Some content of this application is unavailable at the moment.
If this situation persist, please contact us atFeedback&Contact
1. (WO2018085737) PHOTOCHROMIC HYDRAZONE SWITCHES
Note: Text based on automatic Optical Character Recognition processes. Please use the PDF version for legal matters

CLAIMS

What is claimed is:

1. A compound of Formula I or a salt thereof:

wherein

X represents a double bond having either E or Z stereochemistry;

A is an aryl or heteroaryl moiety;

B is an aryl or heteroaryl moiety;

R is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkenone, haloalkyl, heteroalkyl, aryl, heterocyclyl, heteroaryl, OH, O-R', O-CO-R', S-H, S-R', NH2, NH(R'), N(R')2, NH(CO-R'), N(R')(CO-R'), NHOH, NR'OH, NR'OR', NC(R")=C(R")2, and C≡C-R",

where:

each R' is independently azide, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, or heteroaryl, or

optionally for N(R')2, N(R')(CO-R'), or NR'OR', the two R' together with the atoms to which they are attached form a 5-10 member carbocyclic ring, which ring is saturated or unsaturated, which ring optionally contains one or two additional heteroatom ring members, which ring is optionally fused to a benzene ring, and which ring is optionally substituted; each R" is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, or heteroaryl, and

where in the alkenyl and alkynyl groups for R' and R", the double or triple bond is not at the alpha-beta position in the alkenyl or alkynyl group;

Ri and R2 are independently, for each occurrence, selected from the group consisting of azide, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, heteroaryl, halo, haloalkyl, alkylamino, dialkylamino, hydroxyl, nitro, cyano, carboxyl, carboxyalkyl, carboxamido, an amino acid group, OH, O-R', O-CO-R', S-H, S-R', NH2, NH(R'), N(R')2, NH(CO-R'), N(R')(CO-R'), NHOH, NR'OH, NR'OR', NC(R")=C(R")2, and

C≡C-R", where R' and R"are as defined above; or

two adjacent Ri together with the atom(s) to which they are attached optionally form a 5-6-member carbocyclic ring or heterocyclic ring, which ring is saturated or unsaturated, which ring is optionally substituted and which ring optionally contains 1-4 heteroatoms; or R and one of R2 are optionally linked by a 3-8 carbon linker, which is optionally substituted;

n is 0, 1, 2, 3, 4 or 5; and

m is O, 1, 2, 3, 4, 5, 6 or 7.

2. The compound of claim 1, wherein at least one of A or B is a group other than phenyl.

3. The compound of claim 1, wherein n +m is 4 or more.

4. The compound of clam 1, wherein n is 2 or m is 3.

5. The compound of any one of claims 1-4, wherein each Ri and R2 is selected from the group consisting of heterocyclyl, halo, alkylamino, dialkylamino, diphenyl amino, hydroxyl, nitro, cyano, carboxyl, carboxylalkyl and carboxamido.

6. The compound of any one of claims 1-5, wherein A is selected from phenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, quinolin-2-yl or thien-2-yl.

7. The compound of any one of claims 1-5, wherein (Ri)n-A- is selected from 4-dialkylaminophenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, 6-dialkylaminonaphth-2-yl, thien-2-yl or 5(piperidin-l-yl)thien-2-yl.

8. The compound of any one of claims 1-5, wherein B is selected from phenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, quinolin-2-yl or thien-2-yl.

9. The compound of any one of claims 1-5, wherein (R2)m-B- is selected from 4-dialkylaminophenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, 6-dialkylaminonaphth-2-yl, quinolin-2-yl, thien-2-yl or 5(piperidin-l-yl)thien-2-yl.

10. The compound of any one of claims 1-5, wherein A and B are independently selected from phenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, quinolin-2-yl or thien-2-yl.

11. The compound of any one of claims 1-5, wherein (Ri)n-A- is selected from 4-dialkylaminophenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, 6-dialkylaminonaphth-2-yl, thien-2-yl or 5(piperidin-l-yl)thien-2-yl and B is selected from phenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, quinolin-2-yl or thien-2-yl.

12. The compound of any one of claims 1-5, wherein (R2)m-B- is selected from 4-dialkylaminophenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, 6-dialkylaminonaphth-2-yl, thien-2-yl or 5(piperidin-l-yl)thien-2-yl and A is selected from phenyl, pyridine-2-yl, naphth-2-yl, naphth-l-yl, quinolin-2-yl or thien-2-yl.

The compound of claim 1 of formula:

wherein

X represents a double bond having either E or Z stereochemistry;

R is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkenone, haloalkyl, heteroalkyl, aryl, heterocyclyl, heteroaryl, OH, O-R', O-CO-R', S-H, S-R', NH2, NH(R'), N(R')2, NH(CO-R'), N(R')(CO-R'), NHOH, NR'OH, NR'OR', NC(R")=C(R")2, and C≡C-R",

where:

each R' is independently azide, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, or heteroaryl, or optionally for N(R')2, N(R')(CO-R'), or NR'OR', the two R' together with the atoms to which they are attached form a 5-10 member carbocyclic ring, which ring is saturated or unsaturated, which ring optionally contains one or two additional heteroatom ring members, which ring is optionally fused to a benzene ring, and which ring is optionally substituted;

each R" is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, or heteroaryl, and

where in the alkenyl and alkynyl groups for R' and R", the double or triple bond is not at the alpha-beta position in the alkenyl or alkynyl group;

Ri, R2, and R3 are independently, for each occurrence, selected from the group consisting of azide, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, heteroaryl, halo, haloalkyl, alkylamino, dialkylamino, hydroxyl, nitro, cyano, carboxyl, carboxyalkyl, carboxamido, an amino acid group, OH, O-R', O-CO-R', S-H, S-R', NH2, NH(R'), N(R')2, NH(CO-R'), N(R')(CO-R'), NHOH, NR'OH, NR'OR',

NC(R")=C(R")2, and C≡C-R", where R' and R"are as defined above or

two adjacent Ri together form a 5-6-member carbocyclic ring or heterocyclic ring, which ring is saturated or unsaturated, which ring is optionally substituted and which ring optionally contains 1-4 heteroatoms;

n is 0, 1, 2, 3, 4 or 5;

m is 0, 1, 2 or 3; and

p is 0, 1, 2 or 3.

14. The compound of claim 13, wherein n, m and p are each 0.

15. The compound of any one of claims 1-5 or claim 13, wherein R is OR' and R' is C1_6 alkyl.

16. The compound of any one of claims 1-5 or claim 13, wherein R is OR' and R' is ethyl.

17. The compound of claim 13, wherein n, m and p are each 0, R is OR' and R' is C1-6 alkyl.

18. The compound of any one of claims 1-5, 13 or 17, wherein A represents a double bond having E or Z stereochemistry.

19. The compound of any one of claims 1-5, 13, or 17, wherein A represents a double bond having E stereochemistry.

20. The compound of any one of claims 1-5, 13 or 17, wherein A represents a double bond having Z stereochemistry.

21. The compound of claim 1 of structure selected from:


22. The compound of claim 1 of structure:


or a salt thereof,

wherein

each Rio independently is hydrogen or alkyl.

23. The compound of claim 22, wherein B is selected from phenyl, naphthyl, or quinolinyl.

24. The compound of claim 22, wherein m is 0.

25. The compound of claim 22, of structure:

or a salt thereof.

26. The compound of claim 1 of structure:


or a salt thereof.

27. The compound of claim 26, wherein B is phenyl, naphthyl, or quinolin-2-yl.

28. The compound of claim 1 of structure:


or a salt thereof

wherein R11 is selected from hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, alkoxy, aryl, heteroaryl, halo, haloalkyl, alkylamino, dialkylamino, hydroxyl, nitro, cyano, carboxyl, carboxyalkyl, and carboxamido;

29. The compound of claim 28, wherein B is phenyl, naphthyl, or quinolin-2-yl.

30. The compound of claim 28, wherein R11 is alkyl, cycloalkyl, or heterocyclyl,

31. The compound of claim 28, wherein R11 is piperidin-2-yl.

32. The compound of any one of the preceding claims, wherein the E stereoisomer has a thermal relaxation half-life of at least 10, 20, 50, 100, 1000 or 2000 years.

33. A composition comprising both the E and Z stereoisomer of a compound of any one of the preceding claims.

34. A molecular switch comprising a compound of any one of the preceding claims.

35. The molecular switch of claim 34, comprising both the E and Z stereoisomers of the compound.

36. A molecular switch comprising one or more compounds selected from the group consisting of:


and salts thereof.

37. The compound of claim 1 which is a compound of Table 2.

38. A method of optically switching a compound of Formula I, or a salt thereof, or a material comprising the compound of Formula I or a salt thereof:


wherein

X represents a double bond having either E or Z stereochemistry;

A is an aryl or heteroaryl moiety;

B is an aryl or heteroaryl moiety;

R is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkenone, haloalkyl, heteroalkyl, aryl, heterocyclyl, heteroaryl, OH, O-R', O-CO-R', S-H, S-R', NH2, NH(R'), N(R')2, NH(CO-R'), N(R')(CO-R'), NHOH, NR'OH, NR'OR', NC(R")=C(R")2, and C≡C-R",

where:

each R' is independently azide, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, or heteroaryl, or

optionally for N(R')2, N(R')(CO-R'), or NR'OR', the two R' together with the atoms to which they are attached form a 5-10 member carbocyclic ring, which ring is saturated or unsaturated, which ring optionally contains one or two additional heteroatom ring members, which ring is optionally fused to a benzene ring, and which ring is optionally substituted; each R" is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, or heteroaryl, and

where in the alkenyl and alkynyl groups for R' and R", the double or triple bond is not at the alpha-beta position in the alkenyl or alkynyl group;

Ri and R2 are independently, for each occurrence, selected from the group consisting of azide, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, alkoxyalkyl, heteroalkyl, alkoxy, aryl, heteroaryl, halo, haloalkyl, alkylamino, dialkylamino, hydroxyl, nitro, cyano, carboxyl, carboxyalkyl, carboxamido, an amino acid group, OH, O-R', O-CO-R', S-H, S-R', NH2, NH(R'), N(R')2, NH(CO-R'), N(R')(CO-R'), NHOH, NR'OH, NR'OR', NC(R")=C(R")2, and C≡C-R", where R' and R"are as defined above; or

two adjacent Ri together with the atom(s) to which they are attached optionally form a 5-6-member carbocyclic ring or heterocyclic ring, which ring is saturated or unsaturated, which ring is optionally substituted and which ring optionally contains 1-4 heteroatoms; or R and one of R2 are optionally linked by a 3-8 carbon linker, which is optionally substituted;

n is 0, 1, 2, 3, 4 or 5; and

m is 0, 1, 2, 3, 4, 5, 6 or 7;

the method comprising irradiating said compound or material, thereby isomerizing the compound from the E stereoisomer to the Z stereoisomer, isomerizing the compound from the Z stereoisomer to the E stereoisomer.

39. The method of claim 38, wherein A is phenyl or pyridine-2-yl.

40. The method of claim 38, wherein B is phenyl or quinolin-2-yl.

41. The method of claim 38, wherein R is C1_6 alkyl.

42. The method of claim 38, wherein the compound is the compound of any one of claims 1-37 or a salt thereof.

43. The method of claim 38, wherein the compound is the compound of any one of claims 1-5, 13, 17, and 21-36.

44. The method of claim 38, wherein the compound is selected from the group consisting of:


and salts thereof.

45. The method of claim 38, wherein the compound is a compound of Table 2 or the corresponding E or Z stereoisomer thereof.

46. The method of claim 38, wherein the compound is a compound of any one of the formulas in the specification or a salt thereof.

47. The method of any one of claims 38-46, wherein the compound is dissolved and/or suspended in a solvent.

48. The method of any one of claims 38-46, wherein the compound is dissolved in an organic solvent, an aqueous solvent or a miscible mixture of an aqueous solvent and an organic solvent.

49. A method for two photon absorption which comprises the step of irradiating a compound of any one of claims 1-37 with an appropriate wavelength of light to facilitate two photon absorption.