Process for the preparation of tetracarboxynaphthalenediimide compounds disubstituted with heteroaryl groups

Patent metadata

Field	Value
Publication number	US-9000170-B2
Application number	US-201314386131-A
Country	US
Kind code	B2
Filing date	Mar 18, 2013
Priority date	Mar 19, 2012
Publication date	Apr 7, 2015
Grant date	Apr 7, 2015

Abstract

A process for the preparation of a tetracarboxynaphthalenediimide compound disubstituted with heteroaryl groups having general formula (I), comprising the reaction of at least one disubstituted N,N′-dialkyl-1,5,8-tetracarboxynaphthalenediimide with at least one heteroaryl compound. Said tetracarboxynaphthalenediimide compound disubstituted with heteroaryl groups can be advantageously used as monomer in the synthesis of semiconductor polymers which can be advantageously used in the construction of organic field effect transistors (OFET) or of organic thin film transistors (OTFT).

First claim

The invention claimed is:

1. A process for preparing a tetracarboxynaphthalenediimide compound disubstituted with heteroaryl groups of formula (I):

the process comprising:
reacting at least one disubstituted N,N′-dialkyl-1,4,5,8-tetracarboxy-naphthalenediimide of formula (II):

with at least one heteroaryl compound of formula (III):

wherein, in formulae (I)-(III),
R 1 represents a C 1 -C 30 alkyl group;
Y represents an oxygen atom; a sulfur atom; a NR 5 group where R 5 represents a hydrogen atom; or a C 1 -C 20 alkyl group;
Z represents a nitrogen atom; or a CR 2 group where R 2 is defined below;
R 3 represents a hydrogen atom; a linear or branched C 1 -C 20 alkyl group; an optionally substituted cycloalkyl group; an optionally substituted aryl group; a linear or branched C 1 -C 20 alkoxyl group; a polyethyleneoxyl group R 1 —O—[—CH 2 —CH 2 —O] n — where R 1 is defined above and n is an integer of from 1 to 4; a —R 6 —OH group where R 6 represents a linear or branched C 1 -C 20 alkylene group; a —R 6 —OR 7 group where R 6 is defined above and R 7 represents a linear or branched C 1 -C 20 alkyl group, or a polyethyleneoxyl group R 1 —O—[—CH 2 —CH 2 —O] n — where R 1 is defined above and n is an integer of from 1 to 4; a —COR 1 group where R 1 is defined above; a —COOR 1 group where R 1 is defined above; a —CHO group; or a cyano group (—CN);
R 2 represents a hydrogen atom; a linear or branched C 1 -C 20 alkyl group; or, when R 3 is different from hydrogen or when R 3 =R 2 , R 2 represents a linear or branched C 1 -C 20 alkoxyl group;
or R 3 and R 2 are optionally bound to each other so as to form, together with the carbon atoms to which R 3 and R 2 are bound, a cycle or polycyclic system containing from 3 to 14 carbon atoms, saturated, unsaturated, or aromatic, optionally containing one or more heteroatoms which are optionally oxygen, sulfur, nitrogen, silicon, phosphorous, and selenium;
R 4 represents a hydrogen atom; a linear or branched C 1 -C 20 alkyl group; an optionally substituted cycloalkyl group; an optionally substituted aryl group; an optionally substituted heteroaryl group; a —CHO group; a —COR 1 group where R 1 is defined above; a —COOR 1 group where R 1 is defined above; a —CONR 2 group where R 2 is defined above; or a cyano group (—CN);
or R 2 and R 4 are optionally bound to each other so as to form, together with the carbon atoms to which R 2 and R 4 are bound, a cycle or polycyclic system containing from 3 to 14 carbon atoms, saturated, unsaturated, or aromatic, optionally containing one or more heteroatoms which are optionally oxygen, sulfur, nitrogen, silicon, phosphorous, and selenium; and

X represents a halogen atom selected from the group consisting of chlorine, bromine, and iodine.

2. The process according to claim 1 , wherein said process relates to the preparation of 2,6-di-(2,2′-thienyl)-N,N′-dialkyl-1,4,5,8-tetracarboxynaphthal-enediimide corresponding to a tetracarboxynaphthalenediimide compound disubstituted, in positions 2 and 6, with heteroaryl groups having the formula (I) where
R 1 represents an ethyl-hexyl group or a n-heptyl group,
Y represents a sulfur atom,
Z represents a CR 2 group where R 2 represents a hydrogen atom, and
R 3 and R 4 represent a hydrogen atom.

3. The process according to claim 1 , wherein a molar ratio of said disubstituted N,N′-dialkyl-1,4,5,8-tetracarboxy-naphthalenediimide of formula (II) to said heteroaryl compound of formula (III) is from 1:2 to 1:20.

4. The process according to claim 1 , wherein said process is carried out in the presence of at least one weak organic base.

5. The process according to claim 4 , wherein said weak organic base is selected from the group consisting of a carbonate of an alkaline metal, a carbonate of an alkaline-earth metal, and any mixture thereof.

6. The process according to claim 4 , wherein a molar ratio of said disubstituted N,N′-dialkyl-1,4,5,8-tetracarboxynaphthalenediimide of formula (II) to said weak organic base is from 1:2.2 to 1:20.

7. The process according to claim 1 , wherein said process is carried out in the presence of at least one weak organic acid.

8. The process according to claim 7 , wherein said weak organic acid is selected from the group consisting of acetic acid, propionic acid, pivalic acid, isobutyl acid, and any mixture thereof.

9. The process according to claim 7 , wherein a molar ratio of said disubstituted N,N′-dialkyl-1,4,5,8-tetracarboxynaphthalenediimide of formula (II) to said weak organic acid is from 100:10 to 100:50.

10. The process according to claim 1 , wherein said process is carried out in the presence of at least one catalyst containing palladium.

11. The process according to claim 10 , wherein said catalyst containing palladium is selected from the group consisting of a compound of palladium in oxidation state (0), a compound of palladium in oxidation state (II), and any mixture thereof.

12. The process according to claim 10 , wherein a molar ratio of said disubstituted N,N′-dialkyl-1,4,5,8-tetracarboxynaphthalenediimide of formula (II) to said catalyst containing palladium is from 100:0.1 to 100:3.

13. The process according to claim 10 , wherein said process is carried out in the presence of at least one ligand of the catalyst containing palladium.

14. The process according to claim 13 , wherein said ligand is selected from the group consisting of triphenylphosphine, tri-cyclohexylphosphonium tetrafluoroborate, 2-di-cyclohexylphosphine-2′-(N,N-dimethyl-amino)-biphenyl, di-tert-butyl(methyl)-phosphonium tetrafluoroborate, tri-tert-butyl(methyl)phosphonium tetrafluoroborate, and any mixture thereof.

15. The process according to claim 13 , wherein a molar ratio of said disubstituted N,N′-dialkyl-1,4,5,8-tetracarboxynaphthalenediimide of formula (II) to said ligand is from 100:1 to 100:10.

16. The process according to claim 1 , wherein a molar concentration of said disubstituted N,N′-dialkyl-1,4,5,8-tetracarboxynaphthalenediimide of formula (II) is from 0.05 mmoles to 2 mmoles.

17. The process according to claim 1 , wherein said process is carried out in the presence of at least one non-polar organic solvent.

18. The process according to claim 17 , wherein said non-polar organic solvent is selected from the group consisting of toluene, xylene, chlorobenzene, and any mixture thereof.

19. The process according to claim 1 , wherein said process is carried out at a temperature ranging from 80° C. to 170° C.

20. The process according to claim 1 , wherein said process is carried out for a time ranging from 30 minutes to 24 hours.

Assignees

• Eni Spa

Inventors

• Schimperna Giuliana
• Pellegrino Andrea
• Chiaberge Stefano
• Bianchi Gabriele

Classifications

• C07D471/06 Primary

  Peri-condensed systems · CPC title

• C09B57/08

  Naphthalimide dyes; Phthalimide dyes · CPC title