IP Library › Granted Patent US 9,595,680

Granted Patent B2

US 9,595,680 · App. 14/770,867 · Granted Mar 14, 2017

Heterocyclic fluorescent dyes and method of production thereof

Inventors: Daniel T. Gryko (Warsaw, PL); Marek Grzybowski (Szczecin, PL)

Assignee: BASF SE

H01L51/0062 C07D471/22 C07D487/04 C07D487/22 C07D491/22 C07D495/22 C07D517/22 C07D519/00 C08G69/00 C08G69/42 C09B57/004 C09B69/008 C09B69/109 G01N33/52 H01L51/0003 H01L51/0053 H01L51/0071 H01L51/0073 H01L51/0074 H01L51/0558 H01L51/42 Y02E10/549

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Quick Facts

Patent No.: US 9,595,680
App. No.: 14/770,867
Granted: Mar 14, 2017
Kind: B2

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Abstract

The invention relates to novel compounds of formula (III) that can be used as heterocyclic dyes of unique structure and properties. These compounds can be obtained in a three-step synthesis from simple substrates. The compounds according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the compounds according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

Claims (123)

1. A compound of formula (III):

wherein

Ar denotes a homo- or heteroaromatic system, which may be substituted, or unsubstituted; and

R 13 , R 13′ , R 14 and R 14′ are independently of each other hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkenyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by a group E Si or one or more halogen atoms; C 2 -C 25 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl-alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by a group E Si or one or more halogen atoms; C 7 -C 25 arylalkyl, C 7 -C 25 arylalkyl which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by a group E Si or one or more halogen atoms; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by halogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy, or C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms; C 3 -C 10 heteroaryl; C 3 -C 10 heteroaryl, which is substituted by halogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, which may optionally be interrupted by a group D Si , or one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms;

E Si is —SiR 161 R 162 R 163 or —O—SiR 161 R 162 R 163 ;

D Si is —SiR 161 R 162 —, —SiR 161 R 162 —(O—SiR 161 R 162 ) d — or —O—SiR 161 R 162 —;

R 161 , R 162 and R 163 are independently of each other hydrogen, C 1 -C 25 alkyl, C 3 -C 12 cycloalkyl, which might optionally be substituted with C 1 -C 4 alkyl; C 1 -C 25 haloalkyl, C 2 -C 25 alkenyl, —O—SiR 164 R 165 R 166 , —(O—SiR 164 R 165 ) d —R 166 , C 1 -C 25 alkoxy, C 3 -C 24 (hetero)aryloxy, NR 167 R 168 , halogen, C 1 -C 25 acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C 1 -C 25 alkyl, halogen, cyano or C 1 -C 25 alkoxy;

R 164 , R 165 and R 166 are independently of each other hydrogen, C 1 -C 25 alkyl, C 3 -C 12 cycloalkyl, which might optionally be substituted with C 1 -C 4 alkyl; C 1 -C 25 haloalkyl, C 2 -C 25 alkenyl, —O—SiR 169 R 170 R 171 , —(O—SiR 169 R 170 ) d —R 171 , C 1 -C 25 alkoxy, C 3 -C 24 (hetero)aryloxy, NR 167 R 168 , halogen, C 1 -C 25 acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C 1 -C 25 alkyl, halogen, cyano or C 1 -C 25 alkoxy;

R 169 , R 170 and R 171 are independently of each other hydrogen, C 1 -C 25 alkyl, C 3 -C 12 cycloalkyl, which might optionally be substituted with C 1 -C 4 alkyl; C 1 -C 25 haloalkyl, C 2 -C 25 alkenyl, —O—Si(CH 3 ) 3 , C 1 -C 25 alkoxy, C 3 -C 24 (hetero)aryloxy, NR 167 R 168 , halogen, C 1 -C 25 acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C 1 -C 25 alkyl, halogen, cyano or C 1 -C 25 alkoxy;

R 167 and R 168 are independently of each other 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; or C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C 7 -C 25 arylalkyl;

d is an integer from 1 to 50; with the proviso that at least one of R 13 , R 13′ , R 14 and R 14′ is different from hydrogen.

2. The compound of formula (III) according to claim 1 ,

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

wherein the dotted lines denotes the bonds to the 6-membered ring; the dotted line indicates the bond to the carbon atom in para-position to the nitrogen atom, the dotted line indicates the bond to the carbon atom in meta-position to the nitrogen atom,

R 1 , R 1′ and R 1″ are independently of each other H, halogen; cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; 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 hydrogen, halogen; cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; C 1 -C 25 alkyl,

wherein R 22 to R 25 and R 29 to R 33 represent independently of each other H, F, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; 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 one or more halogen atoms, or C 1 -C 25 alkyl; or

R 3 is a group of formula —NA 1 A 1′ , or a group,

wherein

A 1 and A 1′ are independently of each other C 1 -C 18 alkyl,

R 116 , R 117 , R 118 and R 119 are independently of each other hydrogen, C 1 -C 18 alkyl, which may optionally be interrupted by —O—, or C 1 -C 18 alkoxy;

R 5 , R 6 , R 7 and R 8 are independently of each other hydrogen, halogen; cyano, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl substituted with one or more halogen atoms;

X and X 1 are independently of each other 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, halogen; or C 1 -C 18 alkoxy; C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms; or C 7 -C 25 arylalkyl; or

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

wherein

X 92 is O, S, CR 99 R 99′ , or NR 130 , X 93 is O, S, or NR 130 , X 94 is O, S, or NR 130 ,

R 99 , R 99′ , R 99″ and R 99 * are independently of each other hydrogen, C 1 -C 25 alkyl, or C 1 -C 25 alkyl substituted with one or more halogen atoms and/or interrupted by one or more oxygen atoms, or two moieties R 99 and R 99′ or R 99″ and R 99 * can form a 5 or 6 membered alkyl ring, which optionally can be substituted with one or more halogen atoms and/or interrupted by one or more oxygen atoms;

R 121 , R 122 , R 123 , R 124 and R 125 are independently of each other hydrogen, halogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, halogen; or C 1 -C 18 alkoxy; C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms; or C 7 -C 25 arylalkyl;

R 130 is hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, halogen; or C 1 -C 18 alkoxy; C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms; or C 7 -C 25 arylalkyl; and

R 3 is as defined above.

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

wherein

R 1 , R 1′ , and R 1″ are independently of each other H, halogen; cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; 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 hydrogen, halogen; cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; C 1 -C 25 alkyl,

wherein R 22 to R 25 and R 29 to R 33 represent independently of each other H, F, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; 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 one or more halogen atoms, or C 1 -C 25 alkyl; or

R 3 is a group of formula —NA 1 A 1′ , or a group

wherein

A 1 and A 1′ are independently of each other C 1 -C 18 alkyl,

R 116 , R 117 , R 118 and R 119 are independently of each other hydrogen, C 1 -C 18 alkyl, which may optionally be interrupted by —O—, or C 1 -C 18 alkoxy;

X is O, S, Se, or NR 4 ,

and R 4 is hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, halogen; or C 1 -C 18 alkoxy; C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms; or C 7 -C 25 arylalkyl, and

E Si is —SiR 161 R 162 R 163 or —O—SiR 161 R 162 R 163 ;

D Si is —SiR 161 R 162 —, —SiR 161 R 162 —(O—SiR 161 R 162 ) d — or —O—SiR 161 R 162 —;

d is an integer from 1 to 50; with the proviso that at least one of R 13 , R 13′ , R 14 and R 14′ is different from hydrogen; or

which is a compound of formula

R 13 , R 13′ , R 14 and R 14′ may be the same or different and are selected from hydrogen or a C 1 -C 38 alkyl group;

R 99 , R 99′ , R 99″ and R 99 * are independently of each other hydrogen, C 1 -C 25 alkyl, or C 1 -C 25 alkyl interrupted by one or more oxygen atoms; preferably C 3 -C 25 alkyl, or C 3 -C 25 alkyl which is interrupted by one or more oxygen atoms;

R 121 , R 122 , R 123 , R 124 and R 125 are independently of each other hydrogen, halogen, C 1 -C 18 alkoxy or C 1 -C 25 alkyl; preferably hydrogen;

4. The compound according to claim 3 , wherein R 1 , R 1′ , and R 1 * are independently of each other H, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl.

5. The compound according to claim 3 , wherein R 2 is H, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl.

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

7. The compound according to claim 3 , which is selected from

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

R 13 , R 14 and Ar are as defined in claim 1 ,

the method comprising the steps of

a) reacting a diketopyrrolopyrrole of formula (I):

with a compound of formula

wherein X 2 is C, Br, or I; and then

b) submitting the N-alkylated derivative of formula (II) obtained in step a)

in the presence of acid to intramolecular condensation, to obtain the compound of formula (III).

9. The method according to claim 8 , wherein step a) is an alkylation reaction carried out in the presence of tetrabutylammonium hydrogen sulfate, K 2 CO 3 and dimethylformamide (DMF).

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

11. A method of using the compounds of formula (III) according to claim 1 , comprising:

adding the compounds of formula (III) as organic pigments in the development of fluorometric techniques, in modem biomedical techniques and diagnostics including fluorescence imaging and the detection of cations, and in semiconductor devices.

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

13. A semiconductor device, comprising

a compound according to claim 1 , and/or

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

14. The semiconductor device according to claim 13 , which is an organic photovoltaic device, a photodiode, or an organic field effect transistor.

15. Process for the preparation of an organic semiconductor device, which process comprises

applying a solution and/or dispersion of a compound according to claim 1 in an organic solvent to a suitable substrate and

removing the solvent; or which process comprises evaporation of a compound according to claim 1 .

16. A compound of formula

wherein Ar′ is selected from

E Si is —SiR 161 R 162 R 163 or —O—SiR 161 R 162 R 163 ;

D Si is —SiR 161 R 162 —, —SiR 161 R 162 —(O—SiR 161 R 162 ) d — or —O—SiR 161 R 162 —;

d is an integer from 1 to 50; with the proviso that at least one of R 13 , R 13′ , R 14 and R 14′ is different from hydrogen,

R 1 , R 1′ , and R 1″ are independently of each other H, halogen; cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; or C 1 -C 25 alkyl,

R 2 is H, halogen; cyano, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl,

R 5 , R 6 , R 7 , and R 8 are independently of each other hydrogen, halogen; cyano, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl substituted with one or more halogen atoms,

R 3′ is Cl, Br, I,

wherein

X and X 1 are independently of each other O, S, Se, or NR 4 ,

R 22 to R 25 are independently of each other H, F, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; or C 1 -C 25 alkyl and

R 26′ is Cl, Br, or I.

17. The compound according to claim 16 , which is selected from

wherein R 1 , R 1′ , and R 1″ are independently of each other H, halogen; cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; or C 1 -C 25 alkyl,

R 2 is H, halogen; cyano, C 1 -C 25 alkoxy, or C 1 -C 25 alkyl, and

R 13 , R 13′ , R 14 and R 14′ are independently of each other hydrogen, C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkenyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by a group E Si or one or more halogen atoms; C 2 -C 25 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl-alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by a group E Si or one or more halogen atoms; C 7 -C 25 arylalkyl, C 7 -C 25 arylalkyl which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by a group E Si or one or more halogen atoms; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by halogen, C 1 -C 15 alkyl, or C 1 -C 15 alkoxy, or C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms; C 3 -C 10 heteroaryl; C 3 -C 10 heteroaryl, which is substituted by halogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, which may optionally be interrupted by a group D Si , or one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms;

E Si is —SiR 161 R 162 R 163 or —O—SiR 161 R 162 R 163 ;

D Si is —SiR 161 R 162 —, —SiR 161 R 162 —(O—SiR 161 R 162 ) d — or —O—SiR 161 R 162 —;

d is an integer from 1 to 50; with the proviso that at least one of R 13 , R 13′ , R 14 and R 14′ is different from hydrogen,

R 3′ is Cl, Br, I,

wherein

X is O, S, Se, or NR 4 ,

R 24 and R 25 are independently of each other H, F, cyano, C 1 -C 25 alkoxy, C 1 -C 25 alkyl substituted with one or more halogen atoms; or C 1 -C 25 alkyl and

R 26′ is Cl, Br, or I.

18. The compound according to claim 17 , which is selected from

19. A method of using the compounds of claim 16 for the production of polymers, comprising:

adding the compounds of claim 16 as intermediates in the production of polymers.

Assignments (2)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 22, 2020

From: BASF SE

To: CLAP CO., LTD.

Reel/Frame 052459/0201 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 5, 2016

From: GRYKO, DANIEL T.; GRZYBOWSKI, MAREK

To: BASF SE

Reel/Frame 038189/0347 →

Priority Claims (4)

EP 13157961 · Mar 6, 2013 · regional

EP 13173518 · Jun 25, 2013 · regional

EP 13191722 · Nov 6, 2013 · regional

EP 13195706 · Dec 4, 2013 · regional

Continuity (2)

Provisional Application 61773166 · Mar 6, 2013

Related Publication 20150380660A1 · Dec 31, 2015