Dihydropyrene derivatives, processes for preparing the same and their uses

1. A method for treating pathologies sensitive to singlet oxygen, in particular for phototherapy and/or for treating cancers comprising administering to a subject in need thereof a compound of the following formula I

wherein:

n represents 0 or 1,

represents a single bond or no bond,

represents a single or a double bond,

R 1 and R′ 1 represent independently from each other:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

—N(R) 3 + ,

R representing:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

R 2 , R 3 , R 4 and R 5 represent independently from each other:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

—N(R) 3 + ,

R representing:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

X represents one or more physiologically acceptable counter anion(s),

providing that:

at least one of R 1 , R′ 1 , R 2 , R 3 , R 4 and R 5 represents one of the following groups:

or

—N(R) 3 + ,

n, and the bonds 1 to 7 are such as:

n=0, represents a single bond, bonds 1, 4 and 6 represent a double bond, and bonds 2, 3, 5 and 7 represent a single bond, or

n=0, represents no bond, bonds 1, 3, 5 and 7 represent a double bond, and bonds 2, 4 and 6 represent a single bond, or

n=1, represents no bond, bonds 2, 5 and 7 represent a double bond, and bonds 1, 3, 4 and 6 represent a single bond.

2. The method according to claim 1 wherein:

R 1 and R′ 1 are identical;

R 1 and/or R′ 1 represent(s) a linear or branched (C 1 -C 18 )-alkyl, in particular a tert-butyl;

R 2 and/or R 4 represent(s)

R 3 and R 5 representing in particular H;

R 3 and/or R 5 represent(s)

R 2 and R 4 representing in particular H; or

X is (are) chosen from the group consisting in Cl − , PF 6 − , BF 4 − , CH 3 COO − , Br − , F − , SO 4 2− , HSO 4 − , HPO 4 2− , H 2 PO 4 − ; or

R represents a linear or branched (C 1 -C 18 )-alkyl, in particular —CH 3 .

3. The method according to claim 1 wherein the compound is one of the compound of the following formulae:

4. The method according to claim 1 , wherein the compound of formula I forms a complex of the following formula II

B group being chosen from a peptide or an acid residue selected from a hyaluronic acid or a folic acid.

5. A pharmaceutical or diagnostic composition comprising a compound of formula I according to claim 1 as active agent and a pharmaceutically acceptable vehicle.

6. Compound of the following formula I (bis)

wherein:

n is 1,

represents a single bond or no bond,

represents a single or a double bond,

R 1 and R′ 1 represent independently from each other:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

—N(R) 3 + ,

R representing:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

R 2 , R 3 , R 4 and R 5 represent independently from each other:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

—N(R) 3 + ,

R representing:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

X represents one or more counter anion(s), in particular one or more physiologically acceptable counter anion(s),

providing that:

at least one of R 1 , R′ 1 , R 2 , R 3 , R 4 and R 5 represents one of the following groups:

or

—N(R) 3 + f

n, and the bonds 1 to 7 are such as:

n=1, represents no bond, bonds 2, 5 and 7 represent a double bond, and bonds 1, 3, 4 and 6 represent a single bond.

7. Compound according to claim 6 , wherein:

R 1 and R′ 1 are identical;

R 1 and/or R′ 1 represent(s) a linear or branched (C 1 -C 18 )-alkyl, in particular a tert-butyl;

R 2 and/or R 4 represent(s)

R 3 and R 5 representing in particular H;

R 3 and/or R 5 represent(s)

R 2 and R 4 representing in particular H;

X is (are) chosen from the group consisting in Cl − , PF 6 − , BF 4 − , CH 3 COO − , Br − , F − , SO 4 2− , HSO 4 − , HPO 4 2− , H 2 PO 4 − ; or

R represents a linear or branched (C 1 -C 18 )-alkyl, in particular —CH 3 .

8. Compound according to claim 7 , of one of the following formulae:

9. A pharmaceutical or diagnostic composition comprising a compound of formula I according to claim 1 as active agent and a pharmaceutically acceptable vehicle.

10. A pharmaceutical or diagnostic composition comprising a compound of formula I according to claim 2 as active agent and a pharmaceutically acceptable vehicle.

11. A pharmaceutical or diagnostic composition comprising a compound of formula I according to claim 3 as active agent and a pharmaceutically acceptable vehicle.

12. A pharmaceutical or diagnostic composition comprising a complex of formula II according to claim 4 as active agent and a pharmaceutically acceptable vehicle.

13. The method according to claim 4 , wherein the B group is a peptide of the following formula:

14. A compound of the following formula I (bis)

wherein:

n represents 0 or 1,

represents a single bond or no bond,

represents a single or a double bond,

R 1 and R′ 1 represent independently from each other:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

—N(R) 3 + ,

R representing:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

R 2 , R 3 , R 4 and R 5 represent independently from each other:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

—N(R) 3 + ,

R representing:

H,

a linear or branched (C 1 -C 18 )-alkyl,

a (C 3 -C 8 )-cycloalkyl,

X represents one or more counter anion(s), in particular one or more physiologically acceptable counter anion(s),

providing that:

at least one of R 1 , R′ 1 , R 2 , R 3 , R 4 and R 5 represents one of the following groups:

or

—N(R) 3 + ,

n, and the bonds 1 to 7 are such as:

n=0, represents a single bond, bonds 1, 4 and 6 represent a double bond, and bonds 2, 3, 5 and 7 represent a single bond, or

n=0, represents no bond, bonds 1, 3, 5 and 7 represent a double bond, and bonds 2, 4 and 6 represent a single bond, or

n=1, represents no bond, bonds 2, 5 and 7 represent a double bond, and bonds 1, 3, 4 and 6 represent a single bond,

when n=0, R 1 and/or R′ 1 are different from one of the following groups:

or

—N(R) 3 + ,

wherein the compound of formula I(bis) forms a complex of the following formula II(bis)

II (bis)

B group being chosen from a peptide or an acid residue selected from a hyaluronic acid or a folic acid.

15. The compound according to claim 14 , wherein:

R 1 and R′ 1 are identical;

R 1 and/or R′ 1 represent(s) a linear or branched (C 1 -C 18 )-alkyl, in particular a tert-butyl;

R 2 and/or R 4 represent(s)

R 3 and R 5 representing in particular H;

R 3 and/or R 5 represent(s)

R 2 and R 4 representing in particular H;

X is (are) chosen from the group consisting in Cl − , PF 6 − , BF 4 − , CH 3 COO − , Br − , F − , SO 4 2− , HSO 4 − , HPO 4 2− , H 2 PO 4 − ; or

R represents a linear or branched (C 1 -C 18 )-alkyl, in particular —CH 3 .

16. The compound according to claim 14 , of one of the following formulae:

17. The compound according to claim 14 , wherein the B group is a peptide of the following formula: