Synthons for developing organic semiconductors

1. A process for the synthesis of π-conjugated materials of formula (1b)

in which

represents a central polyfunctional unit bearing functions allowing grafting in position 9 of the carbazole nucleus,

n is an integer equal to or greater than 2, advantageously comprised between 2 and 5,

R 1 and R 2 , identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising:

i. hydrogen;

ii. aryl groups, said aryl groups being able to be substituted by at least one straight or branched C 1 -C 5 alkyl group;

iii.

groups in which Ar 1 and Ar 2 , identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from:

a. a hydrogen atom;

b. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

c. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

d. oligoethers; and

e. oligothioethers,

provided that R 1 and R 2 are not simultaneously a hydrogen atom,

R 3 and R 4 , identical or different, occupy the positions left free by R 1 and R 2 and are selected from:

a. hydrogen;

b. halogens;

c. nitro group;

d. sulphonate group;

e. amine groups;

f. carbonyl groups;

g. mono- or polycyclic aromatic groups;

h. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

i. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

j. oligoethers; and

k. oligothioethers,

the process comprising a step of reacting a synthon of formula (I)

in which

W represents an —N(H)— group,

R 1 and R 2 , identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising:

i. hydrogen;

ii. the mono- or polycyclic aromatic groups, said groups being able to be substituted by at least one straight or branched C 1 -C 12 alkyl group, in particular a methyl group, or by a straight or branched C 1 -C 12 alkoxy group, in particular a methoxy;

iii.

groups in which Ar 1 and Ar 2 , identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from:

a. hydrogen atom;

b. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

c. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S,

d. oligoethers; and

e. oligothioethers,

provided that R 1 and R 2 are not simultaneously a hydrogen atom,

R 3 and R 4 , identical or different, occupy the positions left free by R 1 and R 2 and are selected from:

a. hydrogen;

b. halogens;

c. a nitro group;

d. a sulphonate group;

e. amine groups;

f. carbonyl groups;

g. mono- or polycyclic aromatic groups;

h. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

i. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; and

j. oligoethers;

with a compound of formula X-Q-X, in which X represents a halogen atom and Q represents a spacer selected from a group consisting of: C 1 -C 12 alkylenyl groups, arylenyl groups, oligoethers and oligothioethers.

2. The process according to claim 1 , characterized in that in the compound of formula (I), R 1 and R 2 each represent, independently of one another, a group selected from:

i. the phenyl, naphthyl, anthracenyl, indenyl, biphenyl, terphenyl, carbazolyl groups, said groups being able to be substituted by at least one straight or branched C 1 -C 12 alkyl group, in particular a methyl group;

ii.

 groups in which Ra and Rb, identical or different, each represent, independently of one another:

a. either a hydrogen atom;

b. or a straight or branched C 1 -C 12 alkyl group, said alkyl group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

c. or a straight or branched C 1 -C 12 alkoxy group, said alkoxy group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

d. or an oligoether;

e. or an oligothioether.

3. The process according to claim 1 , characterized in that in the compound of formula (I), R 3 and R 4 each represent a hydrogen atom.

4. The process for the synthesis of π-conjugated materials according to claim 1 , further comprising:

a) a step of protecting W when W represents an —N(H)— group in the compound of formula (II)

and

R 3 and R 4 , identical or different, are selected from:

i. hydrogen;

ii. halogens;

iii. a nitro group;

iv. a sulphonate group;

v. amine groups;

vi. carbonyl groups;

vii. mono- or polycyclic aromatic groups;

viii. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

ix. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

x. oligoethers; and

xi. oligothioethers,

provided that if R 3 is in position 2 then R 4 is not in position 7 and if R 3 is in position 3 then R 4 is not in position 6,

to give a compound of formula (III)

in which GP is an amine protecting group,

b) treating the compound of formula (III) with a halogenated derivative, to give a compound of formula (IVb)

in which

R 3 and R 4 are as defined in claim 1 and

X, in position 3 and 6 of the carbazole represents a halogen atom, in particular an iodine or bromine atom,

c) a coupling reaction of said compound of formula (IVb) to give a compound of formula (Vb)

in which R 1 , R 2 , R 3 and R 4 are as defined in claim 1 .

5. A process for the synthesis of π-conjugated materials of formula (Ib′)

in which

R 1 and R 2 , identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising:

i. hydrogen;

ii. the aryl groups, said aryl groups being able to be substituted by at least one straight or branched C 1 -C 12 alkyl group, in particular a methyl group;

iii.

groups in which A 1 and A 2 , identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from:

a. hydrogen atom;

b. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

c. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

d. oligoethers; and

e. oligothioethers,

provided that R 1 and R 2 are not simultaneously a hydrogen atom,

R 3 and R 4 , identical or different, occupy the positions left free by R 1 and R 2 and are selected from:

a. hydrogen;

b. halogens;

c. a nitro group;

d. a sulphonate group;

e. an amine group;

f. a carbonyl group;

g. mono- or polycyclic aromatic groups;

h. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

i. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

f. oligoethers; and

g. oligothioethers;

and

R 6 represents either a straight or branched C 1 -C 12 alkyl group, or a C 6 -C 18 aryl group, in particular a benzene or methoxybenzene (anisole) group, or an amine protecting group, in particular a benzyl group, optionally substituted by a C 1 -C 5 alkoxy group, or a C 6 -C 18 aryl group substituted by a halogen, in particular fluorine or substituted by a straight or branched fluorinated C 1 -C 12 alkyl group, in particular trifluoromethyl (CF 3 ), or a bi-, tri or tetracyclic group comprising from 10 to 18 carbon atoms, such as for example a naphthyl, tetrahydronaphthyl, anthracenyl or pyrenyl group,

the process comprising a step of reacting a synthon of formula (I)

in which

W represents an —N(H)— group,

R 1 and R 2 , identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are selected independently of one another from the group comprising:

i. hydrogen;

ii. the mono- or polycyclic aromatic groups, said groups being able to be substituted by at least one straight or branched C 1 -C 12 alkyl group, in particular a methyl group, or by a straight or branched C 1 -C 12 alkoxy group, in particular a methoxy;

iii.

groups in which A 1 and A 2 , identical or different, each represent independently of one another an aryl group, optionally substituted by one or more substituents, identical or different, selected from:

f. hydrogen atom;

g. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

h. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S,

i. oligoethers; and

j. oligothioethers,

provided that R 1 and R 2 are not simultaneously a hydrogen atom,

R 3 and R 4 , identical or different, occupy the positions left free by R 1 and R 2 and are selected from:

k. hydrogen;

l. halogens;

m. a nitro group;

n. a sulphonate group;

o. amine groups;

p. carbonyl groups;

q. mono- or polycyclic aromatic groups;

r. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

s. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S; and

t. oligoethers;

with a compound of formula X-Q-X, in which X represents a halogen atom and Q represents a spacer selected from a group consisting of: C 1 -C 12 alkylenyl groups, arylenyl groups, oligoethers and oligothioethers.

6. The process according to claim 5 , characterized in that in the compound of formula (I), R1 and R2 each represent, independently of one another, a group selected from:

i. the phenyl, naphthyl, anthracenyl, indenyl, biphenyl, terphenyl, carbazolyl groups, said groups being able to be substituted by at least one straight or branched C 1 -C 12 alkyl group, in particular a methyl group;

ii.

 groups in which Ra and Rb, identical or different, each represent, independently of one another:

a. either a hydrogen atom;

b. or a straight or branched C 1 -C 12 alkyl group, said alkyl group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

c. or a straight or branched C 1 -C 12 alkoxy group, said alkoxy group being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

d. or an oligoether;

e. or an oligothioether.

7. The process according to claim 5 , characterized in that in the compound of formula (I), R3 and R4 each represent a hydrogen atom.

8. The process for the synthesis of π-conjugated materials according to claim 5 further comprising:

a) a step of protecting W when W represents an —N(H)— group in the compound of formula (II)

and

R 3 and R 4 , identical or different, are selected from:

xii. hydrogen;

xiii. halogens;

xiv. a nitro group;

xv. a sulphonate group;

xvi. amine groups;

xvii. carbonyl groups;

xviii. mono- or polycyclic aromatic groups;

xix. straight or branched C 1 -C 12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

xx. straight or branched C 1 -C 12 alkoxy groups, said alkoxy groups being able to be saturated or unsaturated and being able to comprise one or more heteroatoms selected from O and S;

xxi. oligoethers; and

xxii. oligothioethers,

provided that if R 3 is in position 2 then R 4 is not in position 7 and if R 3 is in position 3 then R 4 is not in position 6,

to give a compound of formula (III)

in which GP is an amine protecting group,

b) treating the compound of formula (III) with a halogenated derivative, to give a compound of formula (IVb)

in which

R 3 and R 4 are as defined in claim 1 and

X, in position 3 and 6 of the carbazole represents a halogen atom, in particular an iodine or bromine atom,

c) a coupling reaction of said compound of formula (IVb) to give a compound of formula (Vb)

in which R 1 , R 2 , R 3 and R 4 are as defined in claim 5 .