Патент USA US2115446код для вставки
2,115,446 Patented Apr. 26, 1938 UNITED ‘ STATES PATENT OFFICE 2,115,446 VAT DYESTUFFS OF THE ANTHRAQUINONE AZINE SERIES ' Karl Koeberle and Joachim Mueller, Ludwigs hafen- on-the-Rhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application November 9, 1934, Se rial No. 752,374. In Germany January 20, 1934 13 Claims. vats. The present invention relates to new vat dye the dyestu?s are obtained in a state of high We have found that valuable Vat dyestuffs yielding blue vats are obtained by treating N purity. They may be puri?ed, if desired, by way suitable as initial materials for the purpose of the present invention may be mentioned the N-alkyl anthraquinone-1-2,2’,l’-azines obtainable 1.2- or 2.1~alkylamino-halogenan thraquinones with themselves, if desired in the form of their leuco compounds, or those obtain able by condensing one molecular proportion of 1-alkylamino-2-halogenanthraquinones with one 15 ‘molecular proportion of l-amino-Z-halogenan thraquinone or one molecular proportion 01' 1 halogen-2-alkylaminoanthraquinone with one molecular proportion of l-halogen-Z-aminoan thraquinone. - As dehydrogenating agents suitable for the 20 purpose of the present invention may be men tioned halogens, agents supplying halogen, as for example sulfuryl chloride, phosphorus penta chloride, benzoyl chloride and the addition com ‘pound of bromine and pyridine, furthermore py 25 rolusite in the presence of a mineral acid, lead dioxide, lead tetraacetate, mixtures of concen trated sulfuric and nitric acids and mixtures of alkali metal bromides with chlorsulfonic acid or oleum. ‘ of their salts with strong mineral acids or by removing any impurities by heating them with organic solvents. The following examples will further illustrate how the said invention may be carried out in by. practice, but these examples are no limitation of 10 condensing 30 The outputs are generally very good, and stuffs and a process of producing same. alkyl-anthraquinone-azines with dehydrogenat ing agents. As N-alkyl-anthraquinone-azlnes 5 (Cl. 260-31) I The reaction is, generally speaking, carried out at elevated temperature, especially if halogens the invention. The parts are by weight. 10 Example 1 23 parts of the N-alkyl-anthraquinone-1,2,2’,1’ azine from 1-methylamino-2-bromanthraquinone and 1-amino-2-bromanthraquinone are heated to from 100° to 110° C. for several hours in 230 parts of nitrobenzene, while stirring, after the addition of 2 parts of iodine and 10 parts of bro mine. As soon as a sample withdrawn yields a pure blue vat, the Whole is allowed to cool and the reaction product which separates in the form of reddish blue needles is ?ltered oiT by suction. It yields a blue vat from which powerful clear blue dyeings of excellent fastness properties are obtained. If 23 parts of bromine be employed instead of 10 parts, a dibromo derivative is obtained under the same conditions. This yields somewhat more greenishblue dyeings than the bromination prod~ not obtained according to the foregoing para graph. . ry out the reaction in an organic diluent as for example nitrobenzene or trichlorbenzene. If halogens or agents supplying halogen are Reaction products containing chlorine and bromine and which likewise yield blue vats and blue dyeings are obtained by employing suliuryl chloride in addition to bromine. The reaction products containing chlorine and bromine dis solve in concentrated sulfuric acid usually to give employed, a halogenation of the reaction prod a brown coloration. or agents supplying halogen are employed. In the'latter case, it is of special advantage to'car ucts may occur at the same time. The reaction products obtained by the treatment with other dehydrogenating agents maybe halogenated in a separate operation. Besides, halogen-contain ing reaction products are obtained by employing halogenated N - al k y l — anthraquinone-l,2,2',l' ' azines as initial substances. The reaction products are vat dyestuffs of ex cellent fastness properties. They yield in all cases blue vats, whereas the initial substances yield brown vats. Besides, the new dyestuffs have a greater strength in color, yield clearer shades of better fastness to chlorine, to light, to the in?uence of the atmosphere and kier-boiling and are less soluble in organic solvents than the initial substances. They may advantageously be 55 employed .for dyeing vegetable ?bres from hot 15" 30" . By starting from the N-alkyl-anthraquinone~ 1,2,2’,1’-azine from 1-brom-2-amino—3~?uoran thraquinone and 1.3-dibrom-Z-methylaminoan thraquinone, it is possible to prepare dyestuffs containing ?uorine or ?uorine and other halo~ gens by treatment with halogen at above 100° C. in the presence of nitrobenzene. Example 2 23 parts of the initial material employed in Ex ample 1 are dissolved in 230 parts of chlorsul fonic acid after the addition of 2 parts of iodine 50 and 10 parts of bromine, warmed to from 60° to 65° C. and kept at the said temperature until a sample withdrawn yields a blue vat. The whole is allowed to cool, the reaction mixture is poured into water, ?ltered by suction and the ?lter cake 2,115,446 Washed until ' ‘neutral- The 7 resulting dyestuff a brown solution and‘ yields a pure blue vat from 1 which contains 2 atoms of bromine per molecule J which at between 40° and 60° C. the vegetable yields blue dyeings of very good iastnessprop~ _ ?bre is dyed strong; clear blue; shades of very . erties on ‘vegetable ?bres from a blue vat. ' good fastness properties. . 7 Example.” 3 I' o, 7 » ' a . :Erample 6‘ ' j ‘ ~ >1 .7 ‘a 10 parts of i the N-alkyl-anthraquinone . employed 23 partsofthe every ?nely'divi'ded compound as :initial material in Example 1 ‘in :7 1;1,2;2',1'-azine obtainable by treating 1.3-dibro'm 230 parts of nitrobenzene are‘heated for 3 hours” Z-methyIaminoanthraquinone ' with sodium‘ ace ‘while stirring'at ‘7590. after the addition of 2 tate in nitrobenzene in the presence of a little parts of iodine and 35 parts of sulfuryl chloride; ' copper acetate which contains bromine and'yields and then for another 2 hours at’ 100° C.’ When a brown vat,’ are dissolved in 100 parts of nitro-_ the reaction is completed the whole is allowed benzene. After theaddition of one part of iodine _ V and 15 parts of sulfuryl chloride, the mixture is , 7 v to cool and thevreacrtion product is,isolated vby 15' ?ltration’ by suction or by distilling off’ the sol ' heated-for 3Ihours at about 75° C‘. and then for. vent; if desiredrwith steam. Ablue'crystalline r '20 further2 hours at. about 95°’ Ci Aftercooling, the reaction product containing 3 atoms of chlo- L powder containing 2 atoms of chlorine 'per mole cule is obtained which7dissolves in concentrated. sulfuric acid giving an orange coloration; it yields a blue-greenvat from which vegetable-?bres are dyed powerful greenish blue shades of excellent ' rine and 2 atoms of bromine is ?ltered off by Sue tion and freed from nitrobenzene for example; 7, V by washing with ethanol. It is a greengblue pow .20' der which from a blue vat dyes'vegetable ?bres fastness to kier boiling that is the 'usual soda ’' powerful blue'shades of excellent fastness. boiling stability test and chlorine. " A vat dyestuif containing '2. atomsjof chlorine a _ .A reaction product containing one to't'wo chlo ’ 25 and 2 atoms of bromine having similar properties. rine atoms having similarproperties is obtained , is-obtained if the compound obtainable: by treatev by carrying out the reaction with} chlorine in tri _ ting 1.3~dibrom-2-ethylaminoanthraquinone with. chlorbenzene. ‘ ' ' ' >7 sodium acetate in nitrobenzene in the presence > ‘ If the reaction described in the ?rst paragraph of a little’ copper acetate whichyieldsa'brown or this example be carried out ‘at 40° C’. while vat, is chlorinated in the manner describedabova a0 lengthening the duration of the reaction to_from' ' ‘ V6 to 10‘hours, a N-methyl-N-dihydroanthraqui 7 ‘ 10 ‘parts of the compoundemployed noneazine containing 3 to 4 chlorine atoms is ob ' tainedi which yields somewhat more reddish dye-' 35 Example ‘ A 30 initial material in Example 6 are dissolved in 100, parts ings than the product, obtainable'raccording to the of nitrobenzene. Afterrthe addition of lpart of ?rst paragraphiof this example and which is en iodine and 15 partsnof bromine, the mixture. is; . heated for 3 hours at’ about 75° C. andj;_for-fu_r-f ' tirely fast to chlorine: 'ther 2 hours at about 95° C. Example 4; . V After ‘cooling, the ’ reaction product containing Zjbromine atoms'is" 7 45.6. parts of the initial material employedin, '?ltered off by suction. andfreed from nitroben: ' 40' Example 3 are heated for 6 hours ‘at about 100° zene for example by Washing with ethanol. It C. in 46Qparts of nitrobenzene after the addition ' ‘is argreen blue powder'whichv from a blue vatg) , oft-2 parts" ofiodine and'60'parts of bromine. dyes vegetable ?bres powerful blue shades of exe' ’ ’ ’ The reaction product obtained. in beautiful .cellent ~ > needles’ is a; dibromo derivative according to anal- a"cellent fastness properties which are essentially . fastnes's. ‘ . i a A‘ vat dyestuif having‘similar properties con-n . ysis and yields on vegetable ?bres ‘from a blue 1 taining 2 atoms of bromine is obtained if the_N-: vat at’ 60° C. clear, greenish blue dyeings of ex-, alkyl-anthraquinone-1,2,2’,1’-azine obtainable .50 superior, especially-as regards fastness to chlo- V none with sodium acetate in nitrobenzene in the? rine, to the 'dyeings obtained with the initial ‘ma-. presence. of a little copper- acetate which yields a brown vat,.is treated with bromine in the man Vterial . A reaction free from'halog/en; product having similarproperties , .; i‘ . V V is ‘- obtained when carrying outthe treatment with ' bromine in other organic diluents, such as tri ’ h 55 chlorbenzene' ‘ ' ' ; ~ 7A1 mono-bromo deriva tive isiobtained when em-. by treating 1.3édibrom-2—ethylaminoanthraqui§ ' ner described above. 50: Eirdmplre 8 I ‘ 10 parts of pyrolusitei'are introduced'into a so‘ ' lution of723 parts of theicondensation’ product} ' ' ploying in the process describedjin the ?rst para- ' employed as initial material inrExample 1 in 300“, ' graph of this example .‘16 partsfofbromineg It. parts of sulfuric acid. lThe reaction 'mixtureiis _ yields somewhat more reddish blue dyeings than V heated at 80° C. until a samplerwithdrawn yields thew dibromo derivative of improved fastness to a blue vat. After cooling,‘the whole is ?ltered ' 76o chlorine as compared-with the initial material ‘ . V off'b-y suction, the ?ltrate pouredinto water,jthe The treatment with bromine may also be car > dyestuff precipitated filtered ‘off by'suction and“. ' ried out in‘ chlorsulfonic. acid. Onxgr‘indin'gv the washed with water. 'It is‘ algreen-blue powderf V ?nely divided initial materialiin a ball mill with which yields a>b1ue vat and which dyes’ cotton‘ ' bromine in the presence. of iodine a bromo deriva-v clear powerful blue shades of very good'fastnessi ' I 65 tive is likewise obtained.’ . , . . properties. 7. _ Example 9 ' Example 5 ' 1 23 parts’ of the initial material employed 'in Example 1 are heated‘ to boiling for about 5 ’' 5 parts of’ the condensation product employed as initial material in Example v1 arerboiled'with a .mixture'of 50 parts of nitrobenzenegand 10' hours in'200 parts of nitrobenzene after the addié ‘parts of 'benzoyl chloride for 5 hours.- After .tion 01350 parts of benzoyl chloride and 2 parts working ‘up blue-violet’ ‘needles 7 substantially‘ w of ‘iodine. “After coolingythe reaction? product, chlorine free are obtained which dissolve in con-5‘ whichisksubsta‘ntially'chlorine free, separated in. centrated sulfuric acid giving a brown'coloration lustrous bronze crystalline needles is ?ltered off. ~ and which dye cotton from‘ a blue vat clear blue i .It dissolves’ in concentrated sulfuric acid to give’ shades of very good fastness properties. . 2,115,446 5. Aprocess of producing vat dyestuffs of the anthraquinone-azine series which comprises heat ing N-alkylanthraquinone-1,2,2’,1'-azines with a Example 10 10 parts of the N-alkyl-anthraquinone-1,2,2’,1’ azine obtained by treating 1-methylamino-2 bromanthraquinone with sodium acetate in the chlorinating agent. 6. A process of producing vat dyestuffs of the anthraquinone-azine series which comprises heat presence of nitrobenzene and a little copper oxide are boiled with 100 parts of nitrobenzene after the ing N-alkylanthraquinone-1,2,2’,1'-azines with addition of 1 part of iodine for 5 hours. The dye stulf thus obtained which after working up the reaction mixture forms blue crystals, dyes from 10 a blue vat vegetable ?bres blue shades of ex cellent fastness. sulfuryl chloride. benzoyl chloride. 7 8. Vat dyestuffs of the anthraquinone-azine series yielding blue vats containing up to two alkyl groups of low molecular weight attached to 15 the nitrogen atoms of the azine ring obtainable according to the process claimed in claim 1 exist ing in the crystalline state in the form of blue needles, dissolving in concentrated sulphuric acid 15 to Example 5 are suspended in 100 parts of nitro benzene. After the addition of 10 parts of bro mine and 2 parts of iodine, the mixture is heated for several hours at 120° to» 125° C. After cooling, the reaction product which contains 2 atoms of 20 bromine per molecule separates in crystalline form and is ?ltered off by suction. It dissolves in concentrated sulfuric acid giving a pitch brown with a brown coloration and dyeing cotton clear 20 blue shades of very good fastness to chlorine. 9. Vat dyestuffs of the anthraquinone-azine series yielding blue vats containing up to two alkyl groups of low molecular weight attached to coloration. It dyes vegetable ?bres from a blue vat greenish blue shades of very good fastness. the nitrogen atoms of the azine ring and contain 25 ing halogen obtainable according to a process cov ered by claim 1 existing in the crystalline state in the form of blue needles, dissolving in concen trated sulphuric acid with a brown coloration and dyeingcotton clear blue shades of very good fast 30 Example 12 A mixture of 50 parts of the compound obtain able according to Example 5, 500 parts of nitro benzene, 75 parts of sulfuryl ‘chloride and 2 parts 30 of iodine is heated for several hours at 75° to 85° C. After cooling, the reaction product which con tains 3 atoms of chlorine is isolated in the usual manner. ‘ anthraquinone-azine series which comprises heat 10 ing N-alkylanthraquinone-l,2,2',l’-azinesi with Example 11 20 parts of the compound obtainable according 25 7 7. A process of producing vat dyestuffs of the ness to chlorine. 10. Vat dyestuffs of the anthraquinone-l,2,2',l’ azine series yielding blue vats containing up to two alkyl groups of low molecular weight at tached to the nitrogen atoms of the azine ring and 35 containing halogen atoms of different kind ob tainable according to a process covered by claim‘l existing'in the crystalline state in the form of blue It dissolves in concentrated sulfuric acid giving a yellow brown coloration. It dyes 35 vegetable ?bres from a blue vat clear powerful blue shades of excellent fastness. Example 1 3 12 parts of the reaction product obtainable ac ' needles dissolving in concentrated sulphuric acid 40 cording to Example 5 are suspended in 200 parts with a brown coloration and dyeing cotton clear 40 of nitrobenzene. After the addition of 10 parts of blue shades of very good fastness to chlorine. sulfuryl chloride and 1 part of iodine, the reaction 11. Vat dyestuffs of the anthraquinone-1,2,2’,1' mixture is heated, while stirring, at 70° to- 75° C. azine series yielding blue vats containing up to for 3 hours. Then, after the addition of 15 parts two alkyl groups of low molecular we1ght at 45 of bromine, the temperature is raised to 120° to tached to: the nitrogen atoms of the azine ring and 45 125° C. and the whole kept at this temperature containing chlorine obtainable according to a for another 3 hours. After cooling, the dyestuif process covered by claim 5 existing in the crystal separated is ?ltered off by suction. It contains 4 line state in the form of blue needles dissolving in atoms of chlorine and 1 atom of bromine and dis concentrated sulphuric acid with a brown colora 50 solves in concentrated sulfuric acid giving a brown 7‘ tion and dyeing cotton clear blue shades of very coloration. It dyes vegetable ?bres from a blue good fastness to chlorine. ' vat blue shades of excellent fastness. 12. Vat dyestuffs of the anthraquinone-1,2,2',‘1' What we claim is: azine series yielding blue vats containing up to 1. A process of producing vat dyestuffs of the two alkyl groups of low molecular weight at 55 anthraquinone-azine series which comprises ' tached to the nitrogen atoms of the azine ring and treating N-alkyl - anthraquinone-1,2,2',1’-azines with halogenating agents. 2. A process of producing vat dyestuffs of the anthraquinone-azine 60 series which comprises heating N - alkylanthraquinone - 1,2,2’,1’ - azines with halogenating agents in an organic diluent. 3. A process of producing vat dyestuffs of the anthraquinone-azine series which comprises heating N - alkylanthraquinone - 1,2,2’,1’ - azines with bromine in an organic diluent. ' 4. A process of producing vat dyestuffs of the anthraquinone-azine series which comprises heating N - alkylanthraquinone - 1,2,2’,1' - azines with bromine in an organic diluent in the pres 70 ence of a halogen transferrer. containing bromine obtainable according to the process of claim 3 existing in the crystalline state in the form of blue needles dissolving in concen trated sulphuric acid with a brown coloration and 60 dyeing cotton clear blue shades of very good fast ness to chlorine. ' 13. Trichlor-N-methyl-anthraquinone-1,2,2',1' azines obtainable by heating N-methylanthra quinone-1,2,2',1'-azines with sulphuryl chloride in 65 the presence of nitrobenzene and a little iodine acting as catalyst. KARL KOEBE'RLE. J OACI-HM MUELLER.