Патент USA US2408260код для вставки
Patented Sept.v24, 1946 2,408,259 UNITED ,"STATE SVIPATENT, OFFICE2,408,259‘ ‘ VAT DYESTUFFS A121) PROCESS OF MAKING Theodor Holbro, Basel, Walter'Kern, Sissach‘, and Paul Sutter, Basel, Switzerland, ass’ignors to-So ciety of Chemical Industry in Basic, Basel, Switzerland No Drawing. Application February 4, 1943, Se ,rial No. 474,728. In Switzerland ' January 8, 1942 (01. 2604303) 13 Claims. 2 The present invention is concerned with new vat dyestuffs and a process for producing the same. More particularly the invention is con cerned with vat dyestuffs of the anthraquinone ill-position of the anthraquinonc nucleus are in volved in ring formation. The reaction may be carried out symmetrically in 1:9 and .5:10‘or in 1:9 and 4:10 positions, or according to the circumstances‘?rst one ring and. afterwards a series and still more particularly with those con taining carbonamide groupings and/or hetero cyclic groupings derivable “therefrom. ‘ second ringfmay be closed, whereby asymmetrical A considerable number of vat dyestuffs con Amongst, heterocyclic rings which may ' be anthraquinone derivatives may be obtained...“ ' taining carbonamide groupings is already known.‘ fused on according to. methods knownper se Amongst this group. of vat dyestu?s, generally 10 there are six-membered rings. such as pyridine, speaking, those are of special interest which dye ‘ pyridone, pyridazinapyrimidine and pyrimidone yellow tints because yellow'andmore particu-v larly bright yellow to greenish yellow tints are not easily obtainable with vat dyestuffs of other rings which may carry substituents such as alkyl groups, especially lowerialkyl' groups containing groups. However it is generally known that I many yellow to greenish yellow vat dyestuffs are defective in fastness to light and/or af?nity to cellulosic ?ber and therefore there is still a strong demand for better'dyestuffs. 1 :5-dichl0ranthraquinone-2 : G-dicarboxylic , acid According to the present invention new and can be-transformed by direct reaction with'alkali polysul?des such as sodium disul?de and am valuable vat dyestuffs'are prepared by reacting carboxylic acids of anthraquinone derivatives, containing at least two rings, at least cne'of which is heterocyclic, linked to at least‘two'peri monia i-nto ,, 1-:9,5; l0.-anthradithiazol-2,6-dicar boxylic acid, or the‘same product may be con densed with alkyl-hydrazines,- such as methyl ‘positions of the anthraquinone nucleus, with amines of vattable compounds. up to?vecarbon atoms or carboxylic groups. Insome cases ?ve-membered rings are of espe cially favorable. character'such as thiazole and ‘pyrazole rings which may also carry substite uents as mentioned above. By way .of example l hydrazine I The starting compounds ‘required for the present process viz. anthra'quinone‘ compounds with heterocyclic rings linked to'pperi-positions may be prepared from such anthraquinone sub stitution products containing substituents‘ in at least two ‘alpha-positions which promote ring formation; e. g. halogen, amino, hydroxyl nitro, or carboxylic groups.’ Besides these substituents to . 1:9,5z10-di-(N)-methy1-pyrazol ,anthrone. .For the preparation of other anthra quinone derivatives containing heterocyclic rings other. methods and conditions are necessary, which are-known, per se and only theirapplica .30 tionisto be-adapted to the special case. 7 " If these anthraquinonederivatives containing heterocyclic rings do not yet possessthe desired carboxylic groups or functional derivatives there of, such groups may be introduced into the mole required forring formation the said anthra V35 cule in a separate step, for example by exchange quinone substitution products may contain fur-v or transformation of substituents already present ther' substituents preferably ‘of such nature and/or in such positionsthat'they do‘ not inter fere with the intended formation 'of rings. Amongst such additional substituents carboxylic or purposely introduced, for or into carboxylic groups. I , v ‘ ’ ~ As already. mentioned new vat dyestuffs are made from these anthraquinone derivatives con groups and/or substituents or groupings capable ‘ tainingasv substituents one, preferably two, or of being‘transformed into or of being replaced more .carboxylic groups and having fused ‘on at by carboxylic groups or functional‘ derivatives least-gtwowrings in peri-positions, which rings thereof are to be mentioned. As _there are four may be, .of- the same or of different kind and at combinations‘ of peri-positions in the anthra .45 least'on'e of .the said ringslbeing ‘heterocyclic and quinone nucleus (1:9, 8:9, 4:10, 5:-l0)pto which ' therefore containing one ‘or more hetero-atoms, rings can be linked, the substituents intended for ‘for; examplenitrogen, sulfur and oxygen alone ring formation can be‘ in any two or more than or in combination. The carboxylic groupsnmay two of the four alpha-positions, for example :in be situated in’th'e anthraquinone nucleus or in 1 and 4 or preferably in 1 and 5 (or 4 and'8 re spectively) position whereas it ispreferable, but .50 a. hetero. ring., Some especially valuable dye stuffs are obtained from anthradithiazole car not necessary, that additional substitution oc cupy beta-positions, for example 2 and 7 or pref erably 2 and 6 position if two additionalsub. stituents are present,or only one of ‘these posi: 55 tions or even more. ' For the preparation of the present starting compounds atleast two rings (one atfleast be ing heterocyclic) are linkedyto at least two peri positions whereby preferably both the _9- and‘ the boxylic acids. such as 1:9,5;IO-anthradithiazole 2:6-(or 4:8)-dicarboxylic acid or from the cor responding mono-carboxylic acids, containing only one carboxylic group, for example in 2 position. A ' The new vat dyestuffs are made by reacting ftheisaid carboxylic acids with vattable com pounds containing amino groups. vattable com poundssuitable for this purpose are those for 2,408,259 ' 3 4 The present invention provides inter alia yellow example which belong to the anthra'quinone se dyestuffs of very pure shade possessing very good all-around fastness and especially excellent fast ries. They may be aminoanthraquinones or may contain condensed ring systems containing more ness to light. than three six-membered carbon rings, such as , It is interesting to note that practically all car aminodibenzanthrones and aminopyranthrones, boxylic acids hitherto used for preparing vat dye stuffs of the carbonamide type if combined with or such as are obtained by condensing hetero cyclic rings with an anthraquinone nucleus, as ,Z-aminoanthraquinone yield dyestuffs of such aminoanthrapyrimidines or aminoanthraquinone inferior strength and af?nity for cellulosic ?bers, enzacridones. Amongst the aminoanthra quinones l-aminoanthraquinone and 2-amino 10 that these dyestu?s are devoid of any value. In contradistinction to this the present dyestu?s in anthraquinone may be mentioned and especially which Z-amino-anthraquinone is present as com aminoanthraquinones containing further subs ponent show good affinity and strength. As com tituents such as alkoxy (methoxy) or acylamino pared with the corresponding dyestu?s made groups, wherein the acyl residue may be derived from l:5-anthraquinonedicarboxylic acids and 15 from an aliphatic (e. g. acetic) aromatic (e. g. vattable amines the dyestuffs of the present in benzoic and substituted benzoic) or heterocyclic vention are quite generally distinguished by much (e. g. pyridinecarboxylic) acid, and halogen improved affinity and fastness to light and atoms such asychlorine or bromine. strength. This list of compounds is not limitative but The following examples illustrate the invention only illustrates the invention. Further vattable 20 but are not intended to limit it in any way, the amino-compounds not belonging to the anthra parts being by weight: quinone series may be used, such as amino-sub stitution products of indigo, thioindigo, pyrene Example 1 quinone, dibenzpyrenequinone as well as similar 13 parts of 1:9.5:l0-anthradithiazole-2:6-di compounds, There too substituents as are per 25 carboxylic acid chloride of the formula missible in vat dyestuffs may be present. In several instances such vattable compounds may be used which, for instance in ortho-posi tion to an amino group, contain at least one sub stituent which gives rise to formation of a hetero 30 cyclic ring. Such substituents are for instance the hydroXyl-, mercapto-, nitro- or amino groups as well as halogen atoms. According to the particular conditions oxazole-, thiazole- and imidazol-rings may be formed immediately fol 35 and 800 parts of dry ortho-dichlorobenzene are lowing the reaction with the carboxylic acids or heated to 150-160“ C. while stirring and mixed at this temperature with a hot solution of 23 parts their functional derivatives, or these rings may of 1-amino-5-benzoylaminoanthraquinone in 400 be formed in a separate step, according to gen erally known methods. parts of ortho-dichlorobenzene. The formation For carrying out the reaction with vattable 40 of dyestuff is complete after 2 hours’ stirring at compounds containing amino groups, the car the boil. The crystallized dyestu? is suction-?l boxylic acids mentioned above are used prefer tered in the heat, Washed with ortho-dichloro benzene and alcohol and dried. The dyestuff ably in form of their functional derivatives, ca; which is obtained in very good yield is a yellow pable of reaction, i. e. as acid halides or acid amides. The reaction may be carried out in in 45 powder dissolving in concentrated sulfuric acid different dispersing or dissolving agents, partic to a red solution and dyeing cotton from a yel ularly those having a high boiling point, such as low-olive vat strong reddish yellow tints having very good fastness properties. chlorobenzene, dichlorobenzenes, or nitrobenzene, When substituting l-amino-ll-benzoylaminow at elevated temperatures for instance at the boiling point of such indifferent solvents. In cer 50 anthraquinone for the l-amino-5-benzoylamino anthraquinone there is obtained a red powder by tain instances room temperature or a slightly the same method of working which dissolves in raised temperature may be more suitable. Ac cording to known methods agents capable of bind concentrated sulfuric acid to a red solution and dyes cotton from a yellow-olive vat red-orange ing acid, agents capable of eliminating ammonia or catalytically active agents may be used. The 65 tints having good fastness properties. The 1 : 9,5 : 10-anthradithiazole-2 : G-dicarboxylic addition of tertiary bases such as pyridine to the acid chloride used in this example has been pre reaction medium has proved to be of particular advantage in many instances. Ifdichlorides of pared as follows: dicarboxylic acids are used the proportions of the >__._ reagents are preferably so chosen that all the carboxylic acid groups enter into reaction. The products of the present invention may also be obtained in a somewhat different way by re 16b acting the corresponding carboxylic acid amides , with vattable compounds containing an ex changeable halogen atom. l8.2-5 parts of 1:5-dichloroanthraquinone-2:6 dicarboXylic acid, 16.5 parts of sulfur, 110 parts of crystallized sodium sul?de and~290 parts of ammonia of 12 per cent strength are heated in an autoclave provided with a stirrer for 8 hours to 95-105“ C. When cold the content of the autoclave is suction-?ltered, the ?lter residue is dissolved in 600 parts of boiling water, the solu tion is ?ltered and the disodium salt of the The products of the present invention are vat l : 9,5: IO-anthradithiaZole-Z : S-dicarboxylic acid dyestu?s and may be used accordingly for dyeing is salted out from the ?ltrate with common salt. and printing the most diverse ?bers of animal or vegetable origin, such as wool, silk and leather, 70 It is suction-?ltered, washed with a saturated solution of common salt, the ?lter cake is boiled but especially cotton, hemp, rayon and staple ?bers from regenerated cellulose as well as mix tures of the aforementioned ?bers. They may further be converted according to known meth ods into leuco sulfuric acid esters. with water with addition of some animal charcoal, the solution is ?ltered and the 129,5:10-anthra dithiazole-Z:G-dicarboxylic acid is precipitated 75 from the ?ltrate with hydrochloric acid. After 24085259 5 ?ltering, washing and drying a, yellow-green crystalline powder is obtained in good‘yield which does not melt below 450° C. _ > 11.8 parts of 1:9,5:IO-anthradithiazdle-Z:6-Cli , 6 . a 1 '(N) -2-benzacridone 4-.amino-1': Q-anthrapyrim idine'there is obtained a yellow-brown powder which dyes cotton from a yellow-olive vat yellow shades. carboxylic acid are heated to boiling during 1 5 ' Example 4 hour with 12 parts of thionylchloride and ‘530 19.5 parts of 1:9,5:IO-anthradithiazole-Z:6-di parts of dry ortho-dichlorobenzene. After dis carboxylic acid chloride are heated to 150~160° C. tilling 65 parts of the mixture--the unconsumed thionylchloride being thereby removed—it is suc with 1300 parts of dry trichlorobenzene, while tion-?ltered while hot and the ?ltrate is allowed 10 stirring. and mixed at this temperature with a’ hot solution of 25.5 parts of l-mercapto-2-amino to cool. The 1:9,5:lo-anthradithiazolea:6-di anthraq-uinone in 650'parts of trichlorobenzene. carboxylic acid chloride crystallizes in greenish The splitting off of hydrochloric acid and water yellow laminae melting at 323-325° C. after ?l tering, washing and drying. is complete’ after stirring for 2 hours. The pre cipitated dyestuff is suction-?ltered in the heat, Example 2 Washed with trichlorobenzene and alcohol and dried. A :brown powder is thus obtained which 13 parts of 159,5:10-anthraditlnazole-2:6~di carboxylic acid chloride and '800 parts of dry dissolves in concentrated sulfuric acid 'to a red solution and dyes cotton from a yellow-olive vat ortho-dichlorobenzene are heated to 150-160° C. 20 orange-brown shades. while stirring and mixed at this temperature with The dyestuffs .can be puri?ed as‘ follows: a hot solution of 14.9 parts of a-amino-anthra 2.5 parts of dyestuf.F powder are dissolved in 50 quinone in 400 parts of ortho-dichlorobenzene and parts of concentrated sulfuric acid.- This solu 10 parts of pyridine. The formation of dyestu? tion is poured onto ice, the precipitated dyestuff is complete after stirring for 2' hours at the boil. is suction-?ltered, washed with water and sus The precipitated dyestuif is suction-?ltered in the pended in 200 parts of water. 40 par-ts of sodium heat, washed with ortho-dichlorobenzene and hypochlorite solution of 14 per cent. strength are alcohol and dried. The dyestu? so obtained is a added and stirring is continued for 1/2 hour at yellow powder dissolving in concentrated sulfuric boiling temperature. The dyestuff thus becomes acid with a red solution and dyeing cotton from a orange-"red. It is suction-?ltered, washed and yellow-olive vat strong yellow tints. dried. It dyes cotton orange-brown shades of When using the equivalent quantity of l-amino greater purity than the crude product. G-chloranthraquinone or I-amino-5-methoxy anthraquinone instead of m-aminoanthraquinone, there are obtained dyestuffs which dye cotton from The dyestuif has probably the following con stitution: . ‘ a yellow-olive vat also yellow tints. When substituting ?-aminoanthraquinone for the u-aminoanthraquinone there is obtained a greenish yellow powder which dissolves in concen trated sulfuric acid to a red solution and dyes cot ton from an orange-brown vat strong greenish 40 yellow tints. Example 3 13 parts of 1:9,5:IO-anthradithiazole-Z:6-di carboxylic acid chloride and J700 parts of dry 7 Example 5 nitroberrzene are heated whilestirring to ‘ISO-160° C. and mixed at this temperature with a hot 13 parts of 4: l0;8:9-anthradithiazole-l:5-di solution of 22.7 grams of 4-aminoanthraquinone 1(N) :Z-IbenZacridQne in 700 parts of nitrobenzene 50 and 10 parts of pyridine. The precipitated dye stuff is suction-?ltered after two hours’ .stirring at boiling temperature, washed with nitro-ben zene and alcohol and dried. carboxylic acid chloride of the formula It is a dark olive powder of the formula 55 C10 and. 800 parts of dry ortho-dichlorobenzene are heated to 150—160° C. while stirring and mixed at this temperature with a hot solution of 23 parts of l - amino-5-fbenzoylaminoanthraquinone in 400 parts ‘of ortho-dichlorobenzene. The formation of .dyestuif is complete after stirring for 2 hours at ISO-160° C. The dyestuff is suction-?ltered in the heat, the residue is washed with ortho dichlorobenzene and alcohol and dried. The dye stuff which is obtained in very good yield is a yel low powder dissolving in .concentrated sulfuric acid to a. red solution and dyeing cotton from 70 dissolving in concentrated sulfuric acid to a red solution and dyeing cotton from an olive-brown vat olive shades. ' When using instead of 4-aminoanthraquinone a red-brown vat yellow shades. When substituting 1-amino-4-rbenzoylaminoan thraquinone for the 1-amino-5-benzoylaminoan thraquinone there is obtained a red powder dis solving in concentrated sulfuric acid to a red so lution and dyeing cotton from a violet-brown vat red-orange shades. , . 2,408,259 7 8 zoylaminoanthraquinone, as described in Efrain When using the equivalent quantity of 1- or 2~ amino-anthraquinone instead of l-aminoe5 benzoylamino~anthraquinonc there are obtained dyestu?s dyeing cotton more greenish shades. ple 5. The dyestuii obtained is a brown powder dissolving in concentrated sulfuric acid to a red solution and dyeing cotton from an olive-brown vat yellow-brown shades. The 4:19,8:9-anthradithiazole - 1:5 - dicarbox When substituting l—amino-5~benzoylarnino ylic acid chloride used in this example has been anthraquinone for the l-amino-a-benzoylamino anthraquinone there is obtained a brown powder prepared in analogous manner like the above de scribed 1:9,5:10~anthradithiazole-2:6 - dicarboX dissolving in sulfuric acid to a red-brown solu~ ylic acid chloride from 4:8-dichloroanthraqui none-1:5-dicarboxylic acid. From dichlerobem 10 tion and dyeing cotton from an olive-brown vat brownish yellow shades. zene it is obtained in ?uorescent greenish yel Example 8 low needles. The 4:10,8:9-anthradithiazole l:5~dicarboxylic acid formed as intermediate 1 ‘part of the dyestuff obtained according to product is a yellow-green powder melting at 370° Example 1 (cf. paragraph 1) is suspended in 100 C. with decomposition. parts of water with addition of 4 parts by volume of caustic soda solution of 36° Bé. and the sus Example 6 pension is vatted with 2 parts of sodium hydro 13 parts of di-(N)—rnethyl-1:9;5:iO-anthra~ dipyraoole-Z16-dicarboXylic acid chloride of the sul?te at about 50° C. This stock vat is added to a dye-bath which contains 3 parts by volume 20 of caustic soda solution of 36° Bé.‘ as well as 1 part of sodium hydrosul?te in 2000 parts of water. 100 parts of cotton are entered at 40° C., 25 30 parts of common salt are added after 15 min utes and dyeing is continued at ail-45° C. for further 415 minutes. The cotton-is squeezed out, oxidized on the air, rinsed, acidi?ed in usual manner, rinsed again and soaped at the boil. The cotton is dyed'fast reddish yellow shades. are caused to react at about 150° C. with 15 parts of Laminoanthraquinone in ortho-dichloroben 30 zene, as described in Example 5. The dyestuif thus obtained is a yellow-brown powder dissolv ing in concentrated sulfuric acid to a red solu~ tion and dyeing cotton from an orange-brown vat yellowish orange shades. When substituting 2-a1ninoanthraquinone for What we claim is: 1. A vat dyestufl of the formula wherein R1 stands for the radical of a compound selected from the group consisting of 1:95:10 anthradithiazole and 1 : 9,5 : lil-anthradipyrazole, the respective —CO-— groups being severally at the l-aminoanthraquinone there is obtained a tached to the two terminal benzene rings of the yellow powder dissolving in sulfuric acid to a radical R1, and each R2 stands for the same yel1ow~red solution and dyeing cotton from an radical of a vattable compound of the anthra 40 orange~brown vat strong yellow shades. quinone series. The di- (N) -methyl-1:9,5:lO-anthradipyrazole 2. A vat dyestu? of the formula 2:6-dicarboxylic acid chloride used in this ex ample has been prepared as follows: i—‘l /\ 11 parts of 1:5-dichloroanthraouinone-2:6 dicarboxylic acid, 66 parts of pyridine and 6.6 a‘ ' parts of methylhydrazine of 80 per cent. strength are heated in an autoclave provided with a Rz-NH-O o c O—NH—"R2 \lQl stirrer for 15 hours to 120-125” C. After cooling the content of the autoclave is suction-?ltered and washed with pyridine. The filter residue is 50 wherein each R2 stands for the same radical of a vattable compound of the anthraquinone series. boi‘ed up with dilute caustic soda solution and 3. A vat dyestuff of the formula animal charcoal, the solution is ?ltered and the di-(N) ~methyl - 119,5:10 - anthradipyrazole-2:6 dicarboxylic acid formed is precipitated with hy drochloric acid. When ?ltered, washed and dried 55 it represents a yellow-orange powder dissolving in sulfuric acid to a green-yellow solution and melting above 320° C. with decomposition. For the purpose of converting the compound into the acid chloride '7 parts of the acid are 60 heated to boiling for 1/2 hour with a parts oi CH3 thionyl chloride and 400 parts of dry ortho~di~ chlorobenzene, while stirring. After distilling wherein each R2 stands for the same radical of 40 parts of the mixture the solution is suction’ a vattable compound of the anthraquinone series. iiltered while hot and the ?ltrate is allowed to 65 It. A vat dystnff of the formula cool. The di-(N) -methyl - 1:9,5z10 - anthradi pyrazole-2:G-dicarboxylic acid chloride is crys tallized in yellow-orange needles which, after wherein R1 stands for the radical. of a com ?ltering, washing and drying melt above 360° C. 70 pound selected from the group consisting of with decomposition. 1 :9,5 : lil-anthradithiazole and 129,5:10-anthra Example 7 dipyrazole, the respective -CO—- groups being severally attached to the two terminal benzene 13 parts of di-(N) -methyl-1:9,5:lO-anthradi rings of the radical R1, and each R2 stands for pyrazole - 2:6 - dicarboxylic acid chloride are 75 the same anthraquinone radical. caused to react with 23 parts of l-amino-‘l-ben 2,408,259 ' 10 5. _The compound of the formula 8. A process for the manufacture of vat dye stuff, which comprises reacting a dicarboxylic acid halide selected from the group consisting of 35 1:9,5z10 - anthradithiazole dicarboxylic S——N 0100 acid 7 C 0 Cl halides and '1 : 9,5 : IO-anthradipyrazole dicarbox ylic acid halides containing the respective acid halide groups severally ‘ attached to the two terminal benzene rings, with two molecular pro portions of an amino substitution product of ya vat N—S 40 table compound of the anthraquinone series. 9. A process for the manufacture of a vat dye stu?, which comprises reacting a dicarboxylic‘ acid halide selected from the group consisting of 45 1:9,5z10 - anthradithiazole dicarboxylic with two molecular proportions of Z-aminoan thraquinone. 12. A process for the manufacture of a vat dyestu?; which comprises reacting an anthra dithiazole dicarboxylic acid halide of the formula acid halides and 1:9,5:10-anthradipyrazo1e dicarbox ylic acid halides containing the respective acid halide groupsseverally attached to the two ter 010C 0 0 G1 minal benzene rings, with two molecular propor- 50 tions of an aminoanthraquinone. 10. A process for the manufacture of a vat dye-stuff, which com-prises reacting an anthra dithiazole dicarboxylic acid halide of the formula with two molecular proportions of 1-amino-5 _ benzcylaminoanthraquinone. 55 13.~ A process for the manufactureof a vat dyestuif, which comprises reacting an anthra dithiazole dicarboxylic acid halide of the formula S——N 010 C I C O'Cl ‘00 010C N—\S Y " ' 11. A process for the manufacture of a Vat dyestuff, which comprises reacting anv anthra dithiazole dicarboxylic acid halide of the formula 0001 Y with two molecular proportions of an amino anthraquinone. ll with two molecular proportions of l-amino-B ‘ chloro-anthraquinone. ' THEODOR HOLBRO. WALTER KERN. _ PAUL SUTTER."