Telescoping synthesis of 2-methoxymethyl-P-phenylenediamine

Patent metadata

Field	Value
Publication number	US-9688609-B2
Application number	US-201514926163-A
Country	US
Kind code	B2
Filing date	Oct 29, 2015
Priority date	Nov 4, 2014
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

A telescoping process for the preparation of 2-methoxymethyl-p-phenylenediamine, 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 2-hydroxymethylaniline.

First claim

What is claimed is:

1. A telescoping process for the preparation of 2-methoxymethyl-p-phenylenediamine (I), a cosmetically acceptable salt thereof, or mixture thereof comprising the steps of:
a) synthesizing the intermediate 2-(hydroxymethyl)-4-{3-[2-(hydroxymethyl)phenyl]triaz-1-en-1-yl}aniline (IV) via diazotation using 2-hydroxymethylaniline (II) to obtain the intermediate of formula (III) followed by diazo coupling between the intermediate of formula (III) and 2-hydroxymethylaniline (II):

b) synthesizing the intermediate 2-(hydroxymethyl)-4-{(E)-[2-(hydroxymethyl)phenyl]diazenyl}aniline of formula (V) via rearrangement of the intermediate 2-(hydroxymethyl)-4-{3-[2-(hydroxymethyl)phenyl]triaz-1-en-1-yl}aniline (IV) obtained in step a):

c) synthesizing 2-hydroxymethyl-p-phenylenediamine (VI) and 2-hydroxymethylaniline (II) via hydrogenation of the compound of formula (V):

d) synthesizing 2-methoxymethyl-p-phenylenediamine (I) via acid catalysed etherification of the compound of formula (VI):

2. The process according to claim 1 , wherein the process further comprises the step of converting 2-methoxymethyl-p-phenylenediamine (I) into a cosmetically acceptable salt.

3. The process according to claim 2 , wherein the cosmetically acceptable salt is selected from chloride, sulfate, hydrogensulfate or malonate salt.

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

5. The process according to claim 4 , wherein the nitrosation agent is selected from the group consisting of sodium nitrite, potassium nitrite, dinitrogen pentoxide, nitrosylsulfuric 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.

7. The process according to claim 1 , wherein step a) or b) is carried out in the presence of at least one mineral or organic acid.

8. The process according to claim 7 , wherein the mineral or organic acid is selected from the group consisting of hydrogen chloride, trifluoroacetic acid, sulfuric acid, sulfurous acid, carbonic acid, nitric acid, acetic acid, propionic acid, phosphoric acid and mixtures thereof.

9. The process according to claim 7 , wherein the mineral or organic acid is selected from the group consisting of hydrogen chloride, sulfuric acid, sulfurous acid, acetic acid and mixtures thereof.

10. The process according to claim 1 , wherein the solvent used in step a) or b) is selected from the group consisting of 1,2-dimethoxyethane, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl-tetrahydrofuran, n-pentanol, n-butanol, acetic acid, propionic acid, oxalic acid, malonic acid, sulphuric acid, phosphoric acid, iso-pentanol, t-butanol, isopropanol, n-propanol, ethanol, methanol, glycols, hydrogen chloride, water and mixtures thereof.

11. The process according to claim 1 , wherein step c) carried out in the presence of a hydrogen source selected from hydrazine or H 2 with a metal catalyst selected from the group consisting of Fe, Pd/C, Pd/(OH) 2 , Raney-Ni, Pt/C, PtO 2 and mixtures thereof.

12. The process according to claim 1 , wherein step c) is carried out in the presence of H 2 with a Pd/C catalyst.

13. The process according to claim 1 , wherein the solvent used in step c) is selected from the group consisting of 1,2-dimethoxyethane, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, methylacetate, ethylacetate, n-propylacetate, iso-propylacetate, n-butylacetate, methylpropionate, ethylpropionate, n-propylpropionate, iso-propylpropionate, n-butylpropionate, 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl-tetrahydrofuran, n-butanol, isopropanol, n-propanol, ethanol, methanol, water and mixtures thereof.

14. The process according to claim 1 , wherein the solvent used in step c) is selected from the group consisting of methanol, ethanol, ethylacetate, toluene and mixtures thereof.

15. The process according to claim 1 , wherein the acid used in step d) is selected from the group consisting of hydrogen chloride, hydrogen bromide, sulphuric acid, phosphoric acid, acetic acid, trifluoro acetic acid and mixtures thereof.

16. The process according to claim 1 , wherein the solvent used in step d) is selected from the group consisting of 1,2-dimethoxyethane, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl-tetrahydrofuran, n-pentanol, iso-pentanol, t-butanol, isopropanol, n-propanol, ethanol, methanol, water, glycols and mixtures thereof.

17. The process according to claim 1 , wherein the methylating agent used in step d) is methanol.

18. The process according to claim 1 , wherein 2-hydroxymethyl-aniline (II) is prepared via hydrogenation of 2-nitro-benzyl alcohol (VII):

19. The process according to claim 18 , wherein the hydrogenation of 2-nitro-benzyl alcohol (VII) is carried out in the presence of a hydrogen source selected from hydrazine or H 2 with a metal catalyst selected from the group consisting of Fe, Pd/C, Pd/(OH) 2 , Raney-Ni, Pt/C, PtO 2 and mixtures thereof.

20. The process according to claim 18 , wherein the solvent used for the hydrogenation of 2-nitro-benzyl alcohol (VII) is selected from the group consisting of 1,2-dimethoxyethane, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, methylacetate, ethylacetate, n-propylacetate, iso-propylacetate, n-butylacetate, methylpropionate, ethylpropionate, n-propylpropionate, iso-propylpropionate, n-butylpropionate, 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl-tetrahydrofuran, n-butanol, isopropanol, n-propanol, ethanol, methanol, water and mixtures thereof.

Assignees

• Noxell Corp

Inventors

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

Classifications

• C07C245/08

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

• C07C245/24

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

• C07C213/06 Primary

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

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title