Process for the preparation of nitrodiphenylamines

Details Process for the preparation of nitrodiphenylamines Process for the preparation of nitrodiphenylamines

2004-01-02

2004-11-09

O'Sullivan, Peter (Department: 1621)

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

Organic compounds

Amino nitrogen containing

C564S420000, C564S421000, C564S422000, C564S423000

Reexamination Certificate

active

06815562

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for the preparation of nitrodiphenylamines by reaction of nitrohalogens with anilines, a base and a catalyst, and to a process for the preparation of aminodiphenylamine by hydrogenation of the nitrodiphenylamine intermediately prepared.
BACKGROUND OF THE INVENTION
N-Substituted anilines are important intermediate products for the preparation of agricultural and fine chemicals.
As described in Kirk-Othmer, Encyclopedia of Chemical Technology, 4
th
edition, 1992, vol. 3, page 424-456 and in Ullmann's Encyclopedia of Industrial Chemistry, 5
th
edition, vol. A3, 1985, page 91-111, 4-aminodiphenylamine (4-ADPA) is an important precursor for the synthesis of anti-ageing agents and stabilizers in the rubber and polymers industry.
Hartwig describes in Angew. Chem., Int. Ed. 1998, 37, 2046-2067 and Buchwald in Top. Curr. Chem. 2002, 219, 131-209, that the synthesis of N-substituted anilines can also be carried out by coupling, catalyzed by transition metals, of activated chloro-, bromo- or iodoaromatics with primary or secondary amines, optionally in the presence of a palladium catalyst, a phosphane and a base.
WO-A2 01/66248 discloses that instead of the complex Pd-phosphane complexes, N-heterocyclic Pd-carbene complexes can also alternatively be employed.
The disadvantage of the syntheses described in the prior art cited above is the use of palladium, which is poorly available and subject to wide price variations, and is expensive to recover. The use of the phosphane ligands of the specifications cited in the prior art also presents problems because of their poor availability and their high toxicity.
DE-A 3 246 151, DE-A 3 501 698, DE-A 185 663, U.S. Pat. Nos. 4,670,595, 4,187,249, 4,683,332 and 4,187,248 disclose the preparation of N-substituted anilines from p-nitrochlorobenzene in the presence of an acid acceptor or a neutralizing agent with the aid of copper catalysts.
U.S. Pat. No. 5,840,982 reports that the first stage for the preparation of N-substituted anilines is usually carried out with copper catalysts, and the second with metal components which differ from these, e.g. nickel.
Venkatamaran et al. discloses in Tetrahedron Letters, 2001, 42, 4791-4793 that the preparation of triarylamines from diarylamines and iodoaromatics is possible in high yields with the aid of defined copper-phosphane complexes. Selective preparation of diarylamines, which are very important economically, is not described in this publication.
Buchwald et al. describes in Organic Letters, 2002, 4, 581-584 the general reaction of halogenobenzenes with anilines. The use of the catalyst according to formula (I) is not disclosed.
There was therefore the need to develop catalysts, which are-suitable in an advantageous manner for a process for the preparation of nitrodiphenylamines starting from aryl chlorides and aryl bromides.
Since aryl chlorides are usually significantly slower to react in nucleophilic aromatic substitution than aryl iodides, significantly more drastic conditions, such as high temperatures, must be chosen for such a reaction. This is in general accompanied by a significantly reduced selectivity of the reaction.
The object of the present invention is therefore to provide a process, which renders it possible to react nitrohalogenobenzenes with anilines to give nitrodiphenylamines in high yields and with a high selectivity.
SUMMARY OF THE INVENTION
The present invention is directed to a process for the preparation of nitrodiphenylamines, wherein nitrohalogenobenzenes are reacted with anilines, a base and a catalyst of the formula (I)
wherein
X is a 1,2-ethanediyl or 1,2-ethenediyl radical and
M can be identical or different and represents C
1
-C
19
-alkyl, C
7
-C
19
-aralkyl, C
6
-C
18
aryl groups or C
6
-C
19
-heteroaryls having 1 to 3 nitrogen atoms, wherein two or more radicals M can be bridged in any desired manner by a covalent bridge or by an alkylidene bridge containing 1 to 4 carbon atoms or via an aryl or heteroaryl ring,
Y represents halogen or a trifluoroacetyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl, cyanide, acetyl, fluorinated acetylacetonyl, nitrate, arylsulfonyl, oxinate, phosphate, carbonate or tetrafluoroborate radical,
z represents 1, 2 or 3,
m represents integers from 1 to 6 and
r denotes 0, 1 or 2.
The base for the process according to the present invention can be chosen from the group consisting of bicarbonates, carbonates, methanolates, ethanolates, isopropylates, tert-butanolates, phosphates, fluorides, silazanes, hydrides and acetates of lithium, sodium, potassium and caesium.
The catalyst of the formula (I) can also be prepared in situ for the process according to the present invention.
The present invention also provides a process for the preparation of aminodiphenylamine, wherein the nitrodiphenylamine prepared by the process according to the present invention is hydrogenated, without isolation.
In the general formula (I)
X preferably represents a 1,2-ethenediyl group,
M preferably represents a C
1
-C
12
alkyl group, C
5
-C
7
cycloalkyl group, C
6
-C
12
-aryl group or a C
5
-C
12
heteroaryl group having 1 to 3 nitrogen atoms in the ring, or represents a methyl group, which is bridged in any desired manner with another radical M by a covalent bridge or by an alkylidene bridge containing 1 to 4 carbon atoms or via an aryl or heteroaryl ring. C
1
-C
12
alkyl groups are to be understood as meaning both branched and unbranched alkyl groups. Methyl, ethyl, n-propyl, i-propyl, n-butyl and tert-butyl are preferred. C
5
-C
6
Cycloalkyl groups are preferably to be understood as meaning cyclopentyl and cyclohexyl groups. Phenyl, biphenyl or the naphthyl radical are preferably employed as C
6
-C
12
-aryl groups. Pyridyl or quinolyl radicals are the preferred C
5
-C
12
-heteroaryl radical having 1 to 3 nitrogen atoms.
Y preferably represents chlorine, bromine, iodine or a trifluoromethylsulfonyl or an acetonyl radical.
z preferably represents 1 or 2
m preferably represents 1, 2 or 3
r preferably represents 1 or 2
Copper compounds with a valency level of 0, +I or +II are preferably employed for the preparation of the catalysts. Preferred starting compounds for the catalysts include copper oxides, copper halides, copper cyanides and copper acetates, copper acetylacetonates in fluorinated or non-fluorinated form, copper nitrates, copper trifluoromethanesulfonates, copper arylsulfonates, copper oxinates and copper phosphates, more preferred are copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(II) bromide, copper(II) chloride, copper(II) acetate, copper(II) oxide or copper(II) acetylacetonate, as well as copper powder. Copper(I) chloride, copper(I) bromide or copper(I) trifluoromethanesulfonate are most preferred.
Those catalysts which contain two symmetric, unsymmetric or two bridged ligands are preferred. Symmetric dialkylimidazolidenes, diarylimidazolidenes and diheteroarylimidazolidenes, unsymmetric arylalkylimidazolines and N-substituted imidazolidenes bridged via heteroaryls or alkylidene bridges are particularly preferred. N,N′-Dimethylimidazolidene, N,N′-dicyclohexylimidazolidene, N,N′-diphenylimidazolidene, N,N′-di(2,6-diisopropyl)phenylimidazolidene, N,N′-di(2,6-dimethyl)phenylimidazolidene, N,N′-di(2,4,6-trimethyl)phenyl-imidazolidene, N,N′-di(2-pyridyl)imidazolidene, N-benzyl-N′-methyl-imidazolidene and ligands which are formed by two-fold deprotonation of 1,3-bis[N-(N′-methyl)imidazoliummethyl]-5-methylbenzene dihalide, 2,6-bis-[N-(N′-methyl)-imidazoliummethyl]pyridine dihalide, 1,2-bis-[N-(N′-methyl)-imidazolium]-1,2-diphenylethane halide or bis-[N-(N′-methyl)imidazolium]-methane dihalide are very particularly preferred.
Preferred catalysts of the formula (I) include (N,N′-dimethylimidazolidene)-copper(II) bromide, (N,N′-dicyclohexylimidazolidene)-copper[II] bromide, [N,N′-di(2,4,6-trimethyl)phenylimidazolide

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