Heterocyclic fluorescent dyes and method of production thereof

Patent metadata

Field	Value
Publication number	US-8940895-B2
Application number	US-201214363104-A
Country	US
Kind code	B2
Filing date	Dec 17, 2012
Priority date	Dec 21, 2011
Publication date	Jan 27, 2015
Grant date	Jan 27, 2015

Abstract

The invention relates to novel compounds of formula (III) that can be used as heterocyclic dyes of unique structure and properties. These dyes can be obtained in a three-step synthesis from simple substrates.

First claim

The invention claimed is:

1. A compound of formula (III):

wherein Ar is a homo- or heteroaromatic system.

2. The compound according to claim 1 ,
wherein Ar is a homo- or heteroaromatic system, which is selected from

wherein the dotted lines are bonds to the 6-membered ring, the dotted line is a bond to a carbon atom in para-position to the nitrogen atom, the dotted line is a bond to a carbon atom in meta-position to the nitrogen atom, wherein
R′, R 1′ and R 1″ are each independently H, F, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with a halogen atom, or C 1 -C 25 alkyl,
R 2 is H, F, cyano, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl,
R 3 is hydrogen, F, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with a halogen atom, C 1 -C 25 alkyl,

wherein R 22 to R 25 and R 29 to R 33 are each independently H, F, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with a halogen atom, or C 1 -C 25 alkyl, and
R 26 is H, F, cyano, phenyl, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with a halogen atom, or C 1 -C 28 alkyl;
X is O, S, Se, or NR 4 ,
R 4 is hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 25 alkyl, which may optionally be interrupted by an oxygen or sulphur atom and/or is optionally substituted by a halogen atom; or C 7 C 25 arylalkyl.

3. The compound according to claim 2 , which is a compound of formula

wherein
R 1 , R 1′ , R 1″ , R 2 , R 3 and R 4 are as defined in claim 2 .

4. The compound according to claim 1 , wherein the compound is selected from the group consisting of the compounds of formulae 3a, 3b, 3c, 3d, 3e, 3f, 3g, 4a, 4b, and 4c:

5. A method for the production of a compound of formula (III) according to claim 1 :

where Ar is a homo- or heteroaromatic system, the method comprising:
a) alkylating a diketopyrollopyrrole of formula (I):

in a reaction with an acetal, and then
b) subjecting the N-alkylated derivative of formula (II) obtained in the alkylating a)

in the presence of an acid to intramolecular condensation, obtaining the compound of formula (III), wherein R 11 and R 12 are C 1 -C 8 alkyl, or together form a ring

6. The method according to claim 5 , wherein a) the alkylation reaction is carried out in the presence of tetrabutylammonium hydrogen sulfate, K 2 CO 3 and dimethylformamide (DMF), and the product obtained is isolated from the reaction mixture by extraction.

7. The method according to claim 5 , wherein in the subjecting b) the cyclization reaction is carried out in a mixture of ethanol and dioxane in the presence of HCl.

8. The method according to claim 5 , wherein in the subjecting b) the cyclization reaction is carried out in methylene chloride in the presence of trifluoromethanesulphonic acid.

9. An organic semiconductor material, layer or component, comprising a compound according to claim 1 .

10. A semiconductor device, comprising a compound according to claim 1 .

11. The semiconductor device according to claim 10 , which is an organic photovoltaic device, a photodiode, or an organic field effect transistor.

12. A process for the preparation of an organic semiconductor device, comprising either:
applying a solution and/or dispersion of a compound according to claim 1 in an organic solvent to a substrate and removing the solvent; or
evaporating the compound according to claim 1 .

13. A compound of formula

wherein Ar′ is a homo- or heteroaromatic system, which is selected from

wherein the dotted lines are bonds to the 6-membered ring, the dotted line is a bond to a carbon atom in para-position to the nitrogen atom, the dotted line is a bond to a carbon atom in meta-position to the nitrogen atom, wherein R 1 , R 1′ and R 1″ are each independently H, halogen, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with a halogen atom, or C 1 -C 25 alkyl,
R 2 is H, halogen, cyano, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl, R 3′ is Cl, Br, or I,

wherein R 22 to R 25 are each independently H, halogen, cyano, C 1 -C 25 alkoxy, C 1 -C 25 allyl substituted with a halogen atom, or C 1 -C 25 alkyl, and
R 26′ is Cl, Br, or I;
X is O, S, Se, or NR 4 ,
R 4 is hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 25 alkyl, which may optionally be interrupted by an oxygen or sulphur atom and/or is optionally substituted by a halogen atom; or C 7 -C 25 arylalkyl.

14. The compound according to claim 13 , which is a compound of formula

wherein R 1 , R 1′ , R 1″ , R 2 , R 3′ and R 4 are as defined in claim 13 .

15. The compound according to claim 13 , wherein the compound is selected from

wherein R 1 and R 1 are each independently hydrogen or C 1 -C 25 alkyl.

16. The compound according to claim 2 , wherein R 1 , R 1′ , and R1″ are each independently H, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl.

17. The compound according to claim 2 , wherein R 2 is H, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl.

18. The compound according to claim 2 , wherein R 3 is hydrogen, F, cyano, C 1 -C 25 alkyl,

Assignees

• Basf Se

Inventors

• Grzybowski Marek
• Gryko Daniel T

Classifications

• C07D491/22

  in which the condensed system contains four or more hetero rings · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• C07D471/22 Primary

  in which the condensed systems contains four or more hetero rings · CPC title

• C07D495/22

  in which the condensed system contains four or more hetero rings · CPC title

• H10K85/655

  comprising only sulfur as heteroatom · CPC title