One step synthesis for quinacridone compounds

Details One step synthesis for quinacridone compounds One step synthesis for quinacridone compounds

2003-02-24

2003-12-16

Morris, Patricia L. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S049000, C546S056000, C546S057000

Reexamination Certificate

active

06664396

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to the field of organic synthesis and to a process for forming a N,N′-diarylquinacridone compound comprising the step of reacting a N,N′-unsubstituted quinacridone compound with a haloaryl compound in the presence of a metal to arylate the N and N′ positions and form the corresponding N,N′-diarylquinacridone compound.
BACKGROUND OF THE INVENTION
N,N′-diarylquinacridones have become useful materials and have necessitated synthetic methods for preparing them. In U.S. Pat. No. 6,376,107, Heuer et al disclose the preparation of N,N′-dialkylquinacridones by contacting unsubstituted quinacridones and alkyl halides with a base such as sodium hydride, in a solvent such as dimethylacetamide or dimethylformamide. This is however not extended to the case of aryl halides.
According to Sci Finder, Radl et al, in a series of disclosures (Czech patents 262587 and 261338), disclose the reaction of 4-oxodihydroquinolines (not a quinacridone) with nitroaryl halides with a base such as sodium hydride in a solvent such as dimethylformamide. The disclosure teaches the use of aryl nitrohalides.
Song et al (
Org. Letters
, 2002, 4, 1623-1626) have shown a reaction in the presence of cuprous chloride and a dione to form diaryl ethers. They did not extend this reaction to nitrogen compounds such as quinacridones. Goodbrand et al (J. Org. Chem., 1999, 64, 670-674) have shown that Ullman condensation can be accelerated in the presence of a ligand; this was applied to the synthesis of simple triaryl amines, not to deactivated amines, such as quinacridones.
It is a problem to be solved to provide a process for the synthesis of N,N′-diarylacridone compounds that is simple and efficient.
SUMMARY OF THE INVENTION
The invention provides a process for forming a N,N′-diarylquinacridone compound comprising the step of reacting a N,N′-unsubstituted quinacridone compound with a haloaryl compound in the presence of a metal to arylate the N and N′ positions and form the corresponding N,N′-diarylquinacridone compound. The process is simple and efficient.
DETAILED DESCRIPTION OF THE INVENTION
The invention process is summarized above. The process is useful for synthesizing N,N′ aryl quinacridone compounds by a simplified process of reacting an N,N′-unsubstituted quinacridone compound with a haloaryl compound to arylate the N and N′ positions. The phrase “N,N′-unsubstituted” means that neither of the nitrogen atoms of the quinacridone are substituted.
The N,N′-unsubstituted quinacridone compound may be usefully represented by Formula 1:
where R
3
and R
4
can be hydrogen, alkyl, aryl, alkoxy, fluorine, chlorine, nitro or cyano groups; R
6
-R
14
can be hydrogen, or halogen such as chlorine or fluorine, nitro, cyano, carboxyl, or groups which may be further substituted such as alkyl including branched or straight chain, such as methyl, trifluoromethyl, ethyl, alkoxy such as methoxy, ethoxy, propoxy, aryl such as phenyl, 2,4,6, trimethylphenyl, naphthyl, biphenyl, aryloxy such as phenoxy, tolyloxy, carbonamido such as acetamido, benzamido, acyl such as acetyl, phenoxycarbonyl, sulfonyl such as methylsulfonyl, phenoxysulfonyl, acyloxy such as acetyloxy, benzoyloxy, N-substituted carbamoyl, N-substituted sulfamoyl, a heterocyclic oxy group or a heterocyclic thio group; and the heterocyclic nitrogen atoms of 1 have no substituents other than hydrogen atoms. When a molecule may have two or more substituents, the substituents may join together to form a ring, such as a fused ring, unless otherwise provided. Conveniently, R
3
and R
4
may be hydrogen, fluorine, chlorine, methyl, ethyl, propyl, methoxy, ethoxy, phenyl, and R
6
-R
14
may be the same as R
3
and R
4
plus nitro, trifluoromethyl, cyclohexyl, or cyano groups. One or more of R
6
and R
7
or R
8
and R
7
or R
8
and R
9
, or R
12
and R
13
or R
11
and R
12
or R
13
and R
14
can form a fused ring such as a benzene ring, a cyclohexyl ring, or a benzoxazole ring. Desirably, the substituents adjacent to the nitrogen reaction site are hydrogen, or at least one of R
4
and R
9
, and at least one of R
11
and R
3
is hydrogen.
The haloaryl compound is conveniently a halophenyl compound represented by formula 2:
In Formula 2, X represents a halogen atom. Formula 2 is suitably a bromoaryl or iodoaryl compound, and desirably an iodoaryl compound; that is, X is suitably iodine or bromine, and desirably iodine. R
15
represents hydrogen or one or more substituent groups on the phenyl ring, desirably a substituents having a Hammet's &sgr; constant at least 0.05 or more positive than the corresponding methyl group (in the same position). Each R
15
may independently be hydrogen or may be selected by those skilled in the art to attain the desired properties for a specific application and can include the same substituents broadly described above for R
6
-R
14
. Conveniently, R
15
can be hydrogen, fluorine, chlorine, methyl, ethyl, propyl, methoxy, ethoxy, phenyl, nitro, trifluoromethyl, cyclohexyl, cyano. Two R
15
groups can be joined to form a fused ring with the parent benzene ring. Suitably, R
15
can be hydrogen, methyl, ethyl, cyclohexyl, hydroxy, phenyl, methoxy, or ethoxy. Bulky substituents ortho to the halogen are not convenient and it is desirable that at least one of the ortho positions to the halogen be hydrogen.
The amount of the haloaryl compound used, relative to the starting quinacridone as per formula 1, can range from 2-12 equivalents. The resulting product of this process will be an N,N′-diarylquinacridone compound, represented by N,N′-diphenylquinacridone compound 3.
The reaction occurs in the presence of a base. More specifically, the base needed to perform the process is a dissociative base. The term dissociative base herein refers to alkaline substances known in the art to dissociate in certain solvents, and particularly in polar solvents, into discrete cations and anions. Such dissociative bases include, for example, sodium carbonate, trisodium phosphate, alkali metal alkoxides such as sodium tert-butoxide, alkali metal hydroxides such as sodium hydroxide, alkali metal hydrides such as sodium hydride, and tetrabutylammonium ethoxide. Conveniently the base used can be K
2
CO
3
, Cs
2
CO
3
, sodium tert-butoxide, or sodium hydride suitably in the amount of 2-3 equivalents per quinacridone mole.
The metal used to effect the coupling can be in the metallic form, a metal compound, or a mixture thereof. The metal is conveniently a transition metal. In the metallic form, and typically, the metal can be chosen from copper (Cu) and palladium (Pd). For a metal compound, particularly suitable are certain compounds of copper and palladium. Examples of copper compounds effective for this are. copper(I) iodide, copper(I) chloride, and copper(I) oxide, especially copper iodide. The amount of copper compound used can be a molar equivalent or can be in a catalytic quantity, which is herein defined as an amount of 2 mole % to 5 mole % relative to 1. A mixture of a copper compound and copper metal is desireable. In such a case, the amount of copper metal can be in the range of 1 equivalent to 5 mole % relative to 1. Palladium compounds effective for this coupling can include palladium diacetate, tris(dibenzylidine acetone)dipalladium, bis(triphenylphosphine)palladium dichloride, or tetrakis(triphenylphosphine)palladium. The amount of palladium compound used can be a molar equivalent or desireably can be in a catalytic quantity, which is herein defined as an amount of 2 mole % to 20 mole % relative to 1.
In addition to the above metal compounds, the use of certain ligands can enhance the effectiveness of this reaction by lowering the activation energy level of the reaction by comlexing the metal or metal compound. Such ligands include but are not limited to 1, 10-phenanthroline, 1,2-trans-cyclohexyldiamine, tri(tert-butyl)phosphine, tricyclohexylphosphine, triphenylphosphine, beta-keto carbonyl compounds inc

Affiliated with

Also associated with

Rating

One step synthesis for quinacridone compounds does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with One step synthesis for quinacridone compounds, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and One step synthesis for quinacridone compounds will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3163504