Photogenerated reagents
This invention describes reagent precursors and methods for chemical and biochemical reactions. These reagent precursors that can be activated in solution upon irradiation to generate reagents required for the subsequent chemical reactions. Specifically, photogenerated reagents (PGR) are useful for controlling parallel combinatorial synthesis and various chemical and biochemical reactions.
1. A 2-nitroaryl derivative having the formula
wherein
R 1-4 ═H, Cl, Br, NO 2 , CF 3 , CN, OMe, OCH 2 O, Ph, benzyl, O-benzyl, or alkyl, or, aryl, or alkylaryl, or akoxyalkyl having 1-12 carbons;
Ra═H, CH 3 , Cl, Br, phenyl, acetyl, or acyl, or alkyl, or alkylaryl, or akoxyalkyl having 1-12 carbons;
X=a Lewis base.
2. The 2-nitroaryl derivative of claim 1 wherein X is piperidine.
3. The 2-nitroaryl derivative of claim 2 wherein R 1 ═H, R 2 ═H, R 3 ═H, R 4 ═H and R a ═CH 3 .
4. The 2-nitroaryl derivative of claim 2 wherein R 1 ═H, R 4 ═H, R 2 ═OCH 3 , R 3 ═OCH 3 and R a ═CH 3 .
5. The 2-nitroaryl derivative of claim 1 wherein X is hydrazine.
6. The 2-nitroaryl derivative of claim 5 wherein R 1 ═H, R 2 ═H, R 3 ═H, R 4 ═H and R a ═CH 3 .
7. The 2-nitroaryl derivative of claim 5 wherein R 1 ═H, R 4 ═H, R 2 ═OCH 3 , R 3 ═OCH 3 and R a ═CH 3 .
8. The 2-nitroaryl derivative of claim 1 wherein X is tetrazole.
9. The 2-nitroaryl derivative of claim 8 wherein R 1 ═H, R 2 ═H, R 3 ═H, R 4 ═H and R a ═CH 3 .
10. The 2-nitroaryl derivative of claim 8 wherein R 1 ═H, R 4 ═H, R 2 ═OCH 3 , R 3 ═OCH 3 and R a ═CH 3 .
11. The 2-nitroaryl derivative of claim 1 wherein X is thiophenol.
12. The 2-nitroaryl derivative of claim 11 wherein R 1 ═H, R 2 ═H, R 3 ═H, R 4 ═H and R a ═CH 3 .
13. The 2-nitroaryl derivative of claim 11 wherein R 1 ═H, R 4 ═H, R 2 ═OCH 3 , R 3 ═OCH 3 and R a ═CH 3 .
14. A 2-nitroaryl derivative having the formula
wherein
R 1 , R 4 ═H, and Cl, Br, NO 2 , CF 3 , CN, OMe, OCH 2 O, Ph, benzyl, O-benzyl, or alkyl, or, aryl, or alkylaryl, or akoxyalkyl having 1-12 carbons;
Ra═CH 3 ;
X=a Lewis base.
15. The 2-nitroaryl derivative of claim 14 wherein X is piperidine.
16. The 2-nitroaryl derivative of claim 14 wherein X is hydrazine.
17. The 2-nitroaryl derivative of claim 14 wherein X is tetrazole.
18. The 2-nitroaryl derivative of claim 14 wherein X is thiophenol.
19. A method for generating a base by irradiating the composition of claim 1 .
20. A method of generating piperidine by irradiating the composition of claim 2 .
21. A method of generating hydrazine by irradiating the composition of claim 5 .
22. A method of generating tetrazole by irradiating the composition of claim 8 .
23. A method of generating thiophenol by irradiating the composition of claim 11 .
24. A method for generating a base by irradiating the composition of claim 14 .
25. A method of generating piperidine by irradiating the composition of claim 15 .
26. A method of generating hydrazine by irradiating the composition of claim 16 .
27. A method of generating tetrazole by irradiating the composition of claim 17 .
28. A method of generating thiophenol by irradiating the composition of claim 18 .
29. A method for generating a base by irradiating the composition of claim 1 in the presence of a sensitizer.
30. A method for generating a base by irradiating the composition of claim 1 in the presence of solvent.
31. The method of claim 30 wherein the solvent is dimethyl formamide.
32. A method for generating a base by irradiating the composition of claim 1 in the presence of co-reagent.
33. The method of claim 32 wherein the co-reagent is DBU (1,8-diazabicyclo[5.4.0]undec-7-en).
34. A method for generating a base by irradiating the composition of claim 14 in the presence of a sensitizer.
35. A method for generating a base by irradiating the composition of claim 14 in the presence of solvent.
36. The method of claim 35 wherein the solvent is dimethyl formamide.
37. A method for generating a base by irradiating the composition of claim 14 in the presence of co-reagent.
38. The method of claim 37 wherein the co-reagent is DBU (1,8-diazabicyclo[5.4.0]undec-7-en).
39. A method for synthesizing the compounds of claim 1 comprising:
(a) reacting 2-nitroethylbenzene derivatives to produce 2-(2-nitrophenyl)propanol;
(b) reacting the 2-(2-nitrophenyl)propanol with phosgene or diphogene to product the corresponding chloroformate; and
(c) reacting the chloroformate with a nucleophilic Lewis base.
40. The method of claim 39 wherein the 2-nitrobenzene derivative is 1-ethyl-2-nitrobenzene.
41. The method of claim 39 wherein the 2-nitrobenzene derivative is 1-ethyl-(2-nitro-3,4-methylenedioxy)benzen.
42. The method of claim 39 wherein the nucleophilic Lewis base is selected from the group consisting of piperidine, hydrazine, tetrazole and thiophenol.
43. A method of removing protecting moieties in the synthesis of polymers the method comprising:
irradiating the composition of claim 1 to produce a Lewis base; and
contacting the Lewis base with the protected moiety thereby deprotecting the protected moiety.
44. The method of claim 43 wherein the protecting moiety is Lewis base-labile.
45. The method of claim 43 wherein the protecting moiety is Fmoc.
46. The method of claim 43 wherein the protecting moiety is ivDde.
47. The method of claim 43 wherein the protecting moiety is levulinyl.
48. A method of deprotecting initiating moieties attached to a solid surface comprising:
a) contacting the initiating moieties with a liquid solution comprising one or more 2-nitroaryl derivatives of claim 1 ; and
b) irradiating the liquid solution to cause formation of a Lewis base; and
c) the Lewis base deprotecting the initiating moiety.