2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine monomers, methods of manufacture, and copolymers derived therefrom

1. A purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (I)

wherein

R is a C 1-25 hydrocarbyl;

each occurrence of R 2 and R 3 is independently a halogen or a C 1-25 hydrocarbyl;

p is 0 to 4; and

each q is independently 0 to 3, and

wherein the purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (I) has a purity of greater than 99.4%, as determined by high performance liquid chromatography.

2. The compound of claim 1 , wherein the compound is a purified 2-aryl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IA)

wherein

each occurrence of R 1 is independently a phenyl or a C 1-6 alkyl;

each occurrence of R 2 and R 3 is independently a halogen or a C 1-25 hydrocarbyl;

p is 0 to 4;

each q is independently 0 to 3; and

r is 0 to 5, and

wherein the purified 2-aryl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IA) has a purity of greater than 99.4%, as determined by high performance liquid chromatography.

3. The compound of claim 1 , wherein the compound is a purified 2-aryl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IB)

wherein

each occurrence of R 1 is independently a phenyl or a C 1-6 alkyl;

each occurrence of R 2 is independently a halogen or a C 1-25 hydrocarbyl; and

p and r are each independently 0 or 1, and

wherein the purified 2-aryl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IB) has a purity of greater than 99.4%, as determined by high performance liquid chromatography.

4. The compound of claim 1 , wherein the compound is a purified 2-phenyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IC)

wherein the purified 2-phenyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IC) has a purity of greater than 99.4%, as determined by high performance liquid chromatography.

5. A method for the manufacture of the purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine (I) compound of claim 1 , the method comprising:

combining a primary amine of formula (II)

R—NH 2   (II)

with an aqueous acid to provide a first reaction mixture;

adding a fluorescein compound of formula (III)

to the first reaction mixture to provide a second reaction mixture;

heating the second reaction mixture under conditions effective to provide a third reaction mixture comprising a crude phthalimidine;

combining the crude phthalimidine and an aqueous alkali solution to form an aqueous alkaline mixture;

contacting the aqueous alkaline mixture with an adsorbent to provide a semi-purified phthalimidine; and

mixing the semi-purified phthalimidine with an alcohol solution to provide the purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (I),

wherein, in formulas (I), (II), and (III),

R is a C 1-25 hydrocarbyl;

each occurrence of R 2 and R 3 is independently a halogen or a C 1-25 hydrocarbyl;

p is 0 to 4; and

each q is independently 0 to 3.

6. The method of claim 5 , further comprising one or more of

mixing the third reaction mixture with aqueous acid to provide the crude phthalimidine; or

contacting the aqueous alkaline mixture with the adsorbent, then mixing with an acid to provide the semi-purified phthalimidine.

7. The method of claim 5 , further comprising

mixing the semi-purified phthalimidine with an alcohol solution and heating to form a solution comprising the semi-purified phthalimide; and

contacting the solution with an adsorbent, then mixing with deionized water to provide the purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (I).

8. The method of claim 5 , further comprising one or more of:

isolating the crude phthalimidine from the third reaction mixture, and then drying the crude phthalimidine; or

isolating the semi-purified phthalimidine, and then washing the semi-purified phthalimidine.

9. The method of claim 8 , wherein the isolating of the crude phthalimidine comprises:

mixing the third reaction mixture with aqueous acid and water to provide the crude phthalimidine; and

filtering the crude phthalimidine.

10. The method of claim 8 , wherein the isolating of the semi-purified phthalimidine comprises:

contacting the aqueous alkaline mixture and the adsorbent with an acid to provide the semi-purified phthalimidine; and

filtering the semi-purified phthalimidine.

11. The method of claim 5 , wherein the heating of the second reaction mixture is at 100 to 200° C.

12. The method of claim 5 , wherein the heating of the second reaction mixture is for 10 to 40 hours.

13. The method of claim 5 , wherein the heating of the second reaction mixture is at 120 to 180° C. for 15 to 35 hours.

14. The method of claim 5 , wherein the primary amine is a primary arylamine of formula (IIA)

wherein each occurrence of R 1 is independently phenyl or C 1-6 alkyl; and r is 0 or 1.

15. The method of claim 5 , wherein the primary amine is aniline.

16. The method of claim 5 , wherein

the aqueous acid comprises an aqueous solution of a mineral acid, and

the aqueous alkali solution comprises an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide.

17. The method of claim 5 , wherein

the primary amine of formula (II) is present in the second reaction mixture at a concentration of 2 to 5 molar equivalents of the fluorescein of formula (III), and

the aqueous acid is present in the first reaction mixture at a concentration of 0.8 to 1.5 molar equivalents of the primary amine of formula (II).

18. The method of claim 5 , wherein

the purity of the crude phthalimidine is less than 99%,

the purity of the semi-purified phthalimidine is less than 99.5%, and

the purity of the purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound is 99.5% or greater.

19. A method for the manufacture of a polycarbonate, the method comprising polymerizing the purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of claim 1 in the presence of a carbonate source under conditions effective to provide the polycarbonate.

20. The method of claim 19 , wherein the polycarbonate comprises 0 to 0.8 weight percent of an impurity derived from the manufacturing of the purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound.