Process for the preparation of 2-substituted-1,4-benzenediamines and salts thereof

Patent metadata

Field	Value
Publication number	US-9758469-B2
Application number	US-201514926178-A
Country	US
Kind code	B2
Filing date	Oct 29, 2015
Priority date	Nov 4, 2014
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

A process for the preparation of 2-substituted-1,4-benzenediamines, a cosmetically acceptable salt thereof, or mixture thereof. The process according to the present invention is a particularly cost effective process in that it avoids sophisticated chemical steps which requires special equipment or expensive catalysts and in that it comprises a recycling step of one of the starting materials, namely the 2-substituted aniline.

First claim

What is claimed is:

1. A process for the preparation of 2-substituted-1,4-benzenediamines (I), a cosmetically acceptable salt thereof, or mixture thereof comprising the steps of:
a) in situ generation of diazonium salt of formula (III) from the 2-substituted aniline of formula (II) followed by addition of the unreacted 2-substituted aniline of formula (II) to form the triazene intermediate of formula (IV):

wherein R is selected from the group consisting of a hydrogen atom and a C 1 -C 4 alkyl group;
b) rearrangement of the of triazene intermediate of formula (IV) to the diazo compound of formula (V):

c) reduction of the diazo compound of formula (V) to obtain an equimolar amount of 2-substituted-1,4-benzenediamines (I) and the 2-substituted aniline of formula (II):

2. The process according to claim 1 , wherein the process further comprises the step of converting 2-substituted-1,4-benzenediamines (1) into a cosmetically acceptable salt using at least one acid HZ:

wherein R is selected from the group consisting of a hydrogen atom and a C 1 -C 4 alkyl group;
wherein Z is a mineral or an organic anion,
wherein m=0.5, 1 or 2.

3. The process according to claim 2 , wherein R is a methyl group.

4. The process according to claim 1 , wherein step a) is carried out in the presence of at least one nitrosation agent in combination with at least one mineral or organic acid.

5. The process according to claim 4 , wherein the nitrosation agent is selected from the group consisting of sodium nitrite, potassium nitrite, N 2 O 5 , nitrosyl sulphuric acid and mixtures thereof and the mineral or organic acid is selected from the group consisting of hydrogen chloride, sulfuric acid, acetic acid and mixtures thereof.

6. The process according to claim 1 , wherein step a) is carried out in the presence of at least one radical scavenger selected from the group consisting of acrylonitrile, methacrylate, urea and mixtures thereof.

7. The process according to claim 1 , wherein step a) or b) is carried out in the presence of at least one solvent selected from the group consisting of pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, 1,2-dimethoxyethane, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, glycols, n-butanol, isopropanol, n-propanol, ethanol, methanol, water, and mixtures thereof.

8. The process according to claim 1 , wherein step c) is carried out in the presence of at least one reducing agent with at least one metal catalyst.

9. The process according to claim 8 , wherein the catalyst is selected from the group consisting of Raney nickel, nickel, palladium, Lindlar's catalyst, cobalt, copper chromite, platinum, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron, and mixtures thereof.

10. The process according to claim 1 , wherein step c) is carried out in the presence of at least one solvent selected from the group consisting of water, petroleum ether, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.

11. The process according to claim 1 , wherein the acid HZ used in step d) is selected from the group consisting of D,L-malic acid, L-malic acid, D-malic acid, hydrochloric acid, hydrobromic acid, citric acid, acetic acid, lactic acid, succinic acid, tartaric acid, phosphoric acid, or sulfuric acid and mixtures thereof.

12. The process according to claim 1 , wherein step d) is carried out in the presence of at least one solvent selected from the group consisting of pentane, cyclopentane, hexane, cyclo hexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate; acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol and mixtures thereof.

13. The process according to claim 1 , wherein step d) is carried out in the presence of at least one solvent selected from the group consisting of ethanol, water and mixture thereof.

14. The process according to claim 1 , wherein:
i) when R is selected from a C 1 -C 4 alkyl group, the 2-substituted aniline of formula (II) is prepared by etherification of 2-nitrobenzyl alcohol of formula (VI) to obtain 2-alkoxymethyl-nitrobenzene of formula (VII) followed by reduction of 2-alkoxymethyl-nitrobenzene of formula (VII):

or
ii) when R is a hydrogen atom, the 2-substituted aniline of formula I) is prepared by reduction of the 2-nitrobenzyl alcohol of formula (VI)

15. The process according to claim 14 , wherein the etherification is performed by an alkylation reaction, a condensation reaction or a nucleophilic substitution.

16. The process according to claim 1 , wherein the 2-substituted aniline of formula (II) is prepared by alkoxylation of 2-halomethyl-nitrobenzene of formula (VIII) to obtain 2-alkoxymethyl-nitrobenzene of formula (VII) followed by reduction of the 2-alkoxymethyl-nitrobenzene of formula (VII):

wherein Y is an halogen selected from the group consisting of bromine, chlorine and iodine.

17. The process according to claim 16 , wherein the alkoxylating agent used for the alkoxylation is selected from the group consisting of alcohols, sodium alkoxides, potassium alkoxides, zinc alkoxides, calcium alkoxides, magnesium alkoxides, tantalum alkoxides, tributyltin alkoxides, salts thereof and mixtures thereof.

18. The process according to claim 16 , wherein the alkoxylation is carried out using a solvent selected from the group consisting of pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, tetrahydrofuran, methyl-tetrahydrofuran, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.

19. The process according to claim 16 , wherein the reduction is carried out in the presence of at least one reducing agent with at least one metal catalyst.

20. The process according to claim 19 , wherein the catalyst is selected from the group consisting of Raney nickel, nickel, palladium, Lindlar's catalyst, cobalt, copper chromite, platinum, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron, and mixtures thereof.

Assignees

• Noxell Corp

Inventors

• Garrett Garry Steven
• Abel Heike Gertrud
• Osan Armin
• Gardlik John Michael
• Murphy Bryan Patrick
• Speckbacher Markus
• Weber Ingo Reinhold

Classifications

• C07C245/20

  Diazonium compounds · CPC title

• C07C245/24

  Chains of only three nitrogen atoms, e.g. diazoamines · CPC title

• C07C213/02 Primary

  by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups · CPC title

• C07C245/08

  with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene · CPC title

• C07C213/06

  from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups · CPC title