Claims
- 1. A process for preparing a dioxetane salt compound of the formula: ##STR56## having increased storage stability wherein R.sub.3 and R.sub.4 are each selected from the group consisting of acyclic, cyclic and polycyclic organic groups which can optionally be substituted with heteroatoms and which can optionally be joined together to form a cyclic or polycyclic ring group spiro-fused to the dioxetane ring, wherein R.sub.2 is an aryl ring group selected from the group consisting of phenyl and naphthyl groups which can include additional substituents, wherein Z is selected from the group consisting of halogen atoms and alkyl groups of 1-4 carbons, and M is selected from hydrogen, an alkali metal ion or a quaternary ammonium or phosphonium ion comprising the steps of:
- a) reacting a first alkene compound having the formula: ##STR57## wherein RG is a removable group with a Z-substituted malonate ester and a base to produce a malonate-substituted alkene compound having the formula: ##STR58## wherein R' is an alkyl group of 1-4 carbons; b) photooxygenating the malonate-substituted alkene compound by irradiating a sensitizer in the presence of oxygen and the malonate-substituted alkene compound to form a malonate-substituted dioxetane having the formula: ##STR59## c) reacting the malonate-substituted dioxetane with a phosphorylating reagent having the formula WP(O)Y.sub.2 wherein W and Y are each selected from halogen atoms, substituted or unsubstituted alkoxy, aryloxy, aralkyloxy and trialkylsilyloxy groups to form a phosphorylated dioxetane compound having the formula: ##STR60## d) hydrolyzing the phosphorylated dioxetane in an aqueous solvent with a base of the formula M--Q wherein Q is a basic anion to form the dioxetane salt compound.
- 2. The process of claim 1 wherein the step of reacting the malonate-substituted dioxetane compound with the phosphorylating reagent comprises the steps of:
- a) reacting the malonate-substituted dioxetane compound with a phosphorylating reagent having the formula WP(O)Y'.sub.2 wherein Y' is a halogen atom to form a dioxetane phosphoryl halide compound having the formula ##STR61## b) reacting the dioxetane phosphoryl halide compound with a hydroxyl compound of the formula Y--OH, wherein Y is selected from substituted or unsubstituted alkyl groups to form the phosphorylated dioxetane compound.
- 3. The process of claim 1 wherein the reagent WP(O)Y.sub.2 is POCl.sub.3.
- 4. The process of claim 1 wherein R.sub.3 and R.sub.4 are combined together to form a cyclic or polycyclic ring group R.sub.5 spiro-fused to the dioxetane ring and the dioxetane salt compound has the formula: ##STR62##
- 5. The process of claim 4 wherein R.sub.5 is a substituted or unsubstituted adamantyl group.
- 6. The process of claim 1 wherein R.sub.2 is a substituted or unsubstituted meta-phenyl group.
- 7. The process of claim 1 wherein Z is selected from F and CH.sub.3 and M is Na.
- 8. The process of claim 5 wherein Z is selected from CH.sub.3 and F, M is Na and R.sub.2 is a substituted or unsubstituted meta-phenyl group.
- 9. The process of claim 5 wherein Z is CH.sub.3, M is Na, R.sub.2 is an unsubstituted meta-phenyl group, R.sub.5 is an unsubstituted adamantyl group and the dioxetane salt compound has the formula:
- 10. The process of claim 5 wherein Z is F, M is Na, R.sub.2 is an unsubstituted meta-phenyl group, R.sub.5 is an unsubstituted adamantyl group and the dioxetane salt compound has the formula:
- 11. A process for preparing a dioxetane salt compound of the formula: having increased storage stability wherein R.sub.3 and R.sub.4 are each selected from the group consisting of acyclic, cyclic and polycyclic organic groups which can optionally be substituted with heteroatoms and which can optionally be joined together to form a cyclic or polycyclic ring group spiro-fused to the dioxetane ring, wherein R.sub.2 is an aryl ring group selected from the group consisting of phenyl and naphthyl groups which can include additional substituents, wherein Z is selected from the group consisting of halogen atoms and alkyl groups of 1-4 carbons and M is selected from hydrogen, an alkali metal ion, a quaternary ammoniumion or a phosphonium ion comprising the steps of:
- a) reacting a first alkene compound having the formula: ##STR63## wherein RG is a removable group with a Z-substituted malonate ester and a base to produce a malonate-substituted alkene compound having the formula: ##STR64## wherein R' is an alkyl group of 1-4 carbons; b) reacting the malonate-substituted alkene with a phosphorylating reagent having the formula WP(O)Y.sub.2 wherein W is selected from halogens and Y is a halogen atom, to form a phosphorylated alkene compound having the formula: ##STR65## c) reacting the phosphorylated alkene compound with a hydroxyl compound of the formula Y'--OH, wherein Y' is selected from substituted or unsubstituted alkyl groups to form a second phosphorylated alkene compound having the formula: ##STR66## d) hydrolyzing the second phosphorylated alkene compound in an aqueous solvent with a base of the formula M--Q wherein Q is a basic anion to form an alkene salt compound having the formula: ##STR67## e) photooxidizing the alkene salt compound by irradiating a sensitizer in the presence of oxygen and the alkene salt compound in aqueous solution to form the dioxetane salt compound.
- 12. The process of claim 11 wherein R.sub.3 and R.sub.4 are combined together to form a cyclic or polycyclic ring group R.sub.5 spiro-fused to the dioxetane ring and the dioxetane salt compound has the formula: ##STR68##
- 13. The process of claim 12 wherein R.sub.5 is a substituted or unsubstituted adamantyl group.
- 14. The process of claim 11 wherein R.sub.2 is a substituted or unsubstituted meta-phenyl group.
- 15. The process of claim 11 wherein Z is selected from F and CH.sub.3 and M is Na.
- 16. The process of claim 13 wherein wherein Z is selected from F and CH.sub.3, M is Na, R.sub.2 is a substituted or unsubstituted meta-phenyl group.
- 17. The process of claim 13 wherein Z is CH.sub.3, R.sub.2 is an unsubstituted meta-phenyl group, R.sub.5 is the unsubstituted adamantyl group and the dioxetane salt compound has the formula:
- 18. The process of claim 13 wherein Z is F, R.sub.2 is an unsubstituted meta-phenyl group, R.sub.5 is the unsubstituted adamantyl group and the dioxetane salt compound has the formula:
- 19. An alkene compound of the formula: wherein Z is selected from halogen atoms and alkyl groups of 1-4 carbons and each R' is an alkyl group of 1-4 carbons.
- 20. The compound of claim 19 wherein Z is F and R' is ethyl.
- 21. The compound of claim 19 wherein Z is CH.sub.3 and R' is ethyl.
- 22. An alkene compound of the formula: ##STR69## wherein Z is selected from the group consisting of halogen atoms and alkyl groups of 1-4 carbons, each R' is an alkyl group of 1-4 carbons and each Y is selected from halogen atoms, substituted or unsubstituted alkoxy, aryloxy, aralkyloxy and trialkylsilyloxy groups.
- 23. The compound of claim 22 wherein Z is F and each Y is an OCH.sub.2 CH.sub.2 CN group.
- 24. The compound of claim 22 wherein Z is CH.sub.3 each Y is an OCH.sub.2 CH.sub.2 CN group.
- 25. An alkene compound of the formula: ##STR70## wherein Z is selected from halogen atoms and alkyl groups of 1-4 carbons, each R' is an alkyl group of 1-4 carbons and M is selected from hydrogen, an alkali metal ion, a quaternary ammoniumion or a phosphonium ion.
- 26. The compound of claim 25 wherein Z is F and each M is a sodium atom.
- 27. The compound of claim 25 wherein Z is CH.sub.3 and each M is a sodium atom.
- 28. A dioxetane compound of the formula: ##STR71## wherein Z is selected from halogen atoms and alkyl groups of 1-4 carbons and each R' is an alkyl group of 1-4 carbons.
- 29. The compound of claim 28 wherein Z is F and R' is ethyl.
- 30. The compound of claim 28 wherein Z is CH.sub.3 and R' is ethyl.
- 31. A dioxetane compound of the formula: ##STR72## wherein Z is selected from halogen atoms and alkyl groups of 1-4 carbons, each R' is an alkyl group of 1-4 carbons and each Y is selected from a Cl atom and an OCH.sub.2 CH.sub.2 CN group.
- 32. The compound of claim 31 wherein Z is F, Y is Cl and R' is ethyl.
- 33. The compound of claim 31 wherein Z is CH.sub.3, Y is Cl and R' is ethyl.
- 34. The compound of claim 31 wherein Z is F, Y is the OCH.sub.2 CH.sub.2 CN group and R' is ethyl.
- 35. The compound of claim 31 wherein Z is CH.sub.3, Y is the OCH.sub.2 CH.sub.2 CN group and R' is ethyl.
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of applicants' U.S. application Ser. No. 08/748,107 filed on Nov. 8, 1996 now U.S. Pat. No. 5,721,370 which is a continuation-in-part of applicants' U.S. application Ser. No. 08/509,305 filed on Jul. 31, 1995 now U.S. Pat. No. 5,777,135.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
102e Date |
371c Date |
PCT/US97/19618 |
11/7/1997 |
|
|
7/7/1998 |
7/7/1998 |
Publishing Document |
Publishing Date |
Country |
Kind |
WO98/19989 |
5/14/1998 |
|
|
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
5393497 |
Haber et al. |
Feb 1995 |
|
5578253 |
Schaap et al. |
Nov 1996 |
|
5777135 |
Akhavan-Tafti et al. |
Jul 1998 |
|
Continuation in Parts (2)
|
Number |
Date |
Country |
Parent |
748107 |
Nov 1996 |
|
Parent |
509305 |
Jul 1995 |
|