Fiber-reactive Monoazo Kupferkomplexe.

The invention concerns copper complexes of fiber-reactive Monoazoverbindungen and procedures for its production. These complexes find use as reactive coloring materials in conventional Färbeund Druckverfahren.

The subject of the invention are l: L-Kupferkomplexe of the formula I 0 '' “° 0 N N R RK B “H HO3 S” g 1 1 and their salts, where g 1 for hydrogen, halogen, c1 -4AIkyl, C1-4AIkoxy, Carboxy or Sulfo, R3 for hydrogen or Sulfo; RD for hydrogen, Sulfo oder-NR2 - Zx, and RK for hydrogen, Sulfo or NHCO stand, where each remainder of R2 independently hydrogen, c1. - 4AIkyl or C2. - 4Hydroxyalkyl means, for t for 0 or 1, and each remainder Zx independently for Za or stands, where Za the remainder of the formula W1--Za means, where for hydrogen, chlorine or cyanogen stands for %, and which has two T2 the same meaning and each T2 stands for fluorine or chlorine; Shark fluorine or chlorine, and 2 W1/k! - “k - NR2-B1-NR - Nk_. _/N, --*NR2 - C2 _, IAlkylen n \.? - “7--k f k! _î N N-C2 - 4 alkyl NRi, --*N k. _/(SO3H) m or. /”--'k NR2 --N N k. /(S03H) m mean, where m stands for 0 or 1, and which marked N-atom with * to an C-atom of the Triazinringes is bound, B1 for C2. - 6AIkylen; - C2 _3 AIkylen-Q-C2-3AIkylen, where Q -0oder - NR2 - means; by Hydroxy monosubstituted C -4AIkylen, --* (CH2) n " or - (CH2) for ñR4 R4 stands, where n 0 or a number of 1 to 4, R4 hydrogen, C1-4AIkyl, C1-4AIkoxy, Carboxy or CSU] fo mean, and which with * C-atom marked to the NR2 - group is bound, which at the C-atom - [is bound riazinringes; under the condition that at least one of RD and RK means a Zx-containing remainder, in which Za for it stands; H F or RD and RK, if g 1 hydrogen or Sullo means, for - NR2-Zy stand, where both Zy have the same meaning and each Zy for e.g. or for CI ù stand, wor, for n Y Y a unsubstituierte or substituted amino group, --W1 - E.g. or - NR2 - W2 - SO2 - X meant, where W1 and R2 are defined as above, W2 for an aliphatic or aromatic bridge member, which further unsubstituiert or substituted is, or for an aliphatic bridge member, which through - (3oder - NR2 -, and X für-CH=CH2 oder-CH2 CH2 is interrupted --[X stand, where T× Hydroxy or a remainder split offable under alkaline conditions means; and, N F e.g. stands for 3 for a Pyrimidinylrest, which contains an unstable Fluoroder chlorine substituent under the condition that everyone e.g. another meaning than N hat.

H F if nothing else is indicated, can in a connection of the formula I each alkyl, Alkoxy or alkyls linear or to be branched out. In a hydroxysubstituierten A] of kyloder group of alkyls, which is bound at nitrogen, the hydroxy group preferably is at an C-atom, which is bound to this nitrogen atom not directly. In each alkyl chain, which is interrupted by -0oder - NR2 - and is bound to an N-atom, -0oder - NR2 - is preferentially at an C-atom, not directly to this N-atom bound ist.

Has] ogen as substituent of a Phenylrestes meant prefer F] uor, chlorine or bromine, in particular Chlor.

G 1 stands preferentially for Ria as hydrogen, chlorine, methyl, Methoxy, Carboxy or Sulfo; more prefers for g 1 b than hydrogen or CSU] fo.

R2 meant prefers R2a, whereby each R2a independently for hydrogen, methyl, ethyl or 2-Hydroxyäthy] stands; more prefers R2b, which means independently hydrogen or methyl; in particular each R2 Wasserstoff.<br means/> Shark stands usually preferentially for Chlor.

R4 stands preferentially for R4a as hydrogen, methyl, Methoxy, Carboxy or Sulfo; more prefers for R4b than hydrogen or Sulfo.

B1 meant prefers B1 A as C2-3Aikylen, - CH2 CH2 --O-CH2 CH2 -, - CH2 CH2 - NR2b-CH2 CH2 -, by Hydroxy monosubstituted C3-4A] kylen, or - (CH2) n7 R4a where n " for 0 or 1 stands; more prefers Blb than C2-3AIkylen, - CH2 CH2 - NH-CH2 CH2 -, - CH2 CHCH2 - or OH particularly preferentially stands for B1 for B1 C than - CH2CH2, - CH2 CH2 CH2 -, - *CH CHoder - CH2 C CH2 -, I 1 CH3 OH R4b where with * marked C-atom itself to the NR2 - group rules, those bound to an C-atom in the Triazinring ist.

W1 meant prefers Wla as/"" k - NRz A-Bz. - Æ2 • -, - N n, k_. /or /--k /--k -- 2b-CH2CH2-N /N- --*N jN-CH2CH2-Æ2b, /---k, N R2 b k__jN -- (S03H) M. /----x N R2 OE --Nk. _jN' 1003H) m RST /---k more prefers W1 b than - NR2 b-B1 b-NR2 more boder - NNk_. _/Za stands preferentially for Za' than remainder of the formula T1, F where Ti' hydrogen or chlorine bedeutet.

; in particular W1 C als-NH-B1 C-NH-.

Zx stands preferentially for Zx " as Za " or the more preferentially stands it for Zx " than Za' or or CI N W1a--- Za' W 1 b--“Za” in particular preferentially stands it for Zx” as or CI F H F one for Y defined unsubstituierte or substituted amino group is preferentially - NR5 R6, where R5 hydrogen, c1. - 4AIkyl or by Hydroxy, cyanogen or Sulfo monosubstituted C2--4Alkyl, and R6 hydrogen, c1--4AIkyl, by Hydroxy, cyanogen or Sulfo of mûnosubstituiertes C2--4AIkyl; Phenyl or Phenyl, which carries or two substituents from the row a chlorine, c1 -.4AIkyl, C -4AIkoxy and Sulfo; Phenyl (c1--4alkyl) or Phenyl (c1 --4alkyl), its Phenylring or two substituents from the row chlorine, c1--4AIkyl, c1--4AIkoxy and Sulfo carry; or - NRsR6 Piperidino or Morpholino bedeuten.

More preferentially stands for Y than amino group for - NRsaRöa, where R5a hydrogen, methyl, Ä.thyl or 2-Hydroxyäthyl, and Röa hydrogen, methyl, Athyl, 2-Hydroxyäthyl, Pheny] or by or two substituents Phenyl substituted from the row methyl and Sulfo; or - NR5aRöa Morpholino bedeuten.

W2 as aliphatic bridge member meant prefers being further unsubstituiert a linear or branched C2-sAIkylenrest, that is or substituted can preferably by Hydroxy or - OSO3 H; or the C2. - 8AIkylenrest knows through - Ooder - NR2 - interrupted sein.

W2 as aromatic bridge member is prefers if necessary by Sulfo or Carboxy of substituted 1,3oder 1,4-Phenylenrest.

W2 meant prefers W2a as - (cri, CH3 CH3 - CH2íHCH2, - CH2 CHz-NR2 b-CH2 CH2 - or -- OS03H R4b where the linkage in the Phenylenrest decay p-constantly is bound and with * marked C-atom to the NR2-Gruppe ist.

More preferentially stands for W2 for W2 b than - (0H2) 2 -4oder R4b where the linkage in the Phenylenrest p-constantly decay ist.

Tx as group split offable under alkaline conditions means for example - OSO3 H, chlorine, bromine, - OPO3H2, - SSO3H, - OCOCH3, - OCOC6 Hs or - OSO2CH3; usually preferentially Tx stands for OSO3 H.<br for Hydroxy or -/> X stands preferentially for Xa as - CH=CH2, - CH2 CH OH or --CH2 CH2 OSO3 H; more prefers for Xb than - CH=CH2 or - CH2 CH2 OSO3 H; in particular prefers for Xt as - CH2 CH2 OSO3 H.

Everyone is e.g. prefers Zb' and corresponds to one of the formulas” ù, \ _ _ < and CI F CN CI F H H it is more preferential e.g. " than remainder of N CI NF or N CI F CN CI Y meant prefers Ya than - NRsRs, - W1 A-e.g. " or - NR2 a-W2 a-SO2 - Xa; more prefers Yb than - NR5aRöa, - W1 b-e.g. " or - NR2b-W2 b-SO2 - Xb; and in particular Yc prefers as - W1 C-e.g. " or - NH-W2b-SO2-Xc.

6 Zy meant Zy' prefers as e.g. " or CI Ya more prefers Zy " as Zb' or in particular Zy'" than Zb'" or CI Yc preferred connections of the formula I corresponds to the formulas la to ID and salts of it:

Ou B. N' N. 1 As P3 R N 3 7 R1a Ia where R7 hydrogen or Sulfo and Z Cl N-- or A NF H F 1 H F mean; Ib Zx' R2 bN--company II I II B - F---T-NICO-- “I where the two remainders of Zx” same or different be can and are preferably alike, and from those at least means the remainder; /cu Oo' O HOfS 5 Td where the two remainders of Zygleich sind.

In the ring A von Verbindungen of the formula la are Ria preferentially in 5-Stellung and the remainder - NR2a-Z prefers in 3-Stellung or also, if Ria hydrogen means, in 4-Stellung; if one of the remainders of R3 and R7 stands for hydrogen and the other one for Sulfo, then this Sulfogruppe is preferably in Ste] lung 6 of the ring B binds; if R3 and R7 mean both Sullo, then the two Sulfogruppen are preferential in the positions 6 and 8 gebunden.

More preferentially than connections of the formula la are such, where (1) Ria for g 1 b stands; (2) W1 A for W1 b stands; (3) Wla for W1 C stands; (4) R2 A for R2 b stands, (5) R2 A for hydrogen stands; (6) such from (1) to (5), where Ria Sulfo is bound meant in position 5 and the Rest-NR2 A-z in 3-Stellung; {7) such of (6), where R3 hydrogen and R7 Sullo in 6-Stellung bedeuten.

In the preferential connections of the formula lb t is preferably 0, if Z stands for Cl N N=' N FF Wla N H F. If R3 hydrogen means, t is preferably 0 and the remainder - NR2 A-z preferably is in position 6 or 7; if R3 stands for Sullo in 6-Stellung, Z means preferentially RST and the group of Z basic remainder is preferentially in 8-Stellung.

Still more preferentially than connections of the formula lb are such, where (1) W1 A for Wlb stands; (2) W1 A for Wlc stands; (3) R2 A for R2b stands; (4) such from (1) to (3), where R2 A hydrogen bedeutet.

In the preferential connections of the formula IC the substituents are preferentially in the following positions of the rings A and B:

a) If g 1 b hydrogen means, is - NR2 b-Zx " preferably in position 3 or 4; b) if g 1 b Sulfo in position 5 means, then is - NR2 b-Zx " preferably in position 3; preferentially Rlb Sullo continues to mean; c) if R3 for hydrogen stands, is preferentially in 6oder 7-Stellung bound the group of Zx " basic remainder and for t is prefers O; d) if R3 for Sulfo in 6-Stellung stands, is t prefers 1 and the group Z×'" basic remainder, in which Zx'" for Za' is located, preferably is in 8-Stellung.

Still more preferentially than connections of the formula IC are such, where (1) of each R2 b for hydrogen stands; (2) Rlb Sulfo meant in 5-Stellung; (3) such of (1) or (2), where both remainders of Zx stand " for Zx "; (4) such of (3), where both Zx stand " for R3 for hydrogen and t for 0 and - NR2b Zx'" in position 7 of the ring B bind ist.

In the preferential connections of the formula ID preferentially as follows is the arrangement of the substituents in the rings A and B:

The Sulfogruppe and the remainder - NR2b-Zy " are in the positions 3 and 5 of the ring A, whereby the Sulfogruppe is bound still more preferentially in position 5; if R3 Sulfo means, then this is in 5oder 6-Stellung, still more preferentially in position 6 of the ring B and the remainder - NR2b-Zy " is in 8-Stellung; or if R3 hydrogen means, is - NR2b-Zy " in position 6 or 7 of the ring B.

Still more preferentially than connections of the formula ID are such, where (1) both Zy'" for Zy'" stands and is alike; (2) of each R2b hydrogen bedeutet.

The condition of the cation of the Sulfogruppen and if necessary additionally existing Carboxygruppen in l: L-Kupferkomplexen of the formula I, if these are present in Salzform, does not represent a critical factor, but it can concern any not chromophores cation usual in the chemistry of reactive coloring materials. A condition participates that the appropriate salts the condition of the water solubility erfüllen.

Examples of suitable cations are alkali metal ions or unsubstituierte or substituted ammonium ions, as for example lithium, sodium, potassium, ammonium, mono, Di, Triund Tetramethylammonium, tri ethyl ammonium and mono, Diund Triäthanolammonium.

Preferential cations are the alkali metal ions and ammonium, preferentially of it particularly are Natrium.

Generally the cations of the Sulfogruppen can be and if necessary Carboxygruppen same or different and a mixture from the above-mentioned cations represent in a connection of the formula 1, i.e. the connection can also in mixed Salzform vorliegen.

The l: L-Kupferkomplexe of the formula I or mixtures of it are manufactured according to invention by one (i) 1 mol of a connection of the formula IL or III RD H HOsS g 1 R7 II C g 1 Rk III where g 1, R-S and R7 as above are defined, Bd for - NR2 - H or and Rkfür W1-H F HO or L_ N [-. /t “NR2 --H W1-H stand, where R2, W1, shark and t have above meaning, with at least 1 mol of 2,4,6-Trifluorpyrimidin condensed; or (ii) 1 mol of a connection of the formula IV, g 1 Rk IV where g 1, R3, RD and Rk as are defined, with at least 1 above mol of 2,4,6-Trifluorpyrimidin and at least 1 mol of a connection Za-Hal, where Za is defined as above and shark stands for fluorine or chlorine, converts or 1 mol of a connection of the formula V H-R2N V g 1 where g 1, R2 and R3 are defined as, with at least 2 above mol of a connection Zy-Hal, where Zy is defined as above and shark stands for fluorine or chlorine, umsetzt.

The conversions of a Aminoverbindung with a halogen connection become favourable in case of the one-sided condensation at ambient temperature to weakly increased temperature and in case of the reciprocal condensation between 10 and 60°C as well as at a preferential pH of 6-7 vorgenommen.

The condensation with a connection Zy-ha [can in a classification reaction or also, if Zy replaced one with Y Chlortriazinylrest meant, over several stages erfolgen.

The isolation of the connections of the formula I can take place in actually well-known way; e.g. the connections can by usual salting out with alkali metal salts from the reaction mixture solitaryly, filtered off and (in the vacuum) at increased temperature dried werden.

As a function of Reaktionsund isolation conditions a connection of the formula I is received as free acid or preferentially in Salzform or as mixed salt and contains then for example or several of the cations specified above. Salts or mixed salts can be manufactured in addition, on the basis of the free acid in actually usual way and in reverse or it can also an actually usual Umsalzung made werden.

Each remainder of Za according to the formula where “1 " 1 hydrogen, cyanogen or chlorine, and T2 fluorine or chlorine mean, and also each remainder e.g., which carries a not fixed Fluoroder chlorine substituent, can occur, in two isomers forms, whereby the not fixed Fluoroder either in position 2 or in position 6 binds chlorine substituent ist.

Generally it is preferential using the reaultierenden coloring material mixtures in such a way as] che without an isolating is made into the individual isomers. However if an isomer isolating should be desired, then this can according to actually usual methods erfolgen.

The parent compounds of the formulas II, III, IV and V as well as the connections Za-shark and Zy-Hal are either well-known or can similarly to well-known methods from appropriate well-known parent compounds by actually usual reactions such as Diazotierung and clutch, oxidative or demethylierende Kupferung and/or condensation reactions received werden.

The connections of the formula I and mixtures of it represent reactive coloring materials; they are suitable for coloring or printing on more hydroxygruppenoder nitrogenous organic substrates. As if preferential substrates are to call leathers and synthetic materials, which from natural or synthetic PP and in particular from natural or regenerated cellulose, as cotton, viscose rayon or Zellwolle exist or these contained. Usually preferential substrate is textile material, that from Baumwo {le exists or these enthält.

The connections of the formula I can be inserted into dye liquors or into Druckpasten after all Färbeoder Druckvertahren common for reactive coloring materials. After the batchwise exhaustion in the temperature range by 30-100°C, in particular with 50-60°C and/or 80-00°C is colored, whereby a Flottenverhä [tnis (substrate to fleet) from 1:6 to 1:30, more prefers from 1:10 to 1:20 assigned wird.

The connections in accordance with the invention know the same class, which comparable dyeing characteristics are used e.g. concerning general genuinenesses, taking off value etc. to possess, as single coloring material or because of their good combinability also as combination element with other reactive coloring materials. The received combination colouring shows just as good genuinenesses as the colouring with Einzelfarbstoff.

11 with the connections of the formula I will receive good Ausziehund of fixing values. The not fixed coloring material portion can be washed easily. The received colouring and pressures show good light fastness like also wet light fastness. As well as they exhibit additionally good wet authenticity characteristics e.g. regarding wash, water, Seewasserund Schweissechtheit and have good stability in relation to oxidative influences as opposite chloric water, Hypochloritbleiche, peroxide-bleach opposite perborathaltigen Waschmitteln.

The following examples serve the illustration of the invention. If nothing else is indicated, parts parts by weight and per cent weight percentage mean in the examples; the temperatures are in centigrades angegeben.

Example 1 of 78 parts in usual way of the manufactured copper complex of the formula CI T HO3 S SO H SO, H are solved neutrally in 700 parts water. One gives 14.7 parts to 2,4,6-Trifluorpyrimidin to the solution and agitates with 20-30% to no free amino group is more provable. During the reaction the freed acid with 20%iger sodium carbonate solution on pH 6-7 is blunted. The received coloring material, which corresponds to the formula (indicated as free acid) CI SOeH H F, filtered off with sodium chloride ausgesalzen, and dried in the vacuum with 50°. It results in violet colouring and pressures, the good genuinenesses on cotton exhibits and is betändig against oxidative Einflüsse.

Example of 2 58.1 parts of the Aminoazokomplexes of the formula was manufactured, jc O - ““O H N 8 s0 H SO3H similarly to actually usual method, in 1000 parts water is solved, whereby a neutral solution (pH 7) is received. Into this solution 16.1 parts 2,4,6-Trifluorpyrimidin are dripped, whereby by steady additive of 15%iger sodium carbonate solution a pH of 6,5-7,0 einge12 RST will hold. After terminated condensation the reaction mixture on ambient temperature becomes abgekühlt.

The formed coloring material filtered off with sodium chloride ausgesalzen, and dried in the vacuum with 50°. It corresponds to the formula (aforementioned as free acid) F N HN. L ..

F H SOsH and results in ruby-red colouring on cellulose material and in particular on cotton. These colouring shows very good Echtheitseigenschaften.

Examples 3-51 similar to the method described in example 1 or 2 know further l under employment of appropriate parent compounds: L-Kupferkomplexe of the formula I to be manufactured, which is arranged in the following tables 1-3. The structural formula applicable for the individual tables is initially in each case the table concerned aforementioned, in which the symbols defines sind.

In the tables 1 and 3 is under the column - Wxdas with * marked N-atom to an C-atom of the Triazinringes gebunden.

With the coloring materials of the examples 3-51 can substrates, which consist of cellulose fibers or contain these, and in particular are colored or printed on for textile material from cotton in ruby-red to violet tones after usual Ausziehund printing processes. The received colouring and pressures on cotton are well lichtund wet genuine and steady opposite oxidative Einflüssen.

13 table 1/examples 3-20 connections of the formula (TI) o/1 u ° g 1 W1 TN H F position ex. No. RZ R7 R3 R2 - NR2 - - CR - (tl) 3 4 H H H 5-SOsH 6-SOs H H DO. H H DO. H H ó H DO. H H 7 3-C00H H H H 8 H 5-S03 H H CH 9 H DO. H do.

3-Ci DO. 6-SO3 H H IL H DO. DO. H 12 H DO. H H 13 3-COOH H H CH3 14 H 5-SO3 H H - CHzCH3 H DO. H H 16 3-S03 H H 6-S03 H H 3-C! 17 18 5-S03H H CH3 DO. 6-S03 H H 8 6 6 7 7 6 6 8 8 7 6 7 6 8 - NHCH2CHzCH2NHdo.

--t'NHCH2CHNHl CH do.

do.

do.

- NHCH2 HCH2NHOH do.

do.

do.

do.

do.

do.

- ZNHCH2CHNHI CH3 do.

19 H H DO. H H DO. H CH3 6 7 do.

- NHCH2CH2CH2NH14 RST table 2/examples 21-34 connections of the formula (T2) RI (T2) ex. No. RI R7 R3 position - NHCOR2 21 H 5-S03H O H 22 3-S03 H DO. H 0 23 DO. DO. H 0 24 H DO. 6-SO H 0 H DO. H 0 26 3-CI DO. H 0 H H H H H 6 7 8 7 6 27 3-SO3 H H 28 3-CHi 5-SO H 0 0 CH3 7 29 3-Ci DO. 6-SO3 H H DO. do.

31 3-S03 H DO. do.

32 H DO. do.

1 1 1 1 8 8 8 8 H H H CH3 4 3 3 4 33 3-S03 H do.

do.

8 do.

4 34 3-COOH do.

8 table 3/examples 35-51 connections of the formula (T3) [_ resound to q (T3) position ex. No. RZ R2 - NR= R7 q Hal - WzH H 4 S03 H 0 36 S03 H H 3 DO. 0 37 DO. CH3 3 H 0 38 DO. DO. 3 SO3 H 1 Cl 39 H H 4 DO. 1 c1 S03 H H 3 H I c1 41 DO. H 3 H 1 c1 42 DO. H 3 H 1 F 43 DO. H 3 H 1 c1 44 H H 4 SO H I c1 H CH3 3 DO. 1 Cl 46 H H 4 DO. 1 F 47 H H 4 DO. 1 c1 48 S03 H H 3 DO. 1 c1 49 DO. H 3 H I Cl DO. H 3 H 1 Cl 51 DO. - CH2 CH2 0H 3 H 1 Cl - NHCH2CH2CH2NHdo.

do.

--*NHCH2CHzCHzNCH3 do.

--îNHCH2CHNHI CH3 do.

do.

do.

- NHCH2? HCH2NHOH do.

do.

- N Ndo, 16 RST example of 52 51.6 parts in usual way of the manufactured Aminoazokomplexes of the formula OU “HOFS' H2N/N NHz H is solved neutrally IN SUCH A WAY in 1000 parts water. With 40-45° 34.5 parts 2,4,6-Trifluorpyrimidin are then course-dripped, whereby the pH is held by constant additive of 15%iger sodium carbonate solution between 6,5 and 7,0. After terminated condensation one leaves the reaction mixture cooling. The received coloring material, which forms] jcu. O,” “O F. __N HN. J. _N=N. L _. - Nù. F /---k T HO3 S”” “2-=í F H SOsH H F corresponds, with sodium chloride ausgesalzen, filtered off and in the vacuum with 50° dried. It colors cellulose material and in particular cotton in very genuine Rubinoltönen.

Example 53 59.6 Teífe of the Aminoazoverbíndung of the formula manufactured on üblíchem way (ìu - o HzN -- ìs HOs8 " S03 H SO3H are solved in 700 parts water and dripped with 15-20° to a suspension from 37 parts of Cyanurchlorid in 300 parts water, whereby the pH is held by constant additive of 15%iger sodium carbonate solution between 6,0 and 7,0. After terminated condensation one heats N-Äthyl-2-methylanilin up on 50-60° and adds at pH 6.5-7.5 then 29.5 parts. The reaction product filtered off with sodium chloride ausgesalzen, and dried in the vacuum with 50°. The received coloring material corresponds to the formula 17 CI H=CH, “O NH I Cl SO=H and results in on cellulose material and in particular cotton violet colouring. The colouring possesses very good Echtheitseigenschaften.

Examples 54-134 similar to the method described in example 52 or 53 know further l under employment of appropriate parent compounds: L-Kupferkomplexe of the formula I to be manufactured, which is arranged in the following tables 4 and 5. The complexes correspond to the formulas 0-4) and (T5).

The structural formula is initially in each case the applicable table aforementioned, in which the individual symbols defines sind.

in these two tables the symbols in the following meaning are used:

NF Z1 for H F N k/CI Z2 for N CN CI Z3 for NF CI F XT for - CH2 CH2 OSO3 H.

With the coloring materials of the examples 54-134 substrates, which from Cel] can do ulosefasern exist or this to be contained, and in particular textile material from cotton in ruby-red to violet tones after usual Ausziehund printing processes be colored or printed on. The received colouring and pressures on cotton are well lichtund wet genuine and steady opposite oxidative Einflüssen.

18 RST table 4/examples 54-69 connections of the formula (T4) /cu 0 o " --0 = YARD " - .i v - L - Jr g 1 where the two remainders of Za identically sind.

(T4) Position RI R3 position ex. No. Za R8 - NRs (position) (position) t - NHCOStellung RZ - NRz54 Zz H 3 5-S03 H H DO. H 3 DO. 6-S03 H 56 DO. CH3 3 DO. H 57 DO. H 4 H 6-S03 H 58 DO. H 4 H H 5g DO. H 3 5-SO3 H H 60 DO. H 4 H 6-S03 H 61 DO. H 3 5-SO3 H H 62 DO. H 3 DO. H 63 Z3 H 3 DO. H 64 Zz H 3 DO. H Z3 H 3 DO. H 66 Z2 H 3 DO. H 67 Z3 B 3 DO. 6-S03 H 68 Zz CH3 3 DO. do.

69 Z3 H 5 3-S0sH 5-SOsH o 0 0 0 0 o 1 I 1 0 0 0 0 0 0 0 8 6 7 H H H H CB3 do.

do.

H H H H H H H CH3 H 6 8 6 8 6 7 4 4 3 7 7 6 6 8 8 8 19 ùJ! i table 5/examples 70-134 connections of the formula (T5) cu oJJ o CI CI YT g 1 s where the two remainders of YT just like the two remainders of R2 position RI ex. No. YT R2 - *NR2 - (position) R3 (T5) VT identically sind.

Position - NR2 - CH3 --N-- H 3 5-S0zH I-- CH=CH3 CH3 71 --N-- H 3 do.

CHz S03H 72 --N-H, O H 3 do.

SO3H 73 DO. H 3 do.

74 DO. H 5 3-S0 H 6-S0 H H 8 6 --NH-- > --SO3 H H 3 5-SO3 H SO3H 76 --N'H SO3 H H 3 do.

77 --NI] 0 H 5 3-S0 H S03H 78 __NH NH_Zz H 3 5-S03 H SO3H 6-SO H 5-SO H table 5/continuation ex. No. Y position RZ RZ - *NR2 - (position) R3 position - NR2SO3H 79 --AH-- NH-Zz do.

H 5 3-S03 H H H 3 5-S03 H 6-S03 H SO3H 81 --NH-- NH-Z3 82 do.

83 do.

do.

CH3 3 DO. H H 3 DO. 6-S03 H 6 8 84 86 87 88 89 90 SO3H --NH NH-Z2 --NH --NH-Zz SO3H do.

do.

do.

do.

H 5 3-S03 H 5-S03 H H 3 5-S03 H 6-S03 H H 3 DO. H H 5 3-SO3 H H CH3 3 5-S03 H H H 3 DO. 6-S03 H H 5 3-S03 H 5-S03 H 7 6 8 8 91 92 SO3H do.

5-S03H H 3-S03H 6-S03 H 7 8 21 table 5/continuation ex. No. YT position RI R2 - *NR2 - (position) R3 position - NR293 - NH (CH=) 3 NH-ZI 94 do.

95 do.

96 do.

97 - NH (CH=) 3 NH-Z3 98 do.

99 do.

i00 do.

i01 - NH (CH2) 3 NH-Z2 H 3 5-SO H H CH 3 DO. H H 3 DO. 6-S03 H H 3 DO. 5-S03 H H 3 DO. H CH3 3 DO. H H 3 DO. H H 5 3-S03 H 6-S03 H H 3 5-S03 H do.

7 6 8 8 7 6 6 8 8 102 - NHCH2? HNH-ZI CHs 103 do.

104 do.

105 - NHCH2CHNH-Z3 CH3 106 do.

107 do.

108 do.

109 - NHCH2 {HNH Zî CH3 ii0 - NHCH2 {HCH2NH-ZI OH 111 do.

112 do.

113 do.

114 - NHCH2CHCH2NH-Z3 OH 115 do.

116 do.

H H H H H CH3 H H H CH3 H H B H H 3 3 3 3 3 3 3 3 3 do.

DO. 6-S03 H 3-SO3H H 5-S03H H 3-S03H H 5-SO3H H DO. 6-S0sH DO. do.

do.

DO. H DO. 6-S03 H 3-SO3H do.

5-S03H H DO. 6-S03H 3-S03H do.

8 6 7 7 6 8 8 8 8 7 8 8 22 table 5/continuation ex. No. YT position RZ position R2 - *NR2 - (position) R3 - NR2 - 117 - NHCH2? HCH2NH-Z2 OH 118 - N N-Z2 k__/5-S03H 6-S03 H 8,119 /--k - N N-Zz k__/120 do.

121,122 do.

123 do.

124 - NH S02-XT 125 do.

126 do.

127 - NH - SO2 - XT 128 do.

129 do.

130 - NH (CH2) 3 S02 - Xw 131 do.

132 do.

133 do.

134 do.

DO. DO. 8 H 3 DO. do.

H 5 3-S03 H do.

5-S03H do.

H 5 3-SO3 H do.

H 3 5-SO3 H H H H CH3 3 3 3 3 3 3 3 do.

DO. 6-S03 H DO. H DO. H DO. H DO. 6-S03 H DO. H DO. H 3-S03H H 5-S03H H DO. 6-S03 H 3-S03H 5-S03 H H H H H H H H 8 7 7 6 8 7 7 7 6 8 8 23 in accordance with that managing described method will receive the coloring materials of the examples 1 to 134 as sodium salts. They can be manufactured as a function of selected Umsetzungsund isolation conditions or also by additional measures in actually well-known way in form free the acid or in another Salzform or Salzform also mixed and then for example or several of the cations specified further in the description enthalten.

How in the description introduction already mentions, the coloring materials of the managing examples place, which a Pydmidinylrest with not fixed Fluoroder chlorine substituents contain according to the formula F or CI of 6 N3, concerning this remainder of isomer mixtures; they contain the connection part, in which the not fixed Fluoroder chlorine substituent is in the Pyrimidindng in 2-Stellung, beside the appropriate connection part, where the substituent itself in 6-Stellung befindet.

The received mixtures of isomers coloring materials can be used in all conventional Färbeund printing process. An isolating into the individual isomers normally is unnötig.

Application possibilities of the descriptive coloring materials are following illustriert.

With 50° 10 parts of cotton fabrics (bleached) are registered to instruction for use A into a dyebath, which contains 0.3 parts of the coloring material from example of 2 and 8 parts Glauber's salt (calcined) in 100 parts entmineralisiertem water. After 30 minutes with 50° the additive of 0,4 parts soda (calcined) eñolgt, whereby the temperature is held with 50°. One increases then the temperature on 60° and Iässt during one hour with 60° further-colors. Subsequently, the colored material is rinsed 3 minutes in flowing cold water, then 3 minutes in flowing hot water. The colouring is cooking washed to entmineralisiertem water in presence of 0,25 parts of Marseiller soap during 15 minutes in 500 parts. After rinsing in flowing water (3 minutes hot) and the colouring in the drying furnace with approx. 70° is centrifuged is dried. One receives a ruby-red cotton colouring from very good genuinenesses, in particular high wet genuinenesses shows and is stable opposite oxidative Einflüssen.

Instruction for use B 10 parts cotton material (bleached) are added to a dyebath, which contains 5 parts Glauber's salt (calcined) in 100 parts entmineralisiertem water. The bath is heated within 10 minutes on 50°, then 0.5 parts of the coloring material from example 2 are added. After further 30 minutes with 50° 1 part soda (calcined) is admitted, increased afterwards the temperature to 60° and then still 45 minutes long with 60° weitergefärbt.

The colored material is rinsed with flowing cold water, then with hot water and washed similar to as for regulation A aforementioned cooking. After rinsing and drying a ruby-red cotton colouring will receive, which the characteristics stated in regulation A besitzt.

On similar way as in the Vorschdften A and B descriptive can be used also the coloring materials of the examples 1, 3-52, 54-69 and 78-134 or appropriate coloring material mixtures for coloring. The received ruby-red to violet colouring possess good Echtheitseigenschaften.

Instruction for use C consisting of 1000 parts water, 20 parts Glauber's salt (calcined), 2.5 parts soda (calcined) and 1.0 parts of 1-nitrobenzolo-3-sulfonsaurem sodium 50 parts mercerisierte cotton are added to a dyebath. The bath is warmed up to 40°, then 1.0 parts of the coloring material from example 53 are added. Within 45 minutes the bath on 98° is heated up; twice after in each case minutes 20 parts Glauber's salt (calcined) are added. At the end of the 45 minutes still 7.5 parts soda (calcined) are added. Anschiessend is further-colored long cooking 45 to 60 minutes, then the colored material is removed from the dyebath, rinsed under flowing water hot and washed during minutes in 500 parts to entmineralisiertem water in presence of 0,25 parts of Marseiller soap cooking. After rinsing and drying one receives a violet cotton colouring with good Echtheiten.

24 instruction for use D of 1.0 parts of the Farbstoftes from example 53 is solved in 2000 parts water. 100 parts of cotton fabrics are admitted to the dyebath, the temperature is set within 10 minutes to 80 ". 30 minutes after the addition of 100 parts Glauber's salt (calcined) are added to the dyebath of parts soda (calcined). One Iässt during one hour with 80° further-colors. Subsequently, the colored material is removed from the dyebath, rinsed under flowing water first coldly, then hot and washed similar to as for regulation C aforementioned cooking. After rinsing and drying one receives a violet colouring with good Echtheiten.

On similar way as descriptive in the regulations C and D can be used also the coloring materials of the examples of 70-77 or appropriate coloring material mixtures for coloring cotton. Ruby-red to violet colouring are received, the good authenticity characteristics aufweisen.

Instruction for use E a Druckpaste with the components of 100 35O of 500 1000 parts of the coloring material from example of 2 parts urea Telle water Telle of a 4%igen Natriumalginatverdickung of parts of Natriumbicarbonat Telle altogether is applied on cotton material after the usual printing processes. The printed on material is absorbed 4-8 minutes with 102-104° and rinsed then coldly and hot. Subsequently, the fixed Baumwo is cooking washed] lmaterial (similar to regulation A) and dried. The received violet pressure shows good AIIgemeinechtheiten.

Similar to the regulation E also the coloring materials of the examples 1 and 3-134 or appropriate coloring material mixtures of printing on cotton can be used. In all cases ruby-red to violet pressures with good authenticity characteristics are received.