التفاصيل البيبلوغرافية
| العنوان: |
Convenient Synthesis of Azolines to Azoles |
| Document Number: |
20130012719 |
| تاريخ النشر: |
January 10, 2013 |
| Appl. No: |
13/543403 |
| Application Filed: |
July 06, 2012 |
| مستخلص: |
Azolines are oxidized in the presence of a copper-containing catalyst to azoles in the presence of molecular oxygen. A synthetic scheme converting azolines azoles is also provided. |
| Inventors: |
Williams, Travis J. (Los Angeles, CA, US); Dawsey, Anna C. (Los Angeles, CA, US); Li, Vincent (Los Angeles, CA, US); Hamilton, Kimberly C. (Edison, NJ, US); Wang, Jianmei (Riverside, CA, US) |
| Assignees: |
University of Southern California (Los Angeles, CA, US) |
| Claim: |
1. A method of forming an azole, the method comprising: a) reacting a compound having formula (I) with a copper-containing catalyst in the presence of a base or proton acceptor to form a compound having formula (II): [chemical expression included] wherein: R1 is C1-C10 alkyl; R2 is an optionally substituted phenyl, optionally substituted C5-C18 aryl, or optionally substituted C5-C18 heteroaryl; and E is O, S, or N. |
| Claim: |
2. The method of claim 1 wherein R1 is methyl, ethyl, butyl or pentyl and E is O or S. |
| Claim: |
3. The method of claim 1 wherein the copper-containing catalyst has the following formula: [chemical expression included] wherein: La, Lb, and L3 are each independently two electron ligands; X1− is a negatively charged counter ion; Cu is in Cu(I) or Cu(II) n is 0, 1, 2, or 3; and m is 0, 1, or 2. |
| Claim: |
4. The method of claim 3 wherein L3 is a neutral ligand. |
| Claim: |
5. The method of claim 4 wherein L3 is H2O, NH3, C1-5 primary amine, C2-6 secondary amine, C3-9 tertiary amine, PH3, C1-5 primary phosphines, C2-6 secondary phosphine, C3-9 tertilry phosphines, C1-5 alcohols, CO, N2, C2-8 alkenes, or C2-8 alkynes. |
| Claim: |
6. The method of claim 3 wherein L3 is halide, CF3SO3−, C1-5 alkoxide, or C1-5 carboxylate. |
| Claim: |
7. The method of claim 1 wherein the copper-containing catalyst has the following formula: [chemical expression included] wherein: La, Lb, and L3 are each independently two electron ligands; n is from 0, 1, 2, or 3; W1 is an absent or a C1-18 hydrocarbon moiety attached to L1 and L2 X1− is a negatively charged counter ion; Cu is in Cu(I) or Cu(II) n is 0, 1, 2, or 3; and m is 0, 1, or 2. |
| Claim: |
9. The method of claim 8 wherein X− is halide. CF3SO3−, C1-5 alkoxide, or C1-5 carboxylate. |
| Claim: |
10. The method of claim 8 wherein L1-W-L2 is selected from the group consisting of: [chemical expression included] |
| Claim: |
11. The method of claim 1 wherein the compound having formula (I) is selected from the group consisting of compounds having formula (V) and (VI): [chemical expression included] |
| Claim: |
12. The method of claim 11 wherein the phenyl group in compounds (V) or (VI) is substituted with C1-6 alkyl, fluorine, chlorine, bromine, cyano, or nitro. |
| Claim: |
13. The method of claim 1 wherein compound (I) is selected from the group consisting of: [chemical expression included] |
| Claim: |
14. The method of claim 1 wherein compound (I) is selected from the group consisting of: [chemical expression included] |
| Claim: |
15. The method of claim 1 wherein R2 is: [chemical expression included] and R3 is hydrogen or C1-10 alkyl. |
| Claim: |
16. The method of claim 1 wherein the reaction of step a) is performed in the presence of molecular oxygen. |
| Claim: |
17. The method of claim 1 wherein the base or proton acceptor is 1,8-diazabicyclo [5.4.0]undec-7-ene, 1,8-Bis(dimethylamino)naphthalene (proton Sponge™), 1,8-bis(hexamethyltriaminophosphazenyl)naphthalene, diisopropyl ethyl amine, potassium tert-butoxide, or potassium carbonate. |
| Claim: |
18. A method of forming an azole, the method comprising: a) reacting a compound having formula (I) with a base or proton acceptor in the presence of molecular oxygen to form a compound having formula (II): [chemical expression included] wherein: R1 is C1-C10 alkyl; R2 is an optionally substituted phenyl, optionally substituted C5-C18 aryl, or optionally substituted C5-C18 heteroaryl; and E is O, S, or N, |
| Claim: |
19. The method of claim 18 wherein R2 is methyl, ethyl, butyl or pentyl and E is O or S. |
| Claim: |
20. The method of claim 18 wherein the compound having formula (I) is selected from the group consisting of compounds having formula (V) and (VI): [chemical expression included] |
| Claim: |
21. The method of claim 20 wherein the phenyl group in compounds (V) or (VI) is substituted with C1-6 alkyl, fluorine, chlorine, bromine, cyano, or nitro. |
| Claim: |
22. The method of claim 18 wherein compound (I) is selected from the group consisting of: [chemical expression included] |
| Claim: |
23. The method of claim 18 wherein compound (I) is selected from the group consisting of: [chemical expression included] |
| Claim: |
24. The method of claim 18 wherein R2 is: [chemical expression included] and R3 is hydrogen or C1-10 alkyl. |
| Claim: |
25. The method of claim 18 wherein the reaction of step a) is performed in the presence of molecular oxygen. |
| Claim: |
26. The method of claim 18 wherein the base or proton acceptor is 1,8-diazabicyclo[5.4.0]undec-7-ene. |
| Current U.S. Class: |
548/181 |
| Current International Class: |
07; 07; 07 |
| رقم الانضمام: |
edspap.20130012719 |
| قاعدة البيانات: |
USPTO Patent Applications |
