BIS-THIENOBENZOTHIENOTHIPOHENE COMPOUNDS AND PROCESS FOR THEIR PREPARATION

Abstract

The present invention relates to bis-thienobenzothienothiophene compounds and a process for their preparation. More in particular, the present invention relates to a new angular bis-thienobenzothienothiophene compound and the process for its preparation wherein said process comprises reacting at least one dihalogenated dithiophene compound with at least one terminal alkyne and the subsequent double annulation reaction. Said bis-thienobenzothienothiophene compounds can be appropriately functionalized and polymerized to produce electron donor compounds that can be advantageously used in the construction of photovoltaic devices or semiconductor polymers. Furthermore, said bis-thienobenzothienothiophene compounds, after functionalization, may be advantageously used as spectral converters in luminescent solar concentrators.

Claims

1. Bis-thienobenzothienothiophene compound having the general formula (I): ##STR00030## where R is selected from hydrogen, C.sub.1-C.sub.20 alkyl group, linear or branched, or cycloalkyl group, where said alkyl and cycloalkyl groups are optionally substituted.

2. Compound according to claim 1 in which R is a C.sub.1-C.sub.12 alkyl group.

3. Compound according to claim 1 wherein R is a C.sub.3-C.sub.10 cycloalkyl group.

4. Compound according to claim 1 in which R is 3,7-dimethyloctyl.

5. Compound according to claim 1 in which R is 2-decyltetradecyl.

6. Monomers having one of the following formulas (Im), (In) or (Io), where: R represents a hydrogen atom, a linear or branched, C.sub.1-C.sub.20 alkyl group, or a cycloalkyl group, where said alkyl groups or cycloalkyl groups are optionally substituted, X is selected from chlorine, bromine and iodine, R′, identical or different, represent alkyl groups C.sub.1-C.sub.20 linear or branched, R″ identical or different, represent a hydrogen atom, or a linear or branched C.sub.1-C.sub.20 alkyl group, or the OR″ groups together with other atoms to which they are linked may form a heterocyclic ring having the following formula (1): ##STR00031## in which the substituents R″, identical or different, represent a hydrogen atom, or a linear or branched C.sub.1-C.sub.20 alkyl group, B is boron, and Sn is tin, ##STR00032##

7. (canceled)

8. (canceled)

9. Compounds having the following formulas I1, I2 and I3: ##STR00033## where: R represents a hydrogen atom, a linear or branched C.sub.1-C.sub.20 alkyl group, or a cycloalkyl group, where said alkyl groups of cycloalkyl groups are optionally substituted, X is selected from chlorine, bromine and iodine, R′, identical or different, represent a linear or branched C.sub.1-C.sub.20 alkyl group, R″, identical or different, represent a hydrogen atom, or a linear or branched C.sub.1-C.sub.20 alkyl group, or the OR″ groups together with other atoms to which they are linked may form a heterocyclic ring having the following formula (1): ##STR00034## in which the substituents R′″, identical or different, represent a hydrogen atom, or a linear or branched C.sub.1-C.sub.20 alkyl group, B is boron, and Sn is tin.

10. Compounds of formula ##STR00035## in which: Z represents a heteroatom selected from oxygen (O), sulphur (S) and selenium (Se); R represents a hydrogen atom, a linear or branched C.sub.1-C.sub.20 alkyl group, or a cycloalkyl group, where said groups are optionally substituted alkyl or cycloalkyl, R.sub.1, R.sub.2, identical or different, represent a hydrogen atom; or are selected from a linear or branched C.sub.1-C.sub.20 alkyl group, optionally substituted cycloalkyl groups, aryl groups, optionally substituted, linear or branched C.sub.1-C.sub.20 alkoxy groups, or R.sub.1 and R.sub.2 are linked together so as to form, together with the carbon atoms to which they are linked a cycle, or a polycyclic system containing from 2 to 14 carbon atoms, saturated, unsaturated or aromatic, optionally containing one or more heteroatoms.

11. Process for the preparation of bis-thienobenzothienothiophene compounds having general formula (I): ##STR00036## comprising reacting with a non-nucleophilic organic base at least one bis-alkynylarylene compound having general formula (II): ##STR00037## in which: R represents a hydrogen atom, a linear or branched C.sub.1-C.sub.20 alkyl group, or a cycloalkyl group, where said groups are optionally substituted alkyl or cycloalkyl.

12. The process according to claim 11 wherein the compound of general formula (II) and the non-nucleophilic organic base are used in molar ratios ranging between 1:1 and 1:5.

13. The process according to claim 11, wherein the non-nucleophilic organic base is selected from 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) and 1,4-diazabicycio[2.2.2]octane (DABCO).

14. The process according to claim 13 wherein the base is 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

15. The process according to claim 11 conducted in the presence of at least dipolar aprotic organic solvent.

16. The process according to claim 11 conducted at a temperature between 120° C. and 220° C.

17. The process according to claim 11 in which the compound (II) is prepared by coupling reaction between 2,5-dihalo-3,6-di (3′-thienyl)thieno[3,2-b]thiophene, where the halogen is selected from bromine and iodine and a terminal alkyne of formula RCCH catalyzed by compounds of copper and palladium.

18. Compound of formula (III) ##STR00038##

19. (canceled)

20. The compounds of claim 10 which are luminescent solar concentrators.

21. (canceled)

22. A polymer formed by a method comprising polymerizing at least one of the monomers (Im), (In) and (Io) according to claim 6.

23. The polymer according to claim 22 which is a semiconducting polymer or an electron donor for photovoltaic devices.

24. A method of making a polymer comprising polymerizing the monomer (Im) according to claim 6 with at least one of the following monomers having formula 1a or 1b: ##STR00039## wherein: Sn is tin; B is boron; A represents a heteroarylene group containing from 1 to 4 heteroatoms chosen from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus; or A represents an arylene group, said arylene group optionally being substituted with one or more groups chosen from —C(R.sub.A).sub.3 and —COR.sub.A wherein R.sub.A, identical or different among them, represent a hydrogen atom or a linear or branched C.sub.1-C.sub.20 alkyl group; or with one or more linear or branched C.sub.1-C.sub.20 alkyl groups; or with one or more aryl groups; R′, identical or different, represent a linear or branched C.sub.1-C.sub.20 alkyl group, R″, identical or different, represent a hydrogen atom, or a linear or branched C.sub.1-C.sub.20 alkyl group, or the groups OR″ together with other atoms to which they are linked may form a heterocyclic ring having the following formula (1): ##STR00040## wherein the substituents R″, identical or different, represent a hydrogen atom, or a linear or branched C.sub.1-C.sub.20 alkyl group.

25. A method of making a polymer comprising polymerizing at least one of the monomers of formula (In) or (Io) according to claim 6, with monomers of formula X-A-X, where: A represents a heteroarylene group containing from 1 to 4 heteroatoms chosen from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus; or A represents an arylene group, said arylene group optionally being substituted with one or more groups chosen from —C(R.sub.A).sub.3 and —COR.sub.A wherein R.sub.A, identical or different among them, represent a hydrogen atom or a linear or branched C.sub.1-C.sub.20 alkyl group; or with one or more linear or branched C.sub.1-C.sub.20 alkyl groups; or with one or more aryl groups; X represents a halogen atom.

Description

EXAMPLE 1

Preparation of 2,3,5,6-tetrabromothieno[3,2-b]thiophene having formula (VI) in diagram 5

[0125] The preparation is performed in accordance with L. S. Fuller, B. Iddon, K. A. Smith—J. Chem. Soc. Perkin Trans. 1 1997, 3465 and M. Turbiez, P. Frere, P. Leriche, N. Mercier, J. Roncali—Chem. Comm. 2005, 1161).

[0126] In an inert atmosphere, the bromine (9.2 ml; 28.5 g; 178.2 mmoles) diluted in 40 ml of chloroform is added to a solution of thienothiophene (5 g; 35.7 mmoles) in 40 ml of chloroform, by slow dripping. The temperature is brought to 60° C. After 24 hours, it is brought to 20° C. and a 1M aqueous solution of sodium thiosulfate is added until the excess bromine is completely destroyed. The precipitate is filtered and washed first with water and then with chloroform. 14.6 g of 2,3,5,6-tetrabromothieno[3,2-b]thiophene of formula (VI) are obtained with a 91% yield:

##STR00022##

EXAMPLE 2

Preparation of 3,6-dibromothieno[3,2-b]thiophene having formula (V) in diagram 5

[0127] In an inert atmosphere, the zinc powder (3.5 g; 53.5 mmoles) is added in portions to the suspension of 2,3,5,6-tetrabromothieno[3,2-b]thiophene (14.6 g; 32.2 mmoles) in 1 l of acetic acid. It is brought to 125° C. After 2 hours another portion of zinc is added (2.2 g; 33.6 mmoles) and after 30 minutes another portion (0.8 g; 12.2 mmoles). It is brought to 70° C. and the zinc is removed by filtration. At 20° C., water is added to the filtrate and extracted with ethyl acetate. After washing the organic phase, first with a saturated aqueous solution of sodium bicarbonate and then to neutrality with water, it is dried over sodium sulfate. 7.6 g of 3,6-dibromothieno[3,2-b]thiophene of formula (V) are obtained with a 80% yield:

##STR00023##

EXAMPLE 3

Preparation of 3,6-bis(3′-thienyl)thieno[3,2-b]thiophene having formula (IV) in diagram 5

[0128] The preparation is performed in accordance with C. Ko, W. H. Lam, V. W. Yam—Chem. Com. 2008, 5203.

##STR00024##

EXAMPLE 4

Preparation of 2,5-diiodo-3,6-di(3′-thienyl)thieno[3,2-b]thiophene having formula (III) in diagram 5

[0129] In at inert atmosphere, at 35° C., the N-iodosuccinimide (8.6 g; 38.1 mmoles) is added, in portions, to the solution of 3,6-bis(3′-thienyl)thieno[3,2-b]thiophene (5.8 g; 19.02 mmoles) in 1 l of chloroform and 100 ml of acetic acid. After 10 hours at 25° C. in the dark, a 1M aqueous solution of sodium thiosulfate is added. After filtration and washing of the precipitate first with water and then with ethyl ether, 8.9 g of 2,5-diiodo-3,6-di(3′-thienyl)thieno[3,2-b]thiophene of formula (III) are obtained with a yield of 85%:

##STR00025##

EXAMPLE 5

Preparation of 2,5-bis(5,9-dimethyldec-1-inyl)-3,6-di(3-thienyl)thieno[3,2-b]thiophene having formula (IIa)

[0130] In a 100 ml Pyrex glass flask, equipped with a cooling device, in an inert atmosphere, the following are loaded, in order: (2.7 g; 4.80 mmoles) of 2,5-diiodo-3,6-di(3′-thienyl)thieno[3,2-b]thiophene (5), 50 ml of toluene, 10 ml di triethylamine, (2.4 g; 14.40 mmoles) of 5,9-dimethyldecine, (0.064 g, 0.096 mmoles) of bis(triphenylphosphine)palladium(II)chloride [Pd(PPh.sub.3).sub.2Cl.sub.2] and (0.018 g, 0.096 mmoles) of copper(I)iodide (CuI). The flask is then placed in an oil bath pre-heated to 80° C., for 24 hours. After cooling to room temperature (25° C.), a saturated aqueous solution of sodium chloride (50 ml) is added to the reaction mixture and everything is extracted with diethyl ether (3×25 ml). The organic phase obtained is washed to neutrality with water (3×25 ml), and then dried over sodium sulfate and evaporated. The residue obtained is purified through elution on a silica gel chromatography column (eluent: heptane), obtaining 2.55 g of 2,5-bis(5,9-dimethyldec-1-inyl)-3,6-di(3-thienyl)thieno[3,2-b]thiophene as a white solid (85% yield):

##STR00026##

EXAMPLE 6

Preparation of 2,5-bis(4-decylhexadec-1-inyl)-3,6-di(3-thienyl)thieno[3,2-b]thiophene having formula (IIb)

[0131] In a Pyrex glass flask, equipped with a cooling device, in an inert atmosphere, the following are loaded, in order: (2.7 g; 4.80 mmoles) of 2,5-diiodo-3,6-di(3′-thienyl)thieno[3,2-b]thiophene (5), 50 ml of toluene, 10 ml di triethylamine, (5.2 g; 14.40 mmoles) of 4-hexadecyldecine, (0.064 g, 0.096 mmoles) of bis(triphenylphosphine)palladium(II)chloride [Pd(PPh.sub.3).sub.2Cl.sub.2] and (0.018 g, 0.096 mmoles) of copper(I)iodide (CuI). The flask is then placed in an oil bath pre-heated to 80° C., for 24 hours. After cooling to room temperature (25° C.), a saturated aqueous solution of sodium chloride (50 ml) is added to the reaction mixture and everything is extracted with diethyl ether (3×25 ml). The organic phase obtained is washed to neutrality with water (3×25 ml), and then dried over sodium sulfate and evaporated. The residue obtained is purified through elution on a silica gel chromatography column (eluent: heptane), obtaining 2.51 g of 2,5-bis(4-decylhexadec-1-inyl)-3,6-di(3′-thienyl)thieno[3,2-b]thiophene as a white solid (51% yield):

##STR00027##

EXAMPLE 7

Preparation of 4,10-bis(3,7-dimethyloctyl)benzo[b]thieno[5′,4′-2,3]thieno[4,5-b]thieno[3,2-e]benzo[b]thiophene having formula (Ia)

[0132] In an inert atmosphere, 1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU), (0.33 g; 2.14 mmoles) was added to a solution of 2,5-bis(5,9-dimethyldec-1-inyl)-3,6-di(3′-thienyl)thieno[3,2-b]thiophene having formula (IIa) (1.2 g; 1.78 mmoles) in 20 ml of N-methyl pyrrolidone (NMP). The reaction is then placed in an oil bath pre-heated to 200° C., for 3 hours. After cooling to room temperature (25° C.), the reaction mixture is placed in 100 mL of methanol, the precipitate obtained is filtered and dried under vacuum, obtaining 0.90 g of 4,10-bis(3,7-dimethyloctyl)benzo[b]thieno[5′,4′-2,3]thieno[4,5-b]thieno[3,2-e]benzo[b]thiophene as a white solid (yield 80%):

##STR00028##

EXAMPLE 8

Preparation of 4,10-bis(2-decyltetradecyl)benzo[b]thiophene[5′,4′-2,3]thiophene[4,5-b]thiophene[3,2-e]benzo[b]thiophene having formula (Ib)

[0133] In an inert atmosphere, 1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU), (0.23 g; 1.68 mmoles) is added to a solution of 2,5-bis(4-decylhexadec-1-inyl)-3,6-di(3′-thienyl)thieno[3,2-b]thiophene having formula (IIb) (1.4 g; 1.40 mmoles) in 20 ml of N-methyl pyrrolidone (NMP). The reaction is then placed in an oil bath pre-heated to 200° C., for 3 hours. After cooling to room temperature (25° C.), the reaction mixture is placed in 100 mL of methanol, the precipitate obtained is filtered and dried under vacuum, obtaining 1.14 g of 4,10-bis(3,7-dimethyloctyl)benzo[b]thieno[5′,4′-2,3]thieno[4,5-b]thieno[3,2-e]benzo[b]thiophene of formula (Ib) as a white solid (yield 81%):

##STR00029##