DE631518C - Process for the preparation of dyes of the anthraquinone series - Google Patents

Description

Process for the preparation of dyes of the anthraquinone series Es it was found that new valuable dyes of the anthraquinone series can be obtained, when using anthraquinone derivatives containing exchangeable substituents those arylamines which are in both o-positions to the amino group by alkyl or Halogen substituted and which can also carry further substituents, condensed and optionally the condensation products obtained in sulfonic acids transferred and / or other post-treatments customary in anthraquinone chemistry subject.

Anthraquinone derivatives suitable for carrying out the present process are z. B. i-Amina-2, 4-dihalogenanthraquinones, i-amino- or -alkylamino-q.-halogenanthraquinones, i, q.-, i, 5-, i, ä-dihaloanthraquinones, i-amine (> - 2-alkyl- or -alkoxy- or -sulfo-q.-halogenanthraquinones, quinizarine, halogenanthrapyridones as well as others similarly structured heteronuclear substituted derivatives of anthraquinone.

The arylamines used are those which are at least in the two positions adjacent to the amino group carry substituents such as halogen or alkyl. The two o-position substituents can be identical or different.

The compounds produced by the present process can if they do not contain sulfo groups, for coloring cellulose esters and ethers as well as used by nitrocellulose lacquers.

The sulfo groups necessary for wool dyes can either be in be present in the starting materials or subsequently in the condensation products, either by sulfonation with agents of the sulfuric acid group, or by replacement of reactive atoms or groups of atoms through the sulfo group by means of sulfites, to be introduced.

The new compounds can also be obtained by treatment with aldehydes in neutral or acidic medium in derivatives of diaryl or. Triarylmethane or by treatment with oxidizing agents such as nitric acid, manganese dioxide, etc., in Derivatives of diaryl are converted.

It is also possible to use the dyes obtained by the present process by treating them with carbonic acid amides or ketoacetic acid and malonic acid esters to arrive at pyrimidones or pyridones by known methods.

By using the oo-disubstituted arylamines mentioned here, dyes are obtained which show a shift in hue compared to the known arvlamines obtainable by means of the previously used arylamines. The new dyes enable dyeings of such nuance and liveliness in conjunction with excellent fastness properties that could not be achieved with the known dyes of this type. Example I is heated io parts C-Carbäthoxy-2-methyl-q.-bro@manthfapyridon, 3o parts of i-amino-2, ¢, 6-trimethylbenzene, 4 parts of potassium acetate and o, 1 part of copper powder for 30 minutes runs 15o- bs 16o0. The red melt is diluted with 50 parts of alcohol at = oö °, cold - sucked off and washed with alcohol, then with water. The dried base is stirred in weak oleum for 30 minutes. The solution is poured onto ice and the dye is isolated as usual. It dyes wool a well-leveling, lively yellowish red with good fullness and perspiration fastness.

If in this example the aminotrimethylbenzene is replaced by i-amino-z, q.-dimethy 1-6-bromobenzene, a dye of a similar shade is obtained.

Example 2 20 parts of N-methyl-4-bromoanthrapyridone are mixed with 8 parts Potassium acetate, 0.1 part copper powder and .7o parts i-amino-2,6-dimethylbenzene Heated between 15o and 16o0 until a sample drawn in benzene does not turn any more red, what is the case after about 2 hours. It is allowed to cool to 80 ° and diluted with 100 parts Methyl alcohol and sucks off the precipitated base.

By sulfonating in weak oleum at 0 °, a dye is obtained the wool from acid bath in scarlet-like tones of good mill and perspiration fastness stains. Example 3 2o parts of i-methylamino-q.-bromoanthraquinone, 8 parts of potassium acetate, o, i part copper powder, 7o parts 2, 6-dimethyl-i-aminobenzene are so long on 150 to 16o ° until a sample taken in benzene is no longer bluer, which takes about z: hours. It is allowed to cool and diluted at 80 with 100 parts Methyl alcohol. The base which has separated out is filtered off with suction, washed and dried. It can be used to dye nitrocellulose lacquers.

By sulfonating in weak oleum at 0 °, a dye is obtained which dyes lively red-blue tones with good fastness properties on wool.

The base obtained in this example can be converted into phenolic with urea Convert the solution into a pyrimidone, which is converted into a blue-red dye by sulfonation , can be transformed.

Like the i-methylamina-q.-bromanthrachi "non, the iO, # y-4.-bromoanthraquinone can also be condensed with 2,6-dimethyl-i-aininobenzene. Example q. 10 parts of i-amino-2-methYi- Q. bromoanthraquinone, 3o parts of i-amino-2, q., 6-trimethylbenzene, 4 parts of potassium acetate, o, i part of copper powder are heated briefly to 15 ° to i60 °. The violet become mass wirdbei 80 'with 5o parts of methyl alcohol By sulfonating the base in weak oleum at 40 °, a dye is obtained which dyes wool from an acid bath in lively blue-violet shades of good millfastness and lightfastness. Example 5 20 parts of 1,4-dichloroanthraquinone; 18 parts Potassium acetate, 0.1 part of copper powder, 70 parts of 2,6-dimethyl-i-aminobenzene are stirred at 170 to 180 ° until a sample in benzene is no longer bluer, diluted at 100 ° with 100 parts of alcohol, allowed to cool and The base obtained is free of chlorine.

The sulfonation takes place in weak oleum at 4o0. The received Dye stains wool - a sweat and sweat-proof, chrome-resistant, strong one reddish blue of great vivacity.

If the 1,4-dichloroanthraquinone is replaced by 1,5-dichloroanthraquinone, in the same way, a red dye which is fast and lightfast is obtained. example 6 A mixture of 20 parts of glacial acetic acid, 22 parts of concentrated aqueous ammonia, 40 parts of water with 20 parts of i-amino-2, 4-dibromoanthraquinone, 0.2 parts of copper powder and 100 parts of 2,6-dimethylaminobenzene becomes 2q. Refluxed for hours. One dilutes with 100 parts of alcohol, whereupon the base in beautiful purple needles fails. To convert into 2-sulfonic acid, one part of the base is heated with 2 Parts of 50% potassium sulfite solution and parts of phenol to 1q00 for 16 hours. The phenol is then blown off with steam, diluted with boiling water, The dye solution sucks off little insoluble residue and the dye falls with table salt. He dyes wool and silk in lively reddish blue tones.

A similar dye is obtained if, in this example, the 2,6-Dimethyli-aminobenzene is replaced by 2,6-dichloro-i-aminobenzene. example 7 15 parts of i-amino-4.-brorr, -anthraquinone-2-sulfonsatires sodium, 15 Parts sodium bicarbonate, 15o parts water, 8 'file 2,6-dimethyl-i-aminobenzene and 0.1 part copper powder in a closed vessel at 100 ° for 16 hours. To opening the excess amine with steam blown off and the solution acidified with dilute sulfuric acid. The dye separates in bronzing needles; it is suctioned off and washed with weak salt water. It is identical to the corresponding dye in the previous example.

1 5 parts of the dye are dissolved in 8o parts of sulfuric acid of 930% and partially reprecipitated with 65 parts of water. 1.6 parts of 40 percent by volume of formaldehyde are added and the mixture is heated to 80 for 3 hours. After this time, a sample drawn in cold water is insoluble. The suspension is suctioned off over an acid-proof suction filter, the filter cake is taken up in water and neutralized with potassium hydroxide or sodium hydroxide solution. The dye is filtered off with suction and dried. He dyes wool and silk from acidic and neutral baths in lively, reddish blue tones. The dyeings on wool are very good mill, sweat, potting and lightfast.

A blue dye with similar good properties is obtained, if the i-amino-2-sulfo-4 (6 '2'-dimethylphenyl-i') aminoanthraquinone in sulfuric acid Solution oxidized at low temperature with manganese dioxide to the diphenyl derivative. example 8 2o parts by volume alcohol, 19 parts by volume glacial acetic acid, 24 parts by volume ammonia (stored weight 0.9i), 2o parts by weight i-amino-2, 4-dibromoanthraquinone, 8o parts by volume 6-ethyl-2, 4-dimethyl-i-aminobenzo, l and o, 2 parts by weight of copper powder are 24 hours on Refluxed. It is diluted with alcohol and the blue precipitate is filtered off with suction.

15 parts of the washed and dried base are stirred in 45 parts by volume of weak oleum at 40 to 45 ° until a sample drawn in water is clearly soluble. It is poured into ice and salt water, the dye is suctioned off and washed neutral. The moist paste is heated to 10 ° for 16 hours with 30 parts by volume of 50% potassium sulfite solution and 60 parts by weight of phenol. After blowing off the phenol with steam, the dye solution is filtered and salted out. The new dye turns a very washable, pure blue on Walle.

If you use instead of 6-ethyl-2, 4-dimethyl-i-aminohenzols 2, 4,6-Trimethyl-i-aminobenzene, you get a redder, very vivid blue Dye.

Example 9 2o parts by weight of i-amino-2,4-dibromoanthraquinone-5-sulfonic acid sodium, 5 parts by weight of sodium bicarbonate and 0.2 parts by weight of copper powder with 150 parts by volume of water, 50 parts by volume of ethyl alcohol and 2o parts by volume of r = Amiüo-2, 4, 6- trimethylbenzene refluxed for 20 hours. Alcohol = d base are driven off with steam and then the poorly soluble dye formed is suctioned off and washed out with weak salt water. The dye is heated to 140 ° for 16 hours with 20 parts by volume of potassium sulfite solution of 500 % and 50 parts by volume of water, a new soluble dye being formed. It can be vacuumed directly after cooling. The new dye is less soluble than that of Example B. It dyes wool in very clear blue shades of excellent fastness and can also be used for printing.

In the same way, i-amino-2,4-dibromo-8-sulfonic acid sodium or the technical mixture of the 5- and 8-isomers can be condensed. Example 10 In the same way as indicated in the previous example, i-amino-2, 4-dibromoanthraquinone-6- or 7-sulphonic acid sodium or the technical mixture of the two can be condensed with i-amino-2, 4, 6-trimethylbenzene. Treatment with sulfite converts the sparingly soluble dyes into more easily soluble, clear blue dyes. Example ii 2o parts by weight of the technical mixture of i-amino-4-bromoanthraquinone-2, 5- and 2, 8-disulfonic acid (potassium salt), 5 parts by weight of sodium bicarbonate, 0.2 parts by weight of copper powder are mixed with i 50 parts by volume of water, 50 parts by volume of ethyl alcohol and 2o parts by volume of i-amino-2, 4, 6-trimethylbenzene refluxed for 24 hours. The dye formed is precipitated with hydrochloric acid, filtered off with suction and purified by dissolving from water. The dye is identical to that of Example 9, which was prepared using the technical mixture of isomers. Example i2 A mixture of 10 parts of quinizarine, 10 parts of leucoquinizarine, 6.8 parts of boric anhydride, 20 parts of glacial acetic acid, 10 parts of hydrochloric acid i-amino-2, 4, 6-trimethylbenzene and 6o parts of i-amino-2, 4, 6- trimethylbeiizole is heated to 50 for 20 hours on the reflux condenser with thorough stirring. The air is displaced by carbon dioxide. When the condensation is over, the. Melt in 500 parts water and 100 parts Hydrochloric acid pressed, boiled and sucked off. The base, which is partly made up of leuco bodies is used in the usual way to anthracite quinone derivative oxidized. She will be an example wise with 5oo parts ¢ A4köhol and 3o parts Sodium hydroxide under the leken of air on Boiled reflux, '@is a leuco body more is demonstrable. The: marialized form base obtained wi @ d "sucked off with water washed and dried. The base is identical to the one that according to Example 5 from i, q.-Dichloranthraquinone and i-amino-2, q., 6-trimethylbenzene can be. By sulphonation with weak oleum a dye is obtained from it, wool in lively, pure blue tones of very good quality Color fastness to light, washing and boiling.

Claims (6)

PATENT CLAIMS: i. Process for the preparation of dyes of the anthraquinone series, characterized in that anthraquinone derivatives which contain exchangeable groups are conventionally mixed with arylamines which are substituted in both o-positions to the amino group by allyl or halogen and can also carry further substituents , condensed and, if appropriate, the condensation products obtained are subjected to further post-treatments customary in anthraquinone chemistry. 2. The method according to claim i, characterized in that that one in the obtained arylaminoanthraquinones in the usual way sulfo groups introduces. 3. The method according to claim i and 2, characterized in that the Arylaminoanthraquinones treated with aldehydes in neutral or acidic medium. q .. Process according to claims 1 and 2, characterized in that the arylaminoanthraquinones treated with oxidizing agents. 5. The method according to claim i and 2, characterized in that that the arylaminoanthraquinones in the usual way in anthrapyrimidones or anthrapyrimidines convicted. 6. The method according to claim i and 2, characterized in that the Arylaminoanthraquinones converted into anthrapyridones in the usual way.