Claims
- 1. A process for the preparation of derivatives of octafluoro-[2,2]paracyclophane, which comprises the steps of:reacting octafluoro-[2,2]paracyclophane with a nitronium reagent to provide dinitro octafluoro-[2,2]paracylophane isomers; reducing said dinitro octafluoro-[2,2]paracylophane isomers by reacting the dinitro octafluoro-[2,2]paracyclophane isomers with iron powder in concentrated hydrochloric acid to provide pseudo-meta, pseudo-para and pseudo ortho isomers of diamino octafluoro-[2,2]paracyclophane in good yield; and reacting said diamino octafluoro-[2,2]paracylophane isomers with an aqueous halogen solution to provide pseudo-meta, pseudo-para and pseudo ortho isomers of hetero-annular dihalo-octafluoro- [2,2]paracylophane in good yield.
- 2. The process as recited in claim 1, wherein the step of reacting said dinitro octafluoro-[2,2]paracylophane isomers exist as pseudo-meta, pseudo-para and pseudo-ortho isomers.
- 3. The process as recited in claim 2, wherein said dinitro octafluoro-[2,2]paracylophane isomers are formed in a 1:1:1 ratio.
- 4. The process of claim 1, wherein the dihalo-octafluoro-[2,2]paracylophane isomers formed in the second reacting step comprise dibromo-octafluoro-[2,2]paracylophane and diiodo-octafluoro-[2,2]paracylophane isomers.
- 5. The process of claim 1, wherein diamino octafluoro-[2,2]paracylophane isomers were prepared in isolated yields of from 82-84%.
- 6. The process of claim 4, wherein the dibromo-octafluoro[2,2]paracylophane and diiodo-octafluoro-[2,2]paracylophane isomers were prepared in isolated yields of from 60-78%.
- 7. The process of claim 1, wherein said nitration agent consists of 5 equivalents of NO2PF4 in sulpholane at 80° C.
- 8. Isomeric derivatives of octafluoro-[2,2]paracyclophane, having the structures: wherein X═NH2, Br, or I.
- 9. The isomeric derivatives according to claim 8, wherein X is NH2.
- 10. The isomeric derivatives according to claim 8, wherein X is Br.
- 11. The isomeric derivatives according to claim 8, wherein X is I.
- 12. The isomeric derivatives according to claim 9, wherein said isomeric derivatives are formed by reacting octafluoro-[2,2]paracyclophane with a nitronium reagent to provide dinitro octafluoro-[2,2]paracylophane isomers; reducing said mononitro octafluoro-[2,2]paracylophane by reacting the dinitro octafluoro-[2,2]paracyclophane with iron powder in concentrated hydrochloric acid to provide hetero-annular isomeric diamino octafluoro-[2,2]paracyclophane products.
- 13. The isomeric derivatives according to claim 12, wherein said diamino octafluoro-[2,2]paracyclophane products are formed in a 1:1:1 ratio.
- 14. The isomeric derivatives according to claim 13, wherein said diamino octafluoro-[2,2]paracyclophane products are reacted with an aqueous halogen solution to provide homo-annular dihalo-octafluoro-[2,2]paracylophane isomers in high yields.
- 15. The isomeric derivatives according to claim 8, wherein said derivatives exist as pseudo-meta, pseudo-para and pseudo-ortho isomers.
- 16. The isomeric derivatives according to claim 8, for use as versatile precursors for the production of novel homo- and hetero-annular disubstituted octafluoro-[2,2]paracylcophane derivatives.
Parent Case Info
This application claims benefit of application Ser. No. 60/190,778 filed Mar. 20, 2000.
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
5210341 |
Dolbier et al. |
May 1993 |
A |
5849962 |
Dolbier et al. |
Dec 1998 |
A |
6194620 |
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Provisional Applications (1)
|
Number |
Date |
Country |
|
60/190778 |
Mar 2000 |
US |