DE733756C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the preparation of vat dyes It has been found that vat dyes can be prepared by relying on compounds of the general composition wherein the carbon pair Cl C. is a member of an an.gular fused tetranuclear hydrocarbon radical, which has carbon echsringe and is free of methylene groups, allows o-dicarboxylic acid anhydrides, which may contain halogen, to act and optionally halogenates the reaction products obtained.

The compounds of the above general composition include for example the pyrenolines and chrysenolines.

Phthalic anhydride and phthalic anhydride can be used as o-dicarboxylic acid anhydrides Substitution connections are used.

The action: of the o-dicarboxylic acid anhydrides: on the compounds the mentioned general composition is at a higher temperature in or Absence of inert solvents or diluents such as nitrobenzene or trichlorobenzene, advantageously carried out in the presence of condensing agents. Suitable condensing agents are, for. B. Aluminum halides, such as aluminum chloride or ferric chloride. These condensing agents can be used in the presence of the melting point degrading additives, such as alkali halides (1T: atrium or or and potassium chloride), be used. Halogenating agents are e.g. B. chlorine or bromine.

The dyes obtained can be obtained by crystallization from higher boiling points Solvents, advantageously from nitrobenzene or trichlorobenzene, or by conversion in their salts with strong acids or by treatment with oxidizing agents, like alkali hypochlorite solution.

They can be used for dyeing and printing vegetable fibers such as cotton, be used. The dyeings and prints made with them are very real.

The dyeings and prints of the new dyes are more resistant to soap and washing than the dyeing of the known dye, which is obtained by reacting pyrene with 4-bromophthalates. Example i 3o, 6 parts of 3-pyrenoline (made from 3-aminopyrene due to the action of glycerine rin and sulfuric acid [981 /, i, -] at 130 to i Lgo ° in the presence of nitrobenzene naeh Skraup), id. 4 parts aluminum chloride and 72 parts of Plitlialäureaiiliydri, d become intimate mixed and 20 hours at a temperature ture from 135 to id.o ° baked. -After yours The crushed reaction cake to remove the aluminum rids entered in dilute hydrochloric acid, boiled, filtered and the residue first rides water and then with diluted sodium carbonate solution drawn out hot. The raw one Dye is made from trichlorobenzene and \ itro- benzene recrystallized, with red fine Needles from F. 3.4o to 35o ° can be obtained the ones that are in concentrated sulfuric acid loosen with green paint and cotton ans green-blue vat in red, very real tones to dye. The composition of the color fabric allows for the `` goal of a mono plitlialoyl-3-pyrenolins close. Example 2 i28 parts aluminum chloride, 3o parts ca- lium chloride and 2o parts -Natritirnclilorid are which melted at 112 to 117 °. On that becomes gradually within "., hour a mixture of 10.2 parts of 3-pyreiiolin and 24 parts of Pfithalsäureanliy-drid Stirring entered. -Now the tempe- temperature increased to 165 to 17o ° and 7 hours kept at this temperature: -After your When it cools down, the reaction cake is nert, added to dilute hydrochloric acid, on- boiled, filtered and the residue with Boiled water. The Color: with dilute sodium carborate solution in heat and then with hotter Alcohol undressed. He represents a dark red powder, which is made from triehlobenzene and Nitrobenzene recrystallized «- can and probably yours got in example i Plrtlialoylpyrenolin corresponds. Example 3 io, 2 parts of 3-pyrenoline are in zoo parts Tetrachloroethane distributed, ld. Parts Alurniniuni- chloride and 7 parts of Phtlialäureanliydrid added and while stirring to 6o to 70- heated. -After .lhour stirring, the Temperature increased to g2 to 96 ° and Maintained at this temperature for 16 hours. The decomposition mixture is dissolved in water worn and used to remove the tetra- chloräthans reit Was.serdainpfdestilliert. It is then filtered and the more unchanged 3-pyrenoline by treatment rides hot thin sodium carbonate solution separated. The filtrate is made with dilute hydrochloric acid a n e s. It is then filtered and washed with Water and dry. ; 8 parts of the 3-PyrenolinOvl thus obtained o-lienoic acid and -o parts of Aluniiniunrchlo- rid are intimately mixed and 20 hours baked at 135 to 100 °. The received Dye is, as described in Example i, cleaned and corresponds to that in example i. called plithaloylpyrenoline. example 5.1 parts of 3-pyrenoline and 9 parts of plural acid anhydride are used in i.to parts of trichloro benzene heated to ijo = with stirring. Idie- to be 18 parts _ @ lumin iumchlorid after and after within 1 '.' Hour is called this Temperature entered. After @ 5-r @ it @@ rcrn () hour heating at i 5o - is the settlement finished. plan lets you cool down. sucks and frees the dye by boiling reit dilute hydrochloric acid and j °; roiger Na- trium carbonate solution of impurities. -After your L mcrystallize from trichlorobene- zol and nitrobenzene give a red color. crystalline powder, which is concentrated in I: Sulfuric acid with green color dissolves and Cotton from blue-green isup in red. real tones. - Example j One distributes ao parts of the example i obtained ilonophthaloyl-3-pyrenoline irr 72o parts nitrobenzene, adds some death and charges for i hour at 20 = - 34 parts `ul- add dropwise furylcliloride. Now it will be on 62 bis 6C>, heated up, 16 hours at this "I.'eriilje- held temperature and finally for an hour stirred at 9o to 95 '. -After you have cooled down is filtered, with benzene and alcohol wash and dry. Confused about cleaning the dye in concentrated sulfuric acid redissolved, with the development of hydrochloric acid occurs. The dye represents a red. I: rist <rlli; a powder that has a melting point of 370 to 375 , I have concentrated Sulfuric acid with green color li- # s tund Cotton from green-blue I-cup in red, real tones. Example 6 One distributes 2o parts de: after Peisl- @ iel r obtained Plrtlialoylpyrenolins in 72o parts Nitrohcnzol and leaves within i., Stmide at 20.36 parts of bromine are added dropwise. To adding et @ t-as iodine becomes the Temperature on Sun to 85- erbölit and 16 hours at. at this temperature touched. The dye is filtered off and for cleaning from concentrated sulfur Acid redissolved, with part of the bromine escaping as hydrogen bromide and the brom: erte il-tonophthaloyl-3-pyrenoline as a yellow-red, crystalline powder, which melts at 390 to 395 °, dissolves in concentrated sulfuric acid with a green color and. Cotton from a green-blue vat dyes in real red tones.

Example 7.6 parts of 3-pyrenoline, 20 parts of 3.6 dichloroplithalic acid anhydride and 4o parts of aluminum chloride are intimately mixed and 16 hours at 16o to I65 ° baked. After cooling down, the crushed reaction cake is converted into dilute Hydrochloric acid added, boiled, filtered off, washed out with hot water and with. Treats dilute hot sodium carbonate solution. The Dye recrystallized from trichlorobenzene and nitrobenzene, the 3 ', 6'-dichloromonophthaloyl-3-pyrenoline is obtained as a red, crystalline powder -.lashed in concentrated sulfuric acid dissolves with green paint and dyes cotton from a green vat in real, red tones.

Example S 15 parts of 3-pyrenoline, i.e., parts of 4-bromoplitalic anhydride and so parts of aluminum chloride are intimately mixed and for 20 hours at one Maintained temperature from i.4o to 145 °. -After cooling down, the crushed reaction cake becomes to remove the - #, aluminum chlorine: ds added to dilute hydrochloric acid. It will -then boiled, filtered off and washed out. The raw dye is made by treating with hot dilute sodium carbonate solution and subsequent boiling with finite alcohol purified and recrystallized from trichlorobenzene with the addition of animal charcoal. The q @ -Brommonophthaloy 1-3-pyrenolin represents red needles from F. 33o to 34o, which are concentrated in Dissolve sulfuric acid with green color and put cotton from blue-green vat in blue-tinged red, color real tones.

Example 9 11-Tan distributed io parts of that prepared according to Example S. Broinphthaloylpyrenolines in 48o parts nitrobenzene, add a little iodine and clarify Add dropwise hot 20-17 parts of sulfuryl chloride for 1/2 hour. Uni implementation too Accelerating, the temperature is gradually increased by letting 16 hours at 62 to 66 ° and 1 hour - with go bls 95 '' stirs. After cooling, it becomes: the dye sucked off and redissolved from concentrated sulfuric acid for cleaning. Created a red, crystalline powder that dissolves in concentrated sulfuric acid with green color, has an F. of 95 ° and cotton from a blue-green vat colors in red-blue tones.

Example 10 5.6 parts of z-clirysenolin (manufactured according to the Skraupschen Synthesis), 24 parts of aluminum chloride and 1.2 parts of Plitlialäureanlivdrid «-erden intimately mixed and baked for 16 hours at 138 to 143. After it has cooled down the crushed reaction cake is added to dilute hydrochloric acid. It will then boiled, filtered off, boiled with water and diluted with hot sodium carbonate solution treated. For purification, the dye is recrystallized from nitroben7ol. Man receives a brown powder that dissolves in concentrated sulfuric acid with wine-red Color dissolves, has an F. from -275 to aSo ° and cotton from a wine-red vat in: yellow tones.

Claims (1)

PATENT CLAIMS Process for the preparation of vat dyes, characterized in that one uses compounds of the general composition wherein the Iolilenstoffpa.ar C, C .. is a member of an angularly fused vivlkernigen carbon reagent, which has six carbon rings and is free of methylene groups, o-dicarboxylic acid anhydride, de, d: e halogen, allows it to act and optionally balogenates the reaction products obtained.