US2138113A

US2138113A - Onium-methyl benzenes

Info

Publication number: US2138113A
Authority: US
Publication date: 1938-11-29
Anticipated expiration: 1955-11-29

Description

Patented Nov. 29, 1938 UNITED STATES PATENT OFFICE ONIUM-METHYL BENZENES, USEFUL FOR IMPROVING THE FASTNESS OF DYEINGS 2 Claims.

Our invention relates to compounds useful for improving the fastness of dyeings, and process of producing same.

It is well known that dyeings obtained on cel- 5 lulosic materials by means of substantive dyestuffs can be improved as regards fastness by treatment with salts of certain organic bases. A great number of such bases has already been proposed for this purpose. Most of them are characterized by the fact that they contain in the molecule a long aliphatic carbon chain of at least 7 carbon atoms.

Such bases are capable of improving the fastness to water and to cross dyeings and-as' far as they contain pentavalent nitrogen--to perspiration, but they can not substantially improve the fastness to washing which is of considerably more importance.

Our present invention relates to particular compounds which are capable of improving the fastness to washing of dyeings obtained on cellulosic materials by means of substantive dyestuffs. The new compounds are first characterized by the presence of a radicle of high molecular weight R, which R may contain one or more benzene nuclei or a pyridine radical, but not containing a system of 8 conjugated double bonds, moreover by the presence of a plurality of pentavalent nitrogen atoms or tetravalent sulfur atoms or pentavalent phosphorus atoms and finally by an at least diacid strong basic character.

The favorable effect of the present compounds is obtained by the fact that they do not contain a long aliphatic chain and that therefore their reaction products with dyestufi acids are insoluble not only in water but also in solutions of soaps. By the fact that they contain nitrogen, sulfur or phosphorus atoms of basic character in the highest valency the fact is obtained that the salts of these compounds with the dyestufi-acids of the used substantive dyestuffs are not decomposed by the alkali used for washing the dyeings.

The application of compounds containing the residue of a polymeric aliphatic amine is pro tected by application Ser. No. 747,078, filed Octoher 5, 1934, by Ferdinand Miinz and Karl Keller. In contrast with these compounds the above described compounds constitute a technical progress because they exist in great numbers of different constitution and most of them may be easily obtained from easily accessible initial materials.

Our present compounds are distinguished by their superior mode of acting from the products of the French Patent No. 758,199, which products are salts of substantive quaternary ammonium bases containing a system of at least 8 conjugated double bonds in the molecule and likewise suitable for the after-treatment of dyeings obtained on cellulosic materials by means of substantive 60 dyestufls.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees. We wish it, however, to be understood that our invention is not limited to the particular products nor reaction conditions mentioned therein.

Example 1 54 parts of 1,4-phenylenediamine are dissolved in 500 parts of water. Then parts of sodium carbonate are added and. parts of chloracetyl chloride are slowly poured in at about 0 to 5 C. The precipitate formed which is the dichlorodiacetyl-1,4-phenylene-diamine of the following formula:

NH-COOHr-Cl is washed with cold and hot water and alcohol.

50 parts thereof are mixed with 100 partsof pyridine and the mixture is heated to about 100 C. for 20 hours. washed with alcohol and dried. It may be freed from unaltered initial material by redissolving in water, filtering the solution thus obtained and precipitating it by the addition of sodium chloride or alcohol. A dyeing obtained on cotton by means of 3% of Sirius blue BR. (Schultz, Farbstofitabellen, 7th edition, vol. 2, page 197) which is after-treated for half an hour at about 30 C. with a solution containing 2 grs. of the above product per liter exhibits a very good fastness to washing. The new compound is when dry a light brown powder easily soluble in water and insoluble in alcohol.

Example 2 228 parts of 3,4,3,4'-tetraamino-diphenylmethane are mixed with parts of phthalic anhydride and the mixture is heated to about to 200 C. until the splitting off of water is finished. The fused mass obtained is powdered, extracted with hot sodium carbonate solution and dried. 100 parts of the imidazole thus obtained are dissolved in 50 parts of formic acid and 300 parts of water and the free base is precipitated in fine dispersion by the addition of sodium carbonate. The suspension is treated with 200 parts of dimethyl sulfate in the presence of an excess of alkali. Then the product formed is dissolved by the addition of great quantities of water, the solution obtained is filtered and precipitated by the addition of sodium chloride; The products are obtained as a brownish powder, easily soluble in water.

The precipitate formed is mc-c o-on. 1m CHF'ONII and which can be obtained in an analogous manner from 3,4,3,4'-tetraamino-diphenylmethane by the action of acetic acid, exhibit a considerably increased fastness to washing too.

Example 3 A mixture of 224 parts of p-phenylene diglycine (see German Patent No. 145,062) and 216 parts of o-phenylene-diamine is heated to about 200 C. until the splitting oil of water is finished. The imidazole formed which corresponds with the following formula:

may be isolated in a similar manner to that described in Example 2. It is converted into the tertiary base by the action of dimethyl sulphate and sodium carbonate in an aqueous solution. 30 parts of the tertiary base are mixed with 70 parts of the methyl ester of p-toluene-sulphonic acid and the mixture is heated to about 100 C. for 3 hours. The fused mass is dissolved in water and the solution obtained is neutralized and concentrated by evaporation.

The new product is likewise capable of improving considerably the fastness to washing oi dyeings obtained by means of substantive dyestuifs.

Example 4 '10v parts of 2,6-diaminopyridlne (see German Patent No. 399,902) and 46 parts of symmetric dichloro-acetone are dissolved in chloro-benzene and the solution obtained is heated to 100 C. until the precipitation is finished. The precipitate formed is washed with chlorobenzene and the hydrochloride of the base thus obtained is dissolved in water. The solution obtained is treated with 400 parts of dimethyl sulfate in the presence of an excess of alkali at room temperature until the dimethyl sulfate is decomposed.

The new base exhibits asimilar effect to dyeings obtained by means of substantive dyestufls as the above described products.

Example 5 A dyeing obtained on cotton with 3% of Brillantbenzoechtviolett 5RH (Schultz, Farbstofitabellen, 7th edition, vol. 1, page 148, No. 342) is treated for half an hour at 30 to C. with a solution of 1 gr. per liter of dibenzyl-ditriphenylphosphonium dichloride of the following formula:

which compound is obtainable by decomposing the ditolyldichloride of the formula:

crmcQ-Oomm with two molecular proportions of triphenylphosphine with the addition of a small quantity of toluene.

The dyeing exhibits after this treatment a considerably increased fastness to washing.

Example 6 is washed with benzene, dried and then dissolved in water. The solution obtained is freed from small quantities of unaltered initial material by filtering. The aqueous solution can be immediately used. In order to obtain the product in a dry form it may be precipitated from its solution by the addition of acetone. It is a brownish powder easily soluble in water and insoluble in alcohol.

The new base exhibits a similar efiect to dyeings obtained by means of substantive dyestuffs as the above described products.

A sulphonium compound of similar properties which corresponds to the following formula:

is obtained by converting the above said hexabromo-hexamethylbenzene by the action of sodium sulfide into the corresponding mercaptan which is exhaustively methylated.

Example 7 A dyeing obtained on cotton with 3% of Brillantbenzoviolett BBI-I (Schultz, Farbstofl'tabellen, 7th edition, supplement Vol. I, page 73) is treated for half an hour at C. with a solution of 1 gr. per liter of a pyridinium base (described in the German Patent No. 551,872, Example 4) of a resin which is obtained by starting from a technical cresol mixture and by acting thereupon with formaldehyde in the presence of hydrochloric acid.

The dyeing thus treated exhibits a considerably increased fastness to washing.

We claim:

1. Compounds useful for improving the fastness of dyeings which compounds correspond with the formula:

halogen R- OH:X\

wherein X represents an element selected from the group consisting of pentavalent nitrogen and phosphorus and tetravalent sulfur, R stands for a radicle of the benzene series, Y represents an which product is when dry a. brownish powder easily soluble in water and insoluble in alcohol.

FERDINAND MiiNz. KARL KELLER. o'rro TROSKEN.