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UNITED STATE S PATENT OFFICE BENZOTHIOPHENE ANTHRAQUINONE DYESTUFFS - Fritz Max, Staten Island, N

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UNITED STATE S PATENT OFFICE BENZOTHIOPHENE ANTHRAQUINONE DYESTUFFS - Fritz Max, Staten Island, N Patented Oct. 28, 1952 2,615,898 UNITED STATE s PATENT OFFICE BENZOTHIOPHENE ANTHRAQUINONE DYESTUFFS - Fritz Max, Staten Island, N. Y., and Wilhelm Schmidt-Nickels, Little York, N. J., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application October 14, 1948, Serial No. 54,582 . 12 Claims. (CI. 260-329.2) This invention relates to novel dyestuffs of the wherein the first compound has four unsubstis benzothiophene anthraquinone Series. tuted alpha-positions in the anthraquinone nu More specifically, the invention relates to novel cleus and the second compound has three unsub a-amino-benzothiophene anthraquinones which stituted alpha-positions. are valuable as dyestuffs for organic derivatives In preparing the novel dyestuffs suitable for of cellulose, particularly cellulose esters and coloring cellulose esters and ethers in accordance ethers such as cellulose acetate and ethyl cellu with this invention, the aforesaid benzothiophene lose and fibers or textile materials containing the anthraquinones are subjected to nitration by treat same, such dyestuffs being applied to the afore ment With a mixture of concentrated nitric and said materials in the form of an aqueous disper O Sulfuric acids. An d-dinitro benzothiophene an sion. Further, the invention relates to d-aroyl thraquinone is thereby formed wherein the a amino benzothiophene anthraquinones, corre nitro groups apparently occupy the 15- and 1.8- sponding to the aforesaid d-amino derivatives positions of the anthraquinone nucleus. The a and prepared therefrom by reaction with an aryl dinitro compounds are thereupon Subjected to re. carboxylating agent, which are valuable vat dye 5 duction, for example, by heating with an aqueous stuffs suitable for producing colorations on cellu alkali metal sulfide solution, yielding the corre losic fiber and textiles by conventional vat dyeing sponding diamino - benzothiophene anthraquin or printing procedures. OneS. ". The novel dyestuffs of this invention are pre Additional amino groups can be introduced in pared from benzothiophene anthraquinones, ad 20 to the remaining unsubstituted alpha-positions vantageously obtained by the process of our co of the anthraquinone nucleus by acylating the pending application, Serial No. 53,148 filed Octo aforesaid adianino compounds, with oxalic acid, ber 6, 1948, now U. S. Patent 2,533,171, dated De to form the corresponding dioxaminic acid, Sub cember 5, 1950, by condensation of phthalic an jecting this compound to nitration with concen hydride with a dibenzothiophene (diphenylene 25 trated sulfuric acid and nitric acid, reducing the sulfide) and ring closure of the resulting ortho additional nitro groups thereby introduced to 2-dibenzothenoyl benzoic acid in the presence of . amino groups by reaction with alkali metal sulfide a mixture of ortho-phosphoric acid and phos and reconverting the oxaminic acid groups to phorus pentoxide. Since the initial condensation amino groups by alkaline hydrolysis. of dibenzothiophene with phthalic anhydride re 30 The d - polyamino-benzothiophene anthraqui sults in substitution of one of the benzene rings nones of this invention, produced as indicated of the dibenzothiophene nucleus in para-position 3. above, are water-soluble compounds which can be to the sulfur (i. e., the 2-position), the sulfur oc dispersed in aqueous media with a suitable dis cupies a beta-position of the anthraquinone nu persing agent to yield dye baths from which or cleus in the resulting benzothiophene anthra 35 ganic derivatives, particularly ethers and esters, quinone, and the anthraquinone nucleus retains of cellulose, e. g., cellulose acetate, cellulose bu at least three unsubstituted alpha-positions. tyrate, ethyl cellulose, cellulose acetate, butyrate, Thus, the benzothiophene anthraquinones are in the form of a fiber or textile material contain believed to be a mixture of two compounds have ing the same, can be dyed-in brilliant Orange to ing the following nuclear structures: 40 Scarlet to blue Shades of outstanding fastness properties. s. ; : CO The vat dyestuffs of this invention are the poly - d -aroylamino-benzothiophene anthraqui nones corresponding to the aforesaid poly-a- C Yo6O ^Ns 45 amino Compounds. They are conveniently pro duced by reacting the poly-a-amino benzothio. and phene anthraquinones of the invention. With an aryl carboxy acid halide such as benzoyl chloride, 2-methoxy - 3 - naphthoyl chloride, 1-amino 50 anthra.cuinone-2-carboxy acid chloride, or the corresponding bromides or anhydrides, in an or ganic Solvent such as nitrobenzene in the pres ence of a basic compound Such as an alkali metal carbonate. The resulting poly - a - aroylamino 55 benzothiophene anthraquinones can be applied to cellulosic fiber such as cotton or regenerated cel lulose or textile materials containing the same, 3,615,898 3 4. V. V. from an alkaline hydrosulfite vat or printed rivatives of cellulose when applied thereto from thereon in the form of a wait printing composi aqueous dispersions. tion. Upon subsequent aging to effect reoxida tion on the fiber, strong yellow shades of excel Eacample 2 lent fastness properties are produced. 5 The a-diamino-benzothiophene anthraquinone The invention is illustrated by the following of Example 1 is converted to the corresponding examples Wherein the parts and percentages are a-dioxaminic acid by heating it with four times by weight and the temperatures are in degrees its Weight of oxalic acid at a temperature of centigrade. 100-150 until the unreacted diamino compound Eacample 1 is no longer present. Excess oxalic acid is re Owed from the reaction mixture by extraction 47.1 parts of benzothiophene anthraquinone with: Water, and the residue is dried and subjected prepared by condensing phthalic anhydride with to nitration with a mixture of concentrated sul dibenzothiophene in the presence of aluminum furic acid. and nitric acid by the same procedure chloride, and heating the resulting ortho-2-di as that described in Example 1. The nitrated benzothenoyl benzoic acid with an equimolecular product is recovered by drowning the mixture in mixture of Ortho-phosphoric acid and phosphorus ice water. The oxaminic acid groups are recon pentoxide at 170° for 10 minutes, were introduced verted to amino groups by heating with dilute at a temperature below 40° into an agitated mix aqueous caustic Soda. Solution, and the nitro ture of 150 parts of concentrated sulfuric acid groups of the resulting nitrated a -diamino-benzo and 17 parts of a mixture of nitric acid and thiophene anthraquinone are reduced to amino concentrated sulfuric acidina, ratio of 1:2. When groupS by heating with aqueous sodium sulfide, as the addition is complete, the mixture is agitated described in Example 1. The resulting insoluble at 40° for 1 hour, then cooled to 20° and poured a-polyamino-benzothiophene anthraquinone is into ice water. Alpha-dinitro-benzothiophene 25 recovered from the reaction mixture, by filtration, anthraquinone is thereby precipitated, and re Washed with water and dried. The resulting.com covered in the form of a filter cake by filtration. pound contains amino groups in each of the a The filter cake is Washed with Water and intro positions of the anthraguinone nucleus available duced into a solution, heated to 95, Inade by for substitution in the original benzothiophene adding 180 parts of crystalline Sodium sulfide 30 anthraquinone. , (Na2S,9H2O) and 110 parts of 20% aqueous so The resulting a-polyamino-benzothiophene-an dium hydroxide. solution to 875 parts of water. thraquinone can be dispersed in an aqueous dye The resulting mixture is stirred at 95-100 for bath as disclosed in the preceding example and one-half hour to effect complete reduction of the applied in dyeing cellulose acetate fiber, whereby nitro groups to amino groups. The resulting a reddish-blue colorations of good fastness. proper diamino-benzothiophene anthraquinone is re ties can be obtained. covered by filtration in the form of a filter cake, By employing substituted a -diamino-benzothio washed with water until neutral and dried. phene anthraquinones of the preceding example, To prepare a dye bath from the resulting a correspondingly substituted a-polyamino-benzo -diamino compound, 0.6 part thereof can be dis 0. thiophene anthraquinones are obtained in the solved in a Small quantity of a mixture of equal process of this example. parts of alcohol and acetone, followed by admix ture of 40 parts of a 50% aqueous solution of N,N- Eacample 3 Öley methyl tatrine sodium salt or of a similar 9.8 parts of the a-diamino-benzothiophene: an Saponaceous dispersing agent, and diluting the 45 thraquinone of Example 1 are mixed with 120 mixture with 5000 parts of warn Water at 45-55°. parts of nitrobenzene containing 12.2 parts of 100 parts of Cellulose acetate Siki, the form of benzoyl chloride, and 9.1 parts of sodium car yarn or fabric, is then worked into the dye bath bonate are added thereto. The mixture is heated while raising the temperature to 80-90. When while agitating at a temperature of 200-2059 for the dyeing is complete, the dyed material is re 50 5 hours. The reaction mixture is then allowed moved from the dye bath, soaped, rinsed and to cool and the benzoylated product. which sep dried. A billiant Scarlet Shade of good fastness arates from the mixture is recovered by filtration, properties. is produced on the fiber or textile:Ina washed with nitrobenzene and dried. For puri - 'teria. " - fication the resulting product is dissolved in con Instead of unsubstituted benzothiophene an 55 centrated sulfuric-acid, drowned in dilutelaqueous thraquinone employed in the foregoirag eSan alkali metal bichromate, the resulting slurry ple, substituted benzothiophene anthraquinones boiled for a short time and the insoluble product can be used as starting materials containing, for recovered by filtration. The product is then example, chlorine, bromine or a nitro group in boiled with a dilute alkaline sodium hypochlorite the benzene ring of the benzothiophene nucleus 60 Solution, separated by filtration, washed and in para-position to the Sulfur, obtained by ring dried.
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