Method for making a di(aminoaryl)fluorene compound

Patent metadata

Field	Value
Publication number	US-11685707-B2
Application number	US-201917415378-A
Country	US
Kind code	B2
Filing date	Dec 20, 2019
Priority date	Dec 20, 2018
Publication date	Jun 27, 2023
Grant date	Jun 27, 2023

Abstract

The present invention is directed to a method for making a di(aminoaryl)fluorene compound that includes the steps of: (a) reacting a fluorenone compound according structure (I) with excess aminobenzene according to structure (II) wherein: each R1, R2, R3, R4, R12, and R13 is independently a group that is inert in the polymerization of epoxy compounds, and R11 is H or (C1-C6)alkyl, in the presence of an acid catalyst, in a liquid medium comprising an aromatic or substituted aromatic solvent having a boiling point of greater than or equal to 150° C. and in the presence of an acid catalyst, in a liquid medium comprising an aromatic or substituted aromatic solvent having a boiling point of greater than or equal to 150° C. and from which the di(aminoaryl)fluorene compound is crystallizable, to form a crude product mixture comprising the di(aminoaryl)fluorene compound, (b) crystallizing di(aminoaryl)fluorene compound in the product mixture, and (c) separating the product mixture into crystallized di(aminoaryl)fluorene compound and a filtrate.

First claim

The invention claimed is:

1. A method for making a di(aminoaryl)fluorene compound, comprising:
(a) reacting a fluorenone compound according structure (1):

with excess aminobenzene according to structure (II):

wherein:
each R 1 , R 2 , R 3 , R 4 , R 12 , and R 13 is independently a group that is inert in the polymerization of epoxy compounds, and
R 11 is H or (C 1 -C 6 )alkyl,

in the presence of an acid catalyst, in a liquid medium comprising ortho-dichlorobenzene and from which the di(aminoaryl)fluorene compound is crystallizable, to form a crude product mixture comprising the di(aminoaryl)fluorene compound, wherein the acid catalyst is soluble in the liquid medium and is selected from the group consisting of: (i) Lewis acids having an affinity for oxygen, and (ii) Brønsted acids,

(b) crystallizing di(aminoaryl)fluorene compound in the crude product mixture, and
(c) separating the product mixture into crystallized di(aminoaryl)fluorene compound and a filtrate.

2. The method of claim 1 , wherein each R 1 , R 2 , R 3 , and R 4 is independently H or (C 1 -C 6 )alkyl.

3. The method of claim 1 , wherein the aminobenzene is present in from 1.5 to 5 times the stoichiometric amount, based on the amount of the fluorenone compound.

4. The method of claim 1 , further comprising recycling the filtrate from step (c) to step (a).

5. The method of claim 4 , wherein the filtrate comprises solvent, unreacted aminobenzene, unreacted fluorenone compound according structure (1), di(aminoaryl)fluorene compound, and acid catalyst.

6. The method of claim 1 , further comprising washing the di(aminoaryl)fluorene compound with additional ortho-dichlorobenzene.

7. The method of claim 6 , wherein the di(aminoaryl)fluorene compound is washed with 0.5 to 100 parts by weight of ortho-dichlorobenzene per 1 pbw of the di(aminoaryl)fluorene compound.

8. The method of claim 6 , further comprising washing the washed di(aminoaryl)fluorene compound with water, a (C 1 -C 4 )alkanol, or a mixture thereof.

9. The method of claim 8 , wherein the di(aminoaryl)fluorene compound is washed with a mixture of 10 to 90 parts by weight (C 1 -C 4 )alkanol and 10 to 90 parts by weight water.

10. The method of claim 8 , wherein the washed di(aminoaryl)fluorene compound comprises less than 1000 ppm residual acid catalyst.

11. The method of claim 8 , wherein the washed di(aminoaryl)fluorene compound comprises less than 8000 ppm of a combined amount of residual aminobenzene and aromatic or substituted aromatic solvent.

12. The method of claim 1 , wherein the di(aminoaryl)fluorene compound is according to structure (Ill):

wherein:
each R 1 , R 2 , R 3 , R 4 , R 12 , and R 13 is independently a group that is inert in the polymerization of epoxy compounds, and
R 11 is H or (C 1 -C 6 )alkyl.

13. The method of claim 12 , wherein each R 12 is independently H or halogen, provided that at least one R 12 is halogen.

14. The method of claim 13 , wherein R 11 and each R 1 , R 2 , R 3 , R 4 , and R 13 is independently H or (C 1 -C 6 )alkyl.

15. The method of claim 13 , wherein R 11 and each R 1 , R 2 , R 3 , R 4 , and R 13 is H.

16. The method of claim 15 , wherein the di(aminoaryl)fluorene compound is according to structure (III.a):

wherein each R 12 is halo.

17. The method of claim 16 , wherein each R 12 is chloro.

18. A method for making a di(aminoaryl)fluorene compound, consisting essentially of:
(a) reacting a fluorenone compound according structure (1):

with excess aminobenzene according to structure (II):

wherein:
each R 1 , R 2 , R 3 , R 4 , R 12 , and R 13 is independently a group that is inert in the polymerization of epoxy compounds, and
R 11 is H or (C 1 -C 6 )alkyl,

in the presence of an acid catalyst, in a liquid medium comprising ortho-dichlorobenzene and from which the di(aminoaryl)fluorene compound is crystallizable, to form a crude product mixture comprising the di(aminoaryl)fluorene compound, wherein the acid catalyst is soluble in the liquid medium and is selected from the group consisting of: (i) Lewis acids having an affinity for oxygen, and (ii) Brønsted acids,

(b) crystallizing di(aminoaryl)fluorene compound from the crude product mixture,
(c) separating the product mixture into crystallized di(aminoaryl)fluorene compound and a filtrate, and, optionally, recycling at least a portion of the filtrate to step (a),
(d) washing, in one or more iterations, the di(aminoaryl)fluorene compound with aromatic or substituted aromatic solvent,
(e) washing, in one or more iterations, the di(aminoaryl)fluorene compound produced in step (d) with water, a (C 1 -C 4 )alkanol, or a mixture thereof, and
(f) drying the di(aminoaryl)fluorene compound produced in step (e).

19. The method of claim 18 , wherein the acid catalyst is selected from: AlCl 3 , YbCl 3 , GdCl 3 , TiCl 2 , Al 2 (SO 4 ) 3 , CuSO 4 , Yb(SO 4 ) 3 , ytterbium trifluoromethane sulfonate, methane sulfonic acid, ethane sulfonic acid, 1,2-ethane disulfonic acid, propane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, trifluoromethane sulfonic acid, H 2 SO 4 , HCl, and H 3 PO 4 .

20. The method of claim 1 , wherein the acid catalyst is selected from: AlCl 3 , YbCl 3 , GdCl 3 , TiCl 2 , Al 2 (SO 4 ) 3 , CuSO 4 , Yb(SO 4 ) 3 , ytterbium trifluoromethane sulfonate, methane sulfonic acid, ethane sulfonic acid, 1,2-ethane disulfonic acid, propane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, trifluoromethane sulfonic acid, H 2 SO 4 , HCl, and H 3 PO 4 .

21. The method of claim 1 , wherein step (b) comprises adding a quantity of di(aminoaryl)fluorene compound in crystalline form to the crude product mixture to seed crystallization of the di(aminoaryl)fluorene compound.

Assignees

• Cytec Ind Inc

Inventors

• Meegan Jonathan E
• Maruani Victor
• Schanen Vincent
• Cross Paul

Classifications

• C07C209/84 Primary

  Purification · CPC title

• C07C209/24 Primary

  by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds · CPC title

• C07C211/52

  the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups · CPC title