# US 11,078,212 B2 · 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine monomers, methods of manufacture, and copolymers derived therefrom

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- Number: US 11,078,212 B2
- Document ID: US11078212B2
- Status: Granted
- Kind: B2
- Application number: 16/428,082
- Filed: 2019-05-31
- Published: 2020-01-02
- Granted: 2021-08-03
- Earliest claimed: 2018-06-29
- Assignees: Shpp Global Technologies B.V.
- Applicants: Sabic Global Technologies B.V.
- Inventors: Lohith Kenchaiah; Vijayakumar Venkatesh Sugur; Rashmi R. Deshpande; Hariharan Ramalingam; James Alan Mahood
- Web page: https://patentgrep.com/patent/US11078212B2

## CPC

- C07D 491/10: Spiro-condensed systems
- C07D 491/107: with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C08G 64/12: containing nitrogen
- C08G 64/305: {and alcohols}
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

A purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (I): wherein R is a C1-25 hydrocarbyl; each occurrence of R2 and R3 is independently a halogen or a C1-25 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.

## Claims

### Claim 1

A purified 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (I)
wherein
R is a C1-25 hydrocarbyl;
each occurrence of R2 and R3 is independently a halogen or a C1-25 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.

### Claim 2 (depends on 1)

The compound of claim 1, wherein the compound is a purified 2-aryl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IA)
wherein
each occurrence of R1 is independently a phenyl or a C1-6 alkyl;
each occurrence of R2 and R3 is independently a halogen or a C1-25 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.

### Claim 3 (depends on 1)

The compound of claim 1, wherein the compound is a purified 2-aryl-3-(dihydroxyfluoresceinyl)phthalimidine compound of formula (IB)
wherein
each occurrence of R1 is independently a phenyl or a C1-6 alkyl;
each occurrence of R2 is independently a halogen or a C1-25 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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

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—NH2 (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 C1-25 hydrocarbyl;
each occurrence of R2 and R3 is independently a halogen or a C1-25 hydrocarbyl;
p is 0 to 4; and
each q is independently 0 to 3.

### Claim 6 (depends on 5)

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.

### Claim 7 (depends on 5)

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).

### Claim 8 (depends on 5)

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.

### Claim 9 (depends on 8)

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.

### Claim 10 (depends on 8)

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.

### Claim 11 (depends on 5)

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

### Claim 12 (depends on 5)

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

### Claim 13 (depends on 5)

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

### Claim 14 (depends on 5)

The method of claim 5, wherein the primary amine is a primary arylamine of formula (IIA)
wherein each occurrence of R1 is independently phenyl or C1-6 alkyl; and r is 0 or 1.

### Claim 15 (depends on 5)

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

### Claim 16 (depends on 5)

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.

### Claim 17 (depends on 5)

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).

### Claim 18 (depends on 5)

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.

### Claim 19 (depends on 1)

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.

### Claim 20 (depends on 19)

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.