms to which they are attached form a 4 to 6-membered ring fused to an aryl or heteraryl, wherein said aryl or heteraryl is optionally substituted by one or more groups independently selected from halogen atoms, CN, N3, C1-C6-alkyl, [SO3]−, SO3H, SO2C1, OH, C1-C6-alkoxy, C(═O)OH and C1-C6-alkoxycarbonyl, C1-C12-hydroxyalkyl, C1-C12-thioalkyl;
- (iii) addition of a protonic acid HA to form a compound of formula (A), wherein said HA is a suitable acid preferably selected from an inorganic acid or an organic acid, and
- wherein further preferably said inorganic acid is selected from HBr, HCl, HI, HBF4, HPF6 and HClO4, and said organic acid is selected from (C1-C5-alkyl)C(═O)OH, aryl-CH2-C(═O)OH, [aryl-C(═O)OH, H3PO4, (C1-C6-alkyl)SO3H, aryl-CH2-SO3H and aryl-SO3H, and wherein again further preferably said inorganic acid is selected from HBr, HCl, HBF4, HPF6 and HClO4, and said organic acid is selected from (C1-C6-alkyl)SO3H.
37 more elements
Dependencies are inferred from the claim text.