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US RE44,175 E1Granted

Process for preparing 4-aminodiphenylamines

OwnerRoger Keranen Rains, Ralph Albert Genetti +2inventors

InventorsRoger Keranen Rains, Ralph Albert Genetti, Edward Albert Lambers, Antonius Johannes van Hengstum

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Abstract

A process for preparing an optionally substituted 4-aminodiphenylamine comprising reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the water content so as to ensure a molar ratio of water to the base charged of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine and/or salts thereof. The coupling reaction is followed by a hydrogenation reaction where the coupling reaction product is hydrogenated in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation. Aqueous and organic phases are obtained and the optionally substituted 4-aminodiphenylamine recovered from the organic phase.

Claims74

Dependent claims

Claim 1A process for preparing an optionally substituted 4-aminodiphenylamine · 169 words41 dependent Claim 40A process for preparing 4-aminodiphenylamine · 248 words1 dependent Claim 45A process for preparing an optionally substituted 4-aminodiphenylamine · 240 words1 dependent Claim 47A process for preparing an optionally substituted 4-aminodiphenylamine · 217 wordsNo dependents Claim 48A process for preparing an optionally substituted 4-aminodiphenylamine · 263 words1 dependent Claim 49A process for preparing an optionally substituted 4-aminodiphenylamine · 237 words6 dependent Claim 50A process for preparing an optionally substituted 4-aminodiphenylamine · 247 words1 dependent Claim 51A process for preparing an optionally substituted 4-aminodiphenylamine · 262 words8 dependent Claim 52A process for preparing an alkylated derivative of an optionally substituted 4-aminodiphenylamine comprising (i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4 · 241 wordsNo dependents Claim 53A process for preparing 4-aminodiphenylamine · 247 words1 dependent Claim 54A process for preparing an optionally substituted 4-aminodiphenylamine · 240 words1 dependent Claim 62A process for preparing an optionally substituted 4-aminodiphenylamine · 249 words1 dependent

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase.

2 more elements

A process for preparing 4-aminodiphenylamine comprising:

(i) reacting aniline and nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating 4-aminodiphenylamine from the organic phase;
(v) reusing the aqueous phase to form a subsequent step (i) reaction mixture;
(vi) reusing the hydrogenation catalyst in a subsequent step (ii) hydrogenation;
and
(vii) hydrogenating azobenzene and/or azoxybenzene which may be produced during step (I) (i) and/or step (ii) to aniline and isolating the aniline for reuse in a subsequent step (i) reaction mixture together with excess aniline that may be recovered from the organic phase in step (iv).

6 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain between 0.0% and 2.0% of the nitrobenzene remaining unreacted with the elapsed time from the start of the nitrobenzene addition to the completion of the reaction not exceeding about 3.5 hours;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture.

4 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4.5:1 at the start of the coupling reaction and not less than about 1.0:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture.

4 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture;
wherein optionally substituted 4-aminodiphenylamine introduced as an impurity into the step (i) reaction in base and/or aniline recycled to form a step (i) reaction mixture is maintained at a level less than a molar ratio of optionally substituted 4-aminodiphenylamine to optionally substituted nitrobenzene of about 0.05.

5 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture;
wherein the hydrogenation catalyst is recycled and reused in a subsequent step (ii) hydrogenation with fresh catalyst added as needed.

5 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture;
wherein after the hydrogenation reaction and before separation of the aqueous phase and the organic phase, water is added in an amount sufficient to allow layer separation to take place.

5 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture;
wherein aniline and nitrobenzene are used in step (i) and by-product comprising azobenzene and/or azoxybenzene is separated-off from the organic phase from step (iv), said by-product is catalytically hydrogenated to form aniline, and said aniline is reused to form a subsequent step (i) reaction mixture.

5 more elements

A process for preparing an alkylated derivative of an optionally substituted 4-aminodiphenylamine comprising

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture;
and
(vi) alkylating the optionally substituted 4-aminodiphenylamine so obtained to form an an alkylated derivative of said optionally substituted 4-aminodiphenylamine.

6 more elements

A process for preparing 4-aminodiphenylamine comprising:

(i) reacting aniline and nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged of not less than about 4.5:1 at the start of the coupling reaction and not less than about 1.0:1 at the end of the coupling reaction to produce 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating 4-aminodiphenylamine from the organic phase;
(v) reusing the aqueous phase to form a subsequent step (i) reaction mixture;
(vi) reusing the hydrogenation catalyst in a subsequent step (ii) hydrogenation;
and
(vii) hydrogenating azobenzene and/or azoxybenzene which may be produced during step (i) and/or step (ii) to aniline and isolating the aniline for reuse in a subsequent step (i) reaction mixture together with excess aniline that may be recovered from the organic phase in step (iv).

6 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4.5:1 at the start of the coupling reaction and not less than about 1.0:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain between 0.0% and 2.0% of the nitrobenzene remaining unreacted with the elapsed time from the start of the nitrobenzene addition to the completion of the reaction not exceeding about 3.5 hours;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture.

4 more elements

A process for preparing an optionally substituted 4-aminodiphenylamine comprising:

(i) reacting an optionally substituted aniline and an optionally substituted nitrobenzene in the presence of water and a base while controlling the amount of water in relation to the base so as to ensure a molar ratio of water to the base charged in the range of not less than about 4:1 at the start of the coupling reaction and not less than about 0.6:1 at the end of the coupling reaction to produce optionally substituted 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine salt;
the end of the coupling reaction including the time for nitrobenzene addition plus any hold time to obtain at most 2.0% of the nitrobenzene remaining unreacted;
(ii) hydrogenating the reaction product of step (i) in the presence of a hydrogenation catalyst and added water so as to ensure a molar ratio of total water to base of at least about 4:1 at the end of hydrogenation;
(iii) separating the hydrogenation catalyst from the reaction mixture;
and
(iv) obtaining an aqueous phase and organic phase from the reaction mixture, separating the organic phase from the aqueous phase and isolating the optionally substituted 4-aminodiphenylamine from the organic phase;
(v) repeating step (i) through step (iv) using the aqueous phase from step (iv) to form a subsequent step (i) reaction mixture;
wherein a molar excess of optionally substituted aniline is used and the excess optionally substituted aniline is recovered from the organic phase and reused to form a subsequent step (i) reaction mixture.

5 more elements

Dependencies are inferred from the claim text.

Facts

Application: 12/764,213Filed 21 Apr 2010 · reissue
Priority: 18 May 1998
Granted: 23 Apr 2013
Term ends: Not estimatedThe source records don’t support an estimate.

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Application60/085,887Us provisional application · filed 18 May 1998
Application09/243,719Reissue · filed 3 Feb 1999
US 6,140,538 AReissue · filed 31 Oct 2000
US RE44,175 E1This patent

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