Bleaching and dyeing; fluid treatment and chemical modification – Dyeing involving animal-derived natural fiber material ,... – Hair dyeing
Reexamination Certificate
2000-09-22
2002-10-08
Gupta, Yogendra N. (Department: 1751)
Bleaching and dyeing; fluid treatment and chemical modification
Dyeing involving animal-derived natural fiber material ,...
Hair dyeing
C008S405000, C008S406000, C008S410000, C008S416000
Reexamination Certificate
active
06461390
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The subject matter of the present invention is a method for making 2-aminomethyl-1,4-diaminobenzene of formula (I) and its physiologically compatible salts with organic or inorganic salts. It also includes compositions and methods for dyeing keratin fibers containing the 2-aminomethyl-1,4-diaminobenzene or its physiologically compatible salts.
2. Prior Art
2-aminomethyl-1,4-diaminobenzene is known as a starting material for making certain heterocyclic compounds and is described in Liebigs Annals of Chemistry (Annalen der Chemie)1978, pp. 398-404. A method of making this compound is however not described. Also attempts to directly produce this compound from commercially obtained 2-amino-5-nitrobenzonitrile of formula (II) have been unsatisfactory in regard to reaction conditions, yield and product quality.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a simple manufacturing method for making 2-aminomethyl-1,4-diaminobenzene that provides easy production of its oxidation-insensitive salts.
It has now surprisingly been found that 2-aminomethyl-1,4-diamino-benzene may be obtained in a simple manner in good yield by aminomethylation of 4-nitrophenol, subsequent conversion to form the corresponding phenoxyacetamide, rearrangement to form the nitroaniline and finally reduction.
The subject matter of the present invention is thus a method for making. 2-aminomethyl-1,4-diaminobenzene or its physiologically compatible salts of formula (I):
wherein n is a number from 0 to 3 and HX represents an inorganic or organic salt, which comprises
a) reacting 2-(N-acylaminomethyl)4-nitrophenol of formula (III) with a halogen acetamide to form the 2-(2-N-acylaminomethyl4-nitrophenoxy)-acetamide of formula (IV);
b) converting the 2-(2-N-acylaminomethyl-4-nitrophenoxy)-acetamide of formula (IV) to the 2-(N-acylaminomethyl)-4-nitroaniline of formula (V);
c) reducing the 2-(N-acylaminomethyl)-4-nitroaniline to form the 1,4-diamino-2-(N-acylaminomethyl)benzene of formula (VI);
d) adding hydrochloric acid to deacylate the 1,4-diamino-2-(N-acyl-aminomethyl)benzene of formula (VI) and form the corresponding trichloride of formula VII; and
e) when n=0 subsequently converting to the free base form of formula I; or when n≠0 respectively converting to a corresponding salt of HX of formula (1), with the proviso that HX is not HCl when n=3.
Either inorganic or organic acids can be used as the acid ingredient in the above process according to the invention. However the following acids are preferred: hydrochloric acid, sulfuric acid, boric acid, citric acid and tartaric acid. Hydrochloric and sulfuric acid are especially preferred.
The aminomethylation of 2-(N-acylaminomethyl)-4-nitrophenol of formula (III) was described by H. E. Zaugg, Synthesis 1984, pp. 85 to 96. Starting from this intermediate the easily accessible 2-(2-N-acylaminomethyl-4-nitrophenoxy)-acetamide of formula (IV) is produced by heating with a halogen acetamide. lodoacetamide and the somewhat less reactive bromoacetamide are ideally suited as the halogen acetamide. When the more economical chloroacetamide is used to reduce costs, it is advantageous to catalyze the reaction with an iodide, especially sodium iodide or potassium iodide. The amount of the iodide that will result in a higher reaction rate is considerably more than 10% (molar); 50% (molar) has proven to be suitable throughout. The reaction can be performed easily in the usual manner in a normal dipolar aprotic solvent under reflux temperature. The dipolar aprotic solvent can be, for example, acetone. Dialkyl ethers of ethylene glycols and their homologs, preferably those with boiling points under 200° C., such as ethylene glycol dimethyl ether, are suitable as additional solvents. The rearrangement to 2-(N-acyl-aminomethyl)-4-nitroaniline of formula (V) occurs subsequently by addition of base in a solvent, such as dimethylformamide, dimethylacetamide or N-methyl-pyrrolidone, analogously to the reaction described in W. R. Baker, J. Org. Chem. 48, 5140 (1983). Besides the bases disclosed in this reference carbonates, such as sodium carbonate or potassium carbonate, can be used as the added base. Since the carbonates are present in a suspension under the conditions of this latter reaction, it is advantageous to provide it as a fine powder and to use it in a two to five fold excess. The powder should be as fine as possible. The reaction can be performed in a wide temperature range. At temperatures below 80° C. the conversion is low, while at temperatures above 140° C. the reaction mixture is darkly colored by by-products, so that the preferred temperature is in a range from 80 to 120° C. The compound of formula (V) is subsequently reduced in an ideal manner according to the conventional method in an ideal way by catalytic hydrogenation with slightly elevated hydrogen pressure or at slightly elevated temperatures. In this catalytic hydrogenation reaction the compound of formula (V) is converted into the 1,4-diamino-2-(N-acylaminomethyl)benzene dihydrochloride of formula (VI). Finally the compound of formula (VI) is deacylated with hydrochloric acid and the 2-aminomethyl-1,4-diaminobenzene is precipitated as the trichloride of formula (VII). This acid adduct may then be easily converted into the free base form or into other salt adducts of the general formula (I). Understandably also one of the intermediates, for example formula (V), could also be used.
Because of the high oxidation sensitivity of the above-mentioned free base form of the compound of formula (I) (n=0) it is preferably isolated as the acid adduct (n≠0) of formula (VII). The trihydrochloride is a special case of the general formula (I) in which n=3 and HX=HCl.
The compounds of formula (I) are outstanding as oxidation dye-precursor compounds for dyeing keratin fibers.
The present invention also includes compositions and methods for dyeing keratin fibers, especially wool, silk or hair, particularly human hair, using the compounds of formula (I).
Although the compounds of formula (I) are especially suitable for dyeing keratin fibers, in principle it would also be possible to dye other natural or synthetic fibers, especially cotton or nylon 66, with these compounds.
The compounds of formula (I) can be used both alone and also in combination with-certain known developer substances and/or coupler substances, generally known for dyeing fiber materials in oxidative dye systems.
The following compounds especially are suitable coupler substances: N-(3-dimethylaminophenyl)urea, 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di-[(2-hydroxy-ethyl)amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)-pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene, 2,4-diamino-1-(3-hydroxypropoxy)benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene, 2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)-amino]aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline, 3-[(2-aminoethyl)-amino]aniline, 1,3-di(2,4-diaminophenoxy)propane, di-(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxybenzene, 2,6-bis-(2-hydroxyethyl)-aminotoluene, 4-hydroxyindol, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl )amino]acetamide, 5-[(2-hydroxy-ethyl)amino]-2-methylphenol, 3-&ls
Goettel Otto
Hayoz André
Pirrello Aline
Elhilo Eisa B
Gupta Yogendra N.
Striker Michael J.
Wella Aktiengesellschaft
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