DE926976C - Process for the production of Kuepen dyes - Google Patents

Description

Process for Making Vat Dyes The invention relates to a process for the preparation of Aryl @ triaz, in-vat dyes.

A number of. 2-aryl-.4,6-dianthraquinonyl-am.i # notriazine: en produced, "-which vat dyes and many of which have good properties (cf. USA patents: tschrift 1 897428). Recently, an excellent process has been developed by which some of these vat dyes can be prepared and which comprises five steps. In the first stage, an aroyl chloride is reacted with dicyandiamide to form an aroyl, d, itcyand: iam: ids. This is hydrolyzed to the corresponding aroyl biuret, the ring is closed by means of alkali, so that a 2-aryl-d., 6-dioxytriazine (also known as aroylguanamide) is formed. This can then be converted into the corresponding 2-aryl-4, 6-dichlorotriazine using phosphorus pentachloride. This dichloro compound is condensed with aminoanthraquinones to form the final dye. The first four stages of the above synthesis are in the USA patents 2407161 and 2401599, in a publication by O str og owits ch (cf. Gazz. Chim. Ital., 62, 229 L19351) and in the USA mentioned at the beginning. U.S. Patent 1,897,428 . They can be represented by the following formula symbols. The above implementations, which are fairly general in nature; fail in a special case in which R is an o-oxy.aryl group. When trying to manufacture such compounds, side reactions occur and the triazine ring does not close. It had therefore hitherto been impossible to produce a 2-o-oxyarylltraz in and the anthrac'hinnonylamino colorants derived from it.

It has now been found that solefie compounds and in particular the 2-o-oxyarylrq., 6-dianthraquinonylamino derivatives of the formula can be produced. In the above formula, Ar is an o-arytane radical and Aq is an, a-anthradhainonyl radical: The new process comprises the preparation of a completely different compound, namely a 2-alkoxyaryl-q., 6-dianthraquinonylaminotriazine, of the following formula: In this formula, Alk means a lower alkyl group, ie one with fewer than 6 carbon atoms. These compounds can be prepared by the general methods mentioned above and described in the above patent specifications and in the publication. The alkoxy compounds can then be de-alkylated by a hydrogen halide with a molecular weight of more than 20, such as hydrogen chloride, hydrogen bromide or hydrogen iodide.

The ab, spakznä the alkyl group can under very different reaction conditions take place. It's an advantage; ' the invention that the method is not very specific Measures is bound. In general, it is desirable to use the alkoxyaryitric azine to be dispersed in an organic solvent and hydrogen halide vapors to pass through at elevated temperature while stirring vigorously. The implementation takes place turns out smoothly and gives a: high yield with no noticeable side reactions, except However, that acid-sensitive in the presence of under the real tion conditions Substituents him anthraquinone nucleus, such as. B. a-alkoxy groups, these also split off and a corresponding oxy-substituted dye: is created. The organic Solution @ smitte, 1 can be aromatic or aldphatis che and should not be advantageous be too volatile, so that the need for wasteful pressure equipment is avoided will. Typical organic solvents are chlorobenzene, xylenes, o-di-chlorobenzene, Nitrobenzene "Propylendichlarid, Tetrahydronaphthalin, r-Chlo @ rnaphthaJÜin, Tetrachloräthylen and d14 The conditions under which the dealkylation by means of the halogen aisiser, substance takes place are not tied to specific measures. The temperature can be En vary widely, although economic, I progressive reaction.s@speed normally cannot be achieved below about 80 °. From roo to 2oo ° excellent results obtained, although the solubility of the hydrogen halide by decreasing organic solvent at the higher temperatures, and temperatures in the middle of this range become common in practice preferred. 2oo ° is about the highest temperature to be used because it is too high Temperatures the tendency to decompose the starting material or the end product consists.

It is an advantage of the invention that the 2-o-alkoxyaryl-4, 6-diantbrachinonylamino-triazines do not need to be isolated. The dealkylation can take place in the same medium take place in which the condensation of the Dic'hlortriazins with the aminoanthraquinone takes place.

The conversion, through which the alkoxy compound is converted into the oxy compound is converted is moderately slow. - The length of time varies, of course the size of the batch, the effectiveness of the stirring, the temperature and others Factors such as are common in discontinuous processes. However, she is racing nibhts excessively and contributes itself. large approaches no more than a few Hours. The work performance of the device is therefore satisfactory.

Isolation of the final product presents little difficulty since, im essentially no side reactions occur and the product in! higher and good Purity. This eats somewhat surprising as the tri; azinrinng, sensitive to acidic reagents dealcoholization seems unusually stable. This only applies to the o-alkoxy.aryl compounds, since the reaction with the m- or p-alkoxy groups does not occur. It is unknown, why the o-alkoxyaryl compounds have this property of the straightforward Entalkyl.ierunig with Ha (liogenwas: to show substances, and the invention should by no means be carried out by any Theory about the anomalous behavior of the o-alkoxy group.

The alkoxy bonds can be made from. a large number of o-allzoxyaroylchloride-ids be produced. So z. B. use the chlorides of the following acids are: o-ani, s acid, o-ethoxybenzoic acid, 2-methoxy-3-naphthoic acid, o-propoxybenzoic acid, 4-chloro-2-methoxybenzoic acid, 5-B: rom-2-p: ropoxybenzoic acid, 4-methyl-2-methoxybenzoic acid, 5-Ni, tro-4-methyl-2-methoxybenzoic acid, i-llethoxy-2-naphthoic acid, 4-nitroi-m @ ethoxy-2-nap @ h, thoic acid, i-MethoxyphenanV, hren-2-ca, rboxylic acid (vg1. D u v a 11 and M o -settig, jou.rn. At the. Chem. Soc.6o, 24o9 [1938]), 3-Methoxyp'h-enant: hren-2-carbonic acid (cf. Gi1-man and Cook, journ. At the. Chem. Soc. 62, 2813 [194o]) and the like. The a-Aminoanthr.achinone, which are condensed with the dichlorotriazine do not only include unsubstituted substances a-Amimoanthraquinone, but also various substituted products, including a limited number of products fused ring systems and heterocyclic products. Typical connections are i-Aminoanthrachi @ non, 2-Methyli-am @ inoanth: rachinon, 4-Methyl-i-aminoantbrachinon, 6- methyl - i -aminoanthraquinone, 3 - bromi-aminoant'h! Rachinon, 5-chloro-i-aminoantihraquinone, 5-Be-nzoylamino-z-aminoanthrach @ inon, 4- and 5-Aminoant @ hrachinon-z (N), 2-bemzacriidone, 4- and 5-aminoanthraquinones-i (S), 2-thioxanthones, 4-aminoanthrapyrimidine, 4-A: mino-2, 3-benzanthraquinone and the like.

The 2-o-oxyaryl-.4., 6-anthraquinonyl: amiho-triaziiine prepared according to the invention represent a new range of vat dyes of various hues and excellent The introduction of the o-hydroxyl group results in a remarkable one Improvement of the properties of the dyes. First up are the shades in general more luminous and; compared to the unsubstituted preventions, there is one considerable hypsochromic shift. For example, the hydroxy group converts a reddish yellow color to a much purer and greener yellow. This hue shift has considerable practical value and [cannot be compared with normal Effects that are achieved by the introduction of hydroxyl groups, which usually have a bathochromic effect. It is not known why at the Tri.azine dyes according to the invention the effect of the hydroxyl group just that Opposite [of what eats normally obtained from: other types of coloring becomes, and the invention is not intended to be any particular in this regard Theory be limited.

The second advantageous property of the dyes according to the invention with the o-hydroxyl group there is a noticeable improvement in the lightfastness and washfastness. This again is quite different from dien Widku, na m, which otherwise by introduction of hydroxyl: groups can be achieved. Usually these groups lower the persistence especially against washing and cooking with soda. As with the abnormal one mentioned above Changing the color tone [here, too, it is not known why the hydroxyl groups in the case of the transnazin dyes according to the invention in such an unusual white.

A third advantage of the dyes of the invention [is their unusual chemical resistance with regard to a range of reaction conditions, which their conversion into other dyes even with the application of vigorous reaction conditions allowed. The compounds according to the invention therefore also constitute starting materials or intermediate products for further dye series and thus offer the vat dye chemist a wide field of work.

Although the present invention broadly encompasses any compounds falling within the general formula above, it has been found that a more limited group eats particularly noticeably. These compounds are represented by the following general formula. In the formula; which represents a preferred subgroup, K and Y are hydrogen or. Chlorine.

The invention should now be based on the following specific examples are explained in more detail. The parts are parts by weight, unless otherwise specified [is. Since some of the intermediate products are new, examples of their manufacture are given and also examples of the production of the final dyes themselves sirnd described. The formula: 1, deir of the compounds obtained are in part listed in the drawings.

Example i A slurry of 120 parts acetone and 21 TeHen Dicyandiamide is cooled to 5 to 10 ° and treated with 26.4 parts of potassium hydroxide. The mixture is stirred at o bis. 5 °, until the reaction has essentially ended, and then becomes the mixture cooled below o °. -It's getting to be a solution of 34.1 parts of o-methoxybenzoylchlo @ rsd: in i2o parts of acetone were added. The stirring is then continued until the reaction has come to the tooth temperature est. It is diluted with about iooo parts of Wasserex and slowly with about 14 parts Acetic acid acidified. The resulting o-methoxybenzoylidieyanide, diiamide is thorough stirred, filltrilerted, washed and air dried. It melts at around 186 '.

A mixture of 8o parts of o-methoxybenzoyldieyan @ gamid, 40o parts Water and 67 parts of concentrated hydrochloric acid are poured into milk while stirring Boiling heated under reflux and heated under reflux until the B_iuretbilidumg finishes eating. The slurry is then cooled to 0-5 ° and filtered. That o-Methoxybenzoyllbiuret is washed with very dilute hydrochloric acid and added to the Air dried. It melts at around 185o.

543 parts of o-methoxybenzoyblbiu, ret wIr: d dissolved in a solution of 30.2 parts of potassium hydroxide in 600 parts of water and stirred at room temperature until the ring closure is effected. The implementation is slower than in the two previous examples. The o-methoxybenzogtuanamide obtained is acidified by careful acidification with approximately 21 parts of vinegar and then cooled and filtered. It melts at around 25o °.

A mixture of 10 parts of o-methoxybenzoguanamnd, 21 parts of phosphorus: antachloride and 46 parts of phosphorus oxychloride are refluxed until the chlorination finished aest. The product is intestine in about Soo parts of a mixture of egg and poured water, stirred vigorously, filtered, washed and dried. It can purified by dissolving in benzene, filtering and evaporating to dryness. It melts at about i36 °.

A mixture of 128 parts of the obtained 2- (o-Methoxyp'henyll) -4, 6, di @ chl # ortri; azins, 223 parts of a-aminoanthraquinone and 100 parts of nitrobenzene is heated to 130 ° with stirring until the condensation anion has ended. Then it will be Allowed to cool to room temperature and filtered. The product (formula i on Table I) is washed with nitrobenzene and alcohol and dried at 60 °.

A slurry of 30 parts of this product of the formula i in 36o parts of nitrobenzene is heated to 135 ° with stirring. A vigorous stream of dry hydrochloric acid gas is passed through the mixture for a few minutes at intervals while the mixture is stirred and gradually heated to 200 °. The mixture is then cooled and filtered. The product (Formula 2 on Table I) is washed with nitrobenzene and alcohol and dried at 60 °. It is a very bright, greenish yellow with excellent persistence and high color intensity. It dyes both rayon and wool as well as cotton and can be made into a paste in the usual way with concentrated sulfuric acid.

Examples A mixture of 15 parts of o-methoxyphenyldiichlorotriazine and 25.3 parts of 3-chloro-i-aminoanthrachnnon in 26o parts of o-dichlorobenzene heated to 140 ° and stirred at this temperature until the condensation has ended est. The reaction mixture is then cooled and filtered. The reaction product is washed with o-dichlorobenzene and then rode alcohol. It will be in excellent Yield obtained. The product is demethylated in the following way.

46 parts of this reaction product become o-dichlorobenzene in 52o parts . Slurried, stirred and heated to 1q "0 ° and with a stream of dry Treated hydrogen bromide at this temperature until the decomposition caused .is. The mixture is then cooled and filtered. The product is treated with o-D.io'hlorbenzol and then washed with alcohol and water. It will be in excellent yield obtain. The product (formula 3 on panel I) dyes cotton and rayon bright greenish-yellow tones from a bright red-colored vat and shows an excellent one Resistance to light, chlorine and washing. The dye can be used in the usual Way from concentrated sulfuric acid to be divided into an acidic paste.

Similar results are obtained under the same reaction conditions obtained when a stream of hydrogen iodide is used in place of hydrogen bromide will.

Example 3 A mixture of 6.4 parts of o-methoxyphenyldichlorotriazine and 17.1 parts of 5-Benzoylaminoi-aminoamthraquinone in iSo parts of nitrobenzene -, vi @ rd stirred at 14o to 15o ° until the condensation is essentially complete. The resulting yellow slurry is cooled to room temperature and filtered. The reaction product is washed with nitrobenzene and then with alcohol and dried. A very high yield is achieved. The demethylation is carried out in the usual Way done. The resulting dye (formula 4 on panel II) turns orange-yellow Dyes with excellent resistance properties on cellulose fibers.

"Be.ispie14 4-Benzoylamino-i-amirnoanthrachimon and o-methoxyphenyl-diichlbrtri, azin are implemented according to the procedure of the previous example. The Demethylfüerung is as follows: io parts of the reaction product are dissolved in 13o parts of o-dichlorobenzene, the i part contains pyridine, slurried and heated with stirring to i 50 ° and treated at this temperature with a stream of dry hydrogen chloride, until dealkylation causes i, st. The mixture is witrd then cooled and filtered, the product with o-Dicihlorbenzol, Alkohot and. Water washed. A very high yield is achieved. The product (Formula 5 on Table II) gives red dyeings on cotton and: artificial silk from a pale brown vat. It shows excellent resistance to light, chlorine and washing. Example A mixture of 4.1 parts 1, 4-Di.ami: noanthradhinon-2-c2rboxyanth.ra lhinony # lami, d and i, i parts of o-methoxyphenyldidhloretri: azine in 50 parts of nitrobenzene-wiird Heated 14o to 150o to cause condensation, and then cooled and ' filtered. The demethylation is carried out with hydrogen chloride in nitrobenzene in the usual, white described above made. It becomes essentially theoretical Yield of dye (Formula '6 on Table. II) obtained from the cellulosic fibers dyes in gray-blue tones from a burgundy red vat.

Example 6 A mixture of 6.4 parts of o-methoxyphenyld-icb-llortri, azin and 13.6 parts of 3-Cli, lor-4-methyl-aminoanthrachi: non in 180 parts of nitrobenzene is heated to 140 to 150 ° and at. this temperatuir stirred until the condensation is finished. The resulting olive-yellow slurry is cooled and filtered. The product is washed with nitrobenzene and then with alcohol. It will be in exuberance Yield obtained. The demethylation is carried out by the method described above causes. The product (formula 7 on table III) gives yellow dyeings on cotton.

At, spie17 a mixture of 3.1 parts of 4 amino-Bz-3 # 5-dichloroanthraquinone-benzacridone and i part of o-methoxypbenyl dichlorotriazine in 3o parts of nitrobenzene is added with stirring heated to about 130 ° until the condensation is complete. The product will filtered and washed with nitrobenzene and then with alcohol. It would be excellent Yield obtained.

The En.tmethyl: ierung is by slurrying 2 parts of this Product in 35 parts of o-di-chlorobenzene b-ei 14o ° and treatment with a stream carried out from gaseous hydrogen bromide to complete demethylation. The product (Formula 8 on Table III) then filtered and washed. There is bright greenish-blue dyeings on cotton from a purple vat. example 8 A slurry of 8 parts 1, 4-diamino-2- (2, 3-anthrac'hi-nonthi, azolyl) -anth, rachinon in 180 parts of nitrobenzene! is at. i20 to 125 ° stirred until it thoroughly digested, and then with a solution of 2.1 parts of o-methoxyphenyldichlortriaz.in treated in 12 parts of nitrobenzene. The mixture is stirred at 130 to 140 °, to cause condensation, and cooled. The product is filtered and with nitrobenzene and alcohol -, wash. It is obtained in excellent yield. The demethylation is carried out by what was described in the previous bet games Procedure causes. The product (formula 9 on panel IV) gives greenish-blue colorations from a blue-violet vat.

Example 9 A mixture of 10.3 parts of o-Me, thoxyp @ he: nyldichlorotriazine, 2o, 6 parts of i-Am, ino, -4-chl-olranthraquinone and 31o parts of o-dichlorobenzo, l heated to 140 ° until condensation has essentially ended. The product is then cooled, filtered and washed with o-di, ie, lo.rbenzol and then with alcohol. The demethylation is carried out by that described in the previous examples Procedure causes. The dye (formula ro on panel IV) dyes cotton from orange-red Vat in yellow tones.

Example ro A mixture of 3i, 5 parts of dicyandiamide and 39.6 parts Potassium hydroxide in i45 parts of acetone is cooled to o to ro °, stirred, blis a flaky precipitate forms, and gradually with a solution of 55.2 parts of o, -Äthoxybenzoylclaori @ d treated in i20 parts of acetone. The mixture is diluted with water, acidified with about 37 parts of glacial acetic acid and filtered. Excellent yield is obtained. The obtained .o, Äthoxybenzoyldicya.ndiaimi, d schm, i.lz: t at about 236 °.

A single mixture of 61.2 parts of o-Ät @ hoxybenzoyldicy @ and, iamid, 39 parts of concentrated hydrochloric acid and 250 parts of water is refluxed to produce biuret. The α-ethoxyb, enzoylibiiu-ne, t obtained is cooled, filtered, washed and dried. It is obtained in good yield and melts around 2050.

54.5 parts of o-Äthoxybenzoylbi.u.ret are in a solution for a long time stirred by 34.2 parts of potassium hydroxide in 78o parts of water. The solution is then Acidified with 36.7 parts of egg, sle; sis @ i @ g, stirred vigorously and filtered. The received o-Ethoxyb, enzoguanamid is washed acid-free and dried. It will be .in excellent Leads received and diminished at about 246 ".

A mixture of 41 parts of o-ethoxybenzoguanamli, d, 195 parts of P @ ho @ sphoroxychlori, d and 73.5 parts of phosphorus pentach @ lo, ri, d w, irld refluxed until a clear solution is obtained. The solution is heated for another 1/2 hour and then in Poured ice water. The obtained o, -äthoxyphenyl-diiahlo @ rtri, azin is filtered, Washed thoroughly and dried at 60 °. It is made by dissolving in benzene, filtering and evaporating to dryness. It is obtained in good yield.

Ein-, MIschunig of 2.6 parts o.-Ät! Hoxyphlenyldiohlo.rtri; az; in and 4.5 parts i-Am @ ino, anth, rachlinon in 72 parts: Nitrobenzene is gradually: Ech heated to 130 ° and at held at this temperature until the condensation has ended. The 'product will. Removing cooled, filtered and washed with nitrobenzene. It is obtained in good yield. The de-ethylation is carried out by slurrying 2 parts of ore of this product in 35 parts of nitrobenzene and gradually increasing the temperature to 180 ° to 200 ° with simultaneous dilution with a stream of hydrogen chloride. The product (formula ii on panel V) is then cooled, filtered, washed and dried. It is identical to the product of example i. , Example ii 28 parts of 2-methoxy-5-chlorobenzoic acid are converted into the acid chloride in the usual way by treatment with thionylchlomide: the reaction is ended by gradual heating and subsequent removal of the excess thionylchlomidis under reduced pressure. The product formed is dissolved in 40 parts of acetone.

A mixture of 23.4 parts of DicyandÄam @ id, 136 parts. Acetone and 1.5 parts of water are cooled to 0 °, with 19.6 parts (pure base) Ka1, iumhydroxydfioaken treated, stirred thoroughly at -about o ° and with the aoetonic prepared above Solution of the 2-methoxy-5-dhlo, rbenzoyldüorids treated slowly. The resulting slurry is poured into ice water and slightly acidified with dilute sulfuric acid. The 2-methoxy-5-ch-lorb, enzoyl @ d @ icyandi.am: i.d is then filtered and acid-free washed. It is obtained in good yield and melts at ehva 220 ° with decomposition.

A solution of 3 parts of 99% sulfuric acid in 70 parts of water becomes 5 parts of the 2 - methoxy - 5 - chlorobenzoyldicyandiam @ i prepared above, ds r given, which was first arigefeurihtet with 12 parts of ethanol. The mix will then heated under reflux until the reaction has ended, and the alcohol is distilled off calmly. The 2-methoxy-5-dhloir #benzoylbiuret is cooled, filtered and with 6o ° dried. It is obtained in good yield, and melts below at about 198 ' Decomposition.

A mixture of 4.4 parts of the 2-methaxy-5-cWo @ rbenzoyrbduuret prepared above, 2.5 parts of Natri.umihy.d@roxycl and 50 parts of water are stirred until the ring closes took place and left overnight. The solution is filtered and weakly acidified with hydrochloric acid of 2.0 ° Be. The resulting slurry will cooled in an ice water bath and filtered. It will never keep a good yield. That 2-methoxy-5-ch! Larbenzo, guanvamide melts at about 25o ° with decomposition. -A mixture of 3.3 Teid @ en of the above prepared 2-methoxy-5-, chlorbenzoguanamids, 6.3 Ted @ len phosphorus pentachloride and 17 parts of P: hospho, ro @ xychlo, ri, d is under Heated to reflux, until the chlorination is complete, then in about 250 parts of ice and poured water and stirred for 1 hour. The 2-Met'hoxy-5-chlorophenyl-dichlortriazi @ n is filtered, washed and dried at 60 °. If desired, it can be purified by extraction with benzene and subsequent evaporation. It melts at about i56 °.

A mixture of 1.2 parts of the 2-methoxy-5-ohlo @ rp @ henyl-di: chlo @ rtriaz; ins, 1.9 parts of a-aminoanthradhinone and 36 parts of mitrobenzoil is: to 100 to 100 ° heated and stirred at this temperature until the condensation has ended, and filtered. The product (Formula 12 on Table V) is made with nitrobenzene and then with Alcohol washed and dried. It is well preserved.

A mixture of 1.6 parts of the product made above and 26 parts of o-dichlorobenzene is: heated to 140 ° and with a stream of dry Treated hydrogen bromide until demethylation is complete. The mix will cooled and filtered and the product (formula 13 on panel V) with o-D@ichlorbenzo.l , and then washed with alcohol. It is obtained in good yield. It colors in bright yellow tones from a wine-red vat.

Example 12, Eiire M, Dissolution of 1.4 parts of 2-methoxy-5-chloroph @@ enyl-, dichlorotriazine and 2.6 parts of i-amino-3-chloranthrachino @ n in 40 parts o-Didhloirbenzol - # vi: r @ d heated to i2o to 145 'until the condensation: causes is, .then cooled and filtered .. The product is washed with o-dichloro, rbenzene, Slurried in 40 parts of the same solvent and with the stream of dry Demethylated hydrogen bromide gas at a temperature of 14o to 15o °. The product (Formula 14 on Table VI) is cooled, filtered and treated with D; i @ chlomb @ enzo, l and Alcohol washed .. It stains in bright greenish-yellow tones.

Example 13 A milk: g of 24.4 parts of Diicyandsiannnd, 136 Share acetone, and. 1.5 parts of water are cooled to 0 ° and with 2o.2 parts of potassium hydroxide (my base) treated and stirred until the constitution is finished. Then at this temperature gradually .a solution of the acid chloride, which consists of 24.8 parts 2-112 @ ethoxy-5-methylb, euzoe @ acid by reaction with Tihionylchlo@r.i.d: on the usual Way prepared was added in 27 parts of acetone. After adding the acid chloride the slurry is stirred until .die Acyliemung is completed at 0 ° ', in ice water poured, weakly acidified with sulfuric acid and filtered. It becomes a good one Yield of 2-methoxy-5-methylbenzoyldicyand @ iam @ i, d obtained at about 2oo ° melts. 5 parts of the 2-methoxy-5-methylbenzoyldicyandiamide prepared above be with 8 dividers; Athanoil mixed into a paste with a solution of 3 Parts of 99% sulfuric acid in 70 parts of water-treated, to boiling, under reflux heated, the alcohol being distilled off, and at 98 '° heated, to effect the conversion into the biuret. The reaction mixture is then cooled and filtered. The 2-methoxy-5-methylben7oylbiuret obtained is mixed with cold water washed and dried at 60 °. It melts at about 199 ° with decomposition.

A solution of, 4.2 parts of 2-M-thOxy-5-methylbenzoyl bisuret and 2.5 Divide sodium hydroxide into parts of water. stirred until the ring ran out takes place, overnight at room temperature: ematur left, filtered with the bundle Hydrochloric acid weakly acidified. The resulting slurry is cooled and filtered. The 2-methoxy-5-methylbenzoguanamide obtained is washed with ice water and dried. It melts at around 238o.

A mixture of 3.3 parts of the 2-methoxy-5-m, e @ thylbenzogu: anami: ds prepared above and 45 parts of Phosp @ ho @ roxychlori, d is heated under reflux until the chlorination finished eating, cooled, poured into 300 parts of ice water and filtered. The received 2-Metho.xy-5-methylphenyl-di, chlo, rtriazin is: dried and can be extracted be cleaned with Beuzol. It melts at around 130 °.

A mixture of 1.3 parts of the 2-methoxy-5-methylphenyl-dichlorotriazine prepared above and 2 parts of a-aminoanthraquinone in 40 parts of nitrobenzene is at 100 to 10 ° stirred until condensation has ended and filtered. The product (Formula 15 on panel VI) is washed with nitrobenzene and then with alcohol. It will be in good Yield obtained.

A slurry of 1.6 parts of the product prepared above in 26 parts of o-dichlorobenzene is heated to 140 ° and with a stream of hydrogen bromide treated for demethylation. The slurry is then cooled and filtered. The product (Formula 16 on Table VI) is made with dichlorobenzene and then with alcohol washed and dried at 100 °. It gives bright yellow tints out of one wine-red vat. Example 14 A mixture of 43.7 parts of dicyandiamide in 40o parts Acetone and 4 parts of water are stirred, cooled to 0 °, with 40 parts of potassium hydroxide Treated of goo / oiger purity, stirred to obtain the potassium salt at 0 ° and gradually with 59.5 parts of 2-methoxy-3-naphthoy 1-chloride in 50 parts of acetone treated. The reaction is ended by additional stirring at 0 °. The mixture is then poured into 150 parts water, the 750 parts ice and 36 parts concentrated Contains sulfuric acid. The obtained 2-methoxy-3-naphthoyldicyandiamide is washed and dried. It is obtained in excellent yield. Its melting point is about 222 °.

A solution of 6 parts of 99% sulfuric acid in 14o parts of water becomes 10 parts of the 2-methoxy-3-naphthoyldicyandiamide prepared above, the had been moistened with 20 parts of alcohol. The resulting slurry is heated to reflux until biuret formation is complete, with the alcohol distilled off, and then cooled and filtered. It becomes 2-methoxy-3-naphthoylbiuret obtained in good yield.

A slurry of 4.8 parts of the 2-methoxy-3-naphthoylbiuret prepared above and 2.5 parts of sodium hydroxide in so parts of water is stirred until solution took place and then left to stand overnight. The solution is then filtered and weakly acidified by the careful addition of hydrochloric acid at 20 ° Be. The yellow 2-Methoxy-3-naphthoguanamide is filtered and dried at Sun to 60 °. It will obtained in good yield.

A mixture of 1.8 parts of the 2-methoxy-3-naphthoguanamide prepared above, 3.2 parts of phosphorus pentachloride and 34 parts of phosphorus oxychloride are used for chlorination heated to reflux, left to stand overnight and, with thorough stirring, in Poured ice water. The 2-methoxy-3-naphthyl-dichlorotriazine obtained is filtered, Washed with ice water and dried on Sun to 60 °. It melts at about 97 ° with decomposition.

A mixture of 1.5 parts of the 2-methoxy-3-naphthyl-dichlorotriazine prepared above, 2.2 parts of a-aminoanthraquinone and 3o parts of nitrobenzene are heated to 100 to 10 °, until the condensation has ended and filtered. The product (Formula 17 on blackboard VII) is washed with nitrobenzene and then with alcohol.

A mixture of 1.8 parts of the product obtained above (formula 17) in 26 parts of o-dichlorobenzene is stirred, heated to about i4o ° and with a Stream of dry hydrogen bromide treated until demethylation is complete is. The resulting thick slurry is filtered. The filter cake is with o-dichlorobenzene and then washed with alcohol and dried on sun to 6o °. the Yield is excellent. The product (Formula 18 on Table VII) is blowing. yellow coloring from a wine-red vat.

Example 15 A mixture of 24.4 parts of dicyandiamide, 136 parts Acetone and 1 "5 parts of water are cooled to 0 °, with 22.4 parts of potassium hydroxide flakes treated, stirred until the potassium salt is formed, and gradually with a solution treated by reacting 27.3 parts of 2, 4-dimethoxybenzoic acid in the in the usual manner with 21.4 parts of thionyl chloride, removal of the excess thionyl chloride prepared in vacuo and dissolving the resulting acid chloride in 3o parts of acetone had been.

The reaction mixture is stirred at about 0 ° to the reaction finish, and poured into ice water containing a little dilute sulfuric acid. the The solution is then weakly acidified and stirred. It'll be a good yield at 2, 4-Dimethoxybenzoyldicyandiamide achieved, which melts at about 220 ° with decomposition.

A mixture of fo parts of the 2,4-dimethoxybenzoyldicyandiamide prepared above, 12 parts of ethyl alcohol, 14o parts of water and 6 parts of 100% sulfuric acid is heated to 98 to 100 ° for the purpose of forming the biuret, while the alcohol is distilled off. The 2,4-dimethoxybenzoylbiuret obtained is then cooled, filtered and washed. It is obtained in good yield and melts at about 220 ° with decomposition.

A mixture of 8.3 parts of the 2,4-dimethoxybenzoyl biuret prepared above and 5 parts of sodium hydroxide in foö parts of water is used at temperatures up to about 40 ° stirred to end the ring closure. The solution is then filtered and that 2,4-Dimethoxybenzogu namide obtained precipitated by careful acidification. It is obtained in good yield and melts at about 254 ° with decomposition.

A mixture of 3.2 parts of the above-prepared 2,4-dimethoxybenz: oguanamids, 6.3 parts of phosphorus pentachloride and 25 parts of phosphorus oxychloride are added with stirring heated on the reflux condenser to stop the chlorination and then cooled. the The reaction mixture is poured into about 500 parts of ice and water and stirred thoroughly and filtered. There will be a good yield of 2,4-dimethoxyphenyl dichlorotriazine obtained, if desired by extraction with benzene and evaporation to dryness can be cleaned. The melting point is around 1710.

A mixture of 44 parts of the 2,4-dimethoxyphenyl-dichlorotriazine prepared above, 2.2 parts of a-aminoanthraquinone and 36 parts of nitrobenzene is stirred to iio heated to 1150 until condensation has ended. The product (formula ig on blackboard VIII) is filtered and washed with nitrobenzene and then with alcohol. It will obtained in good yield.

A slurry of 2.1 parts of the product prepared above . (Formula ig) in 26 parts of δ-dichlorobenzene is heated to about 140 'with stirring, until the demethylation of the o-alkoxy group is complete, with a current of dry hydrogen bromide is treated. The product (formula 2o on panel VIII) is then filtered and washed with o-dichlorobenzene and then with ethyl alcohol. It is obtained in excellent yield. It gives bright, yellow tints from a wine-red vat. In the formula given, the one in the o-position to the triazine ring Methoxy group indicated as demethylated. This is the most likely formula although it is also conceivable that the other methoxy group is demethylated.

Claims (4)

PATENT CLAIMS: i. Process for the preparation of vat dyes of the general formula where Ar is an o-arylene radical and 'Aq is an a-anthraquinonyl radical, characterized in that an alkoxyaryltriazine of the general formula where all denotes a lower alkyl radical with: a hydrogen halide with a molecular weight of over 2o is treated for the purpose of dealkylation. 2. Procedure according to claim i, characterized in that the alkoxyaryltriazine in an inert dispersed organic solvent and the hydrogen halide vapor through the Dispersion is passed at elevated temperature. 3. The method according to claim i or 2, characterized in that the dealkylation at a temperature between 8o and 2oo ° and preferably between foo and 2oo ° is carried out. 4. Procedure according to one of claims i to 3, characterized in that the alkoxyaryltriazine in situ by condensing the corresponding 2-aryl-4, 6-di.halogentriazines with Aminoanthraquinone is formed and the reaction product then with the hydrogen halide is treated.