Patent

1. A compound having formula II

wherein

X 1 to X 4 are N,

X 5 is C or N,

R 1 is H, Hal, —OR′, —NHR′, C1-C12 alkyl, C1-C12alkoxy, C1-C12 alkanoyl, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C12 alkoxy)carbonyl, or (C1-C12 alkylamino)carbonyl, wherein R′ is H or C1-C6 alkyl

R2 is O,

R 3 , R 4 are independently of each other H, formyl, iminomethyl, nitroso, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, or halosubstituted C1-C12 alkanoyl,

R 5 is H, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkanoyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 12 alkoxy)carbonyl, or (C 1 -C 12 alkylamino)carbonyl,

R 6 , R 7 are independently of each other straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , or a group of the formula III

—S 1 —Ar 1 —S 2 — 18 F  III

wherein S 1 and S 2 are independently of each other a single bond, a spacer unit, a straight-chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of the non-adjacent CH 2 groups may independently be replaced by —O—, —CO—, —CO—O—, —O—CO—, —NR′—, —N═, —NR′—CO—, —CO—NR′—, —NR′—CO—O—, —O—CO—NR′—, —NR′—CO—NR′—, —CH═CH—, —C≡C—, —S—, —SO 3 R′—, —PR′—, or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof, and

Ar 1 is a triazole or a tetrazole,

with the proviso that one of R 6 and R 7 is a group of formula III,

m is 0 or 1,

P is 0, 1 or 2, and

q has a value of 1 to 7.

2. A compound according to claim 1 , wherein R 6 is straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and R 7 is a group of formula III.

3. A compound according to claim 1 , wherein R 7 is straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and R 6 is a group of formula III.

4. A compound according to claim 1 wherein S 1 is a single bond, a spacer unit, a straight-chain or branched C 1 -C 18 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of non-adjacent CH 2 groups may independently be replaced by —O—, —CO—, —CO—O—, —NR′—, —NR′—CO—, —CO—NR′—, —CH═CH—, —C≡C—, or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof.

5. A compound according to claim 1 wherein S 2 is a single bond or a straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof.

6. A compound according to claim 1 , which is of formula IV

wherein

X 6 , X 7 are independently of each other C, N or O,

R 8 , R 9 are independently of each other H or straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of embedded, non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—, or a group of the formula V

—S 3 —Ar 1 —S 2 — 18 F  V

wherein S 2 , S 3 are independently of each other a single bond, a spacer unit, a straight chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of the non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —O—CO—, —NR′—, —N═, —NR′—CO—, —CO—NR′—, —NR′—CO—O—, —O—CO—NR′—, —NR′—CO—NR′—, —CH═CH—, —C≡C—, —S—, —SO 3 R′—, —PR′—, or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′represents H or C 1 -C 6 alkyl, or a combination thereof,

Ar 1 is a triazole or a tetrazole,

X 1 to X 4 are N,

X 5 is C or N,

R 1 is H, Hal, —OR′, —NHR′, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C12 alkoxy)carbonyl, or (C1-C12 alkylamino)carbonyl, wherein R′ is H or C1-C6 alkyl R2 is O,

R 3 , R 4 are independently of each other H, formyl, iminomethyl, nitroso, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, or halosubstituted C1-C12 alkanoyl,

R 5 is H, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkanoyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C1-C12 alkoxy)carbonyl, or (C 1 -C 12 alkylamino)carbonyl,

R 6 is a straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , or a group of the formula III

—S 1 —Ar 1 —S 2 — 18 F  III

wherein S 1 and S 2 are independently of each other a single bond, a spacer unit, a straight-chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of the non-adjacent CH 2 groups may independently be replaced by —O—, —CO—, —CO—O—, —O—CO—, —NR′—, —N═, —NR′—CO—, —CO—NR′—, —NR′—CO—O—, —O—CO—NR′—, —NR′—CO—NR′—, —CH═CH—, —C≡C—, —S—, —SO 3 R′—, —PR′—, or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof, and

Ar 1 is a triazole or a tetrazole,

m is 0 or 1,

p is 0, 1 or 2, and

q has a value of 1 to 7,

with the proviso that either R 6 is a group of formula III or at least one of R 8 and R 9 is a group of formula V.

7. A compound according to claim 6 , wherein S 2 and S 3 are independently of each other a single bond or a straight chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof.

8. A compound according to claim 1 wherein Ar 1 is selected from formulae V-c, V-d and V-e

wherein the dotted lines represent linking sites to the spacer groups and R″ is H, Hal, NH—COR′, NH—SO 2 R′, CO 2 R′, or COR′, wherein R′ represents H or C1-C6 alkyl, or straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, OH, NH 2 , SO 3 H, SH, CO 2 H, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof.

9. A compound according to claim 6 , wherein R 6 is CN, Hal, NO 2 , or a group R 5 and at least one of R 8 and R 9 is a group of formula V.

10. A compound according to claim 6 , wherein R 6 is CN, Hal, NO 2 , or a group R 5 , R 8 is H or straight chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal or NO 2 , wherein one or more of embedded, non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—, and R 9 is a group of formula V.

11. A compound according to claim 6 , wherein R 6 is CN, Hal, NO 2 , or a group R 5 , R 9 is H or straight chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal or NO 2 , wherein one or more of embedded, non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—, and R 8 is a group of formula V.

12. A compound according to claim 6 , wherein R 8 and R 9 are independently of each other H or straight chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal or NO 2 , wherein one or more of embedded, non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—, and R 6 is a group of formula V.

13. A compound according to claim 1 having one of formulae VI, VIa or VIb,

wherein

X 1 to X 4 are N,

X 5 is C or N,

X 6 , X 7 are independently of each other C, N or O,

R 1 is H, Hal, —OR′, —NHR′, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C12 alkoxy)carbonyl, or (C1-C12 alkylamino)carbonyl, wherein R′ is H or C1-C6 alkyl R2is O,

R 3 , R 4 are independently of each other H, formyl, iminomethyl, nitroso, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, or halosubstituted C1-C12 alkanoyl,

R 6 is H, CN, Hal, NO 2 , C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkanoyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 12 alkoxy)carbonyl, or (C 1 -C 12 alkylamino)carbonyl,

R 8 , R 9 are independently of each other H or straight chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO2 and wherein one or more of embedded, non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—,

S 2 , S 3 are independently of each other a single bond, a spacer unit, a straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of the non-adjacent CH 2 groups may independently be replaced by —O—, —CO—, —CO—O—, —O—CO—, —NR′—, —N═, —NR′—CO—, —CO—NR′—, —NR′—CO—O—, —O—CO—NR′—, —NR′—CO—NR′—, —CH═CH—, —C≡C—, —S—, —SO 3 R′—, —PR′—, or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof,

Ar 1 is a triazole or a tetrazole,

m is 0 or 1,

P is 0, 1 or 2, and

q has a value of 1 to 7.

14. A compound according to claim 13 wherein S 2 and S 3 are independently of each other a single bond or a straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl.

15. A compound according to claim 13 , wherein Ar 1 is selected from formulae V-c, V-d and V-e

wherein the dotted lines represent linking sites to the spacer groups and R″ is H, Hal, NH—COR′, NH— 50 2 R′, CO 2 R′, or COR′, wherein R′ represents H or C1-C6 alkyl, or straight-chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, OH, NH 2 , SO 3 H, SH, CO 2 H, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof.

16. A compound according to claim 1 , which is one of formulae VIIa to VIIf or VIIIa to VIIIf,

wherein

X 1 to X 4 are N,

X 5 is C or N,

X 6 , X 7 are independently of each other C, N or O,

R 1 is H, Hal, —OR′, —NHR′, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C12 alkoxy)carbonyl, or (C1-C12 alkylamino)carbonyl, wherein R′ is H or C1-C6 alkyl R2 is O,

R 3 , R 4 are independently of each other H, formyl, iminomethyl, nitroso, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, or halosubstituted C1-C12 alkanoyl,

R 6 is H, CN, Hal, NO 2 , C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkanoyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 12 alkoxy)carbonyl, or (C 1 -C 12 alkylamino)carbonyl,

R 8 , R 9 are independently of each other H or straight chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO2 and wherein one or more of embedded, non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—,

S 2 , S 3 are independently of each other a single bond, a spacer unit, a straight-chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of the non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —O—CO—, —NR′—, —N═, —NR′—CO—, —CO—NR′, —NR′—CO—O—, —O—CO—NR′—, —NR′—CO—NR′—, —CH═CH—, —C≡C—, —S—, —SO 3 R′—, —PR′—, or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof,

R″ is H, Hal, NH—COR′, NH—SO 2 R′, CO 2 R′, COR′, or straight-chain or branched C 1 - C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, OH, NH 2 , SO 3 H, SH, CO 2 H, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′represents H or C 1 -C 6 alkyl,

m is 0 or 1,

P is 0, 1 or 2, and

q has a value of 1 to 7.

17. A compound according to claim 16 , wherein R 1 is H, alkyl, —OR′, or —NHR′, wherein R′ represents H or C 1 -C 6 alkyl.

18. A compound according to claim 16 , wherein R 3 is H, formyl, C1-C12 alkyl or C1-C12 alkanoyl.

19. A compound according to claim 16 , wherein R 4 is H, nitroso, C1-C12 alkoxy, or C1-C12 alkanoyl.

20. A compound according to claim 16 , wherein R 5 is H, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkanoyl, (C 1 -C 12 alkoxy)carbonyl, or (C 1 -C 12 alkylamino)carbonyl.

21. A compound according to claim 16 , wherein R 6 is H, CN, Hal, NO 2 , C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkanoyl, or (C 1 -C 12 alkoxy)carbonyl.

22. A compound according to claim 1 , having one of formulae IX, IXa, X or Xa,

wherein,

X 6 , X 7 are independently of each other C, N or O,

Y 1 , Y 2 are independently of each other H, formyl, or straight chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of embedded, non-adjacent CH 2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—,

Y 3 is H, formyl, nitroso, or straight chain or branched C 1 -C 12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of embedded, non-adjacent CH 2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—,

R 8 , R 9 are independently of each other H or straight chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO2, and wherein one or more of embedded, non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —CO—NR′—, —CH═CH—, or —C≡C—,

R″ is H, Hal, NH—COR′, NH—SO 2 R′, CO 2 R′, or COR′, wherein R′ represents H or C1-C6 alkyl, or straight-chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, OH, NH 2 , SO 3 H, SH, CO 2 H, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C 1 -C 6 alkyl, or a combination thereof, and

S 2 , S 3 are independently of each other a single bond, a spacer unit, a straight-chain or branched C1-C12 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , and wherein one or more of the non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —O—CO—, —NR′—, —NR′—CO—, —CO—NR′—, —NR′—CO—O—, —O—CO—NR′—, —NR′—CO—NR′—, —CH═CH—, —C≡C—, or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C1-C6 alkyl, or a combination thereof.

23. A compound according to claim 22 , wherein S 2 and S 3 are independently of each other straight-chain or branched C1-C8 alkyl, which is unsubstituted or substituted by at least one CN, Hal, or NO 2 , or a five- or six-membered aromatic ring, which is unsubstituted or substituted with CN, Hal, NO 2 , COR′, or COOR′, wherein R′ represents H or C1-C6 alkyl.