BE628424A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



  New reactive dyes and their preparation *
The present invention relates to reactive dyes which can be fixed on textile fibers containing hydroxyl and amino groups. It also relates to the process for preparing these dyes.



   The Applicant has found that dyes which can be fixed on textile fibers containing $ hydroxyl and amino groups are obtained by reacting 1 mole of an organic dye corresponding to formula I
 EMI1.1
 in which D represents the residue of an organic dye,
R 'represents hydrogen or a residue

 <Desc / Clms Page number 2>

 lower alkyl and n denotes a positive integer equal to b 2 or,
 EMI2.1
 better, at 1,

   with n mole! of a compound capable of introducing the residue corresponding to formula II
 EMI2.2
 
 EMI2.3
 in which at least one of the symbols XI and X2 tt'tpr4S- represents a fluorine atom and the other
 EMI2.4
 hydrogna or any substituent except the nitro group, and
R represents an optionally substituted amino group or a lower alkyl resto, reaction which results in a dye corresponding to general formula III
 EMI2.5
 
 EMI2.6
 / M <t, .su "AL *" "J" ". '" "."' * .L, amrs4f in which 1, RI and 'n "propc9 do the formula 1 and Xy.t 1 \ have the same 1- cations indicated in, with regard to formula II,

   or by synthesizing the dyes from constituents at least one of which contains the residue of formula II linked by an amino group,
In formulas 1 and III the symbol
 EMI2.7
 D represents more specifically the rent of a component easily accessible to industry, for

 <Desc / Clms Page number 3>

 
 EMI3.1
 example the remainder of an optionally metallized mono- or polyazoyqus dye, of an anthxaquinon3c # u dye, of a nitro dye or of a dye of the phthalocyanine series.



   When D represents the residue of an azo dye, it is preferably the residue of an azo dye.
 EMI3.2
 monoazorque dye, metallic or not, belonging to the berzne.axo series. benzene, benzene-azo-naphthalGno, benzene-azo-pyrazolei or naphthol-azo-naphthalene, or a disazo dye of the benzene-azo series.



  (-87.0 '"b on :: & ny benzine / bu naphthalene-azo-benzene-azo-benzene, metalized or not. When D is the residue of an anthraquinone dye, it is preferably of a 1-amino- residue
 EMI3.3
 4-Phenylamino-, -4-diphenylamino-, -4-alkyl-phenylamino- or -4-halogenophenylamino-anthraquinonic. When D denotes the residue of a dye belonging to the phthalocyanine series, it is preferably a residue of a phthalocyanine-sulfoniquo alkylamide or of optionally halogenated phthalocyanine-sulfoniquo arylamido,
The dyes mentioned may contain the substituents customary in dyes.

   As substitutes of the genus, there will be mentioned halogens such as fluorine, chlorine and bromine, branched or unbranched alkyl groups, such as methyl, ethyl and pro groups.
 EMI3.4
 pyl, butyl and amyl, cycloalkyl groups, such as cyclopentyl and cyclohexyl groups, aralkyl groups, such as benzyl and phenethye groups, eth groups, such as methoxy, ethoxy, ring * hexyloxy, benzyloxy and phenoxy, acid groups carboxylic and tallow acids, with acyl groups
 EMI3.5
 amino, such as acetylamino or bonzoellaminop

 <Desc / Clms Page number 4>

 
 EMI4.1
 back groups carb4mY1Q.

   nitrogen-containing nitrogen, also nitro, amino and hydroxyl groups; R 'represents, for example, the methyl group or the ethyl group; but it is advantageous that it is hydrogen.



   When one of the symbols X1 and X2 represents in formulas II and III, any substituent ..ci / is for example a halogen, such as fluorine, chlorine or bromine. It is advantageous that X denotes fluorine, and the other hydrogen. The symbol R represents the primary amino group or a secondary or tertiary amino group of the aliphatic serial,
 EMI4.2
 cycloaliphatic, ar allphatiquo or aromatic, In tertiary amino residues, the two substituents carried by nitrogen can also be linked to each other and thus form with the nitrogen atom, a heterocycle, for example a ring piperidino or morpholino.



  R is preferably a tertiary amino group of the aliphatic series, for example a dimethylamino, diethylamino group or a methylethylamino group.



   As a lower alkyl residue, R represents, for example, the methyl, ethyl, propyl,
 EMI4.3
 1sopropylet n-, sec. or wrong. butyl; the methyl residue and the ethyl residue are preferred alkyls.



   Formulo 1 organic dyes contain groups of the formula
 EMI4.4
 
 EMI4.5
 either on Io dye skeleton 11.m & mo, or suz de? substituting external $ and in the latter case by

 <Desc / Clms Page number 5>

   example on the benzene ring of bonzoyl group.
 EMI5.1
 amino or phenylamine groups
As amine dyes which can be used according to the invention, there may be mentioned, for example, smine-
 EMI5.2
 4nthraquinonose such as' amlno-4- (m-oup-.m1no. Ph4ny1amtno) -anthrqulnonol and their soldos lultn1.

   What, Me m1no.rhtloQynJn "f CQmmQ 104 product * do vondontotion do phtaUeyanlne-fculfoehieruM ut dialkyibne-diaminat or arylne-diaminûa evontuollo- ment 8u1fon6,., and especially azo dyes * aminds to neck amino. acyler mcît in the component of copulation, roof, -pluis ôvantâgu8omont | dan # the component of dinzotatîono
Azo dyes of formula IV
 EMI5.3
 are particularly interesting azo dyes, In this formula A represents a residue from the benzine, di-phenyl or naphthalene series, optionally carrying other substituents, B represents the residue of a component copulated in a neighboring position relative to a hydroxyl or amino group, and n has the meaning given in connection with the formula I.

   au / Preferably A and B together contain / less deu.
 EMI5.4
 sulfoniquga acid groups, These azole dyes are cbtlent for example by coupling acyl, amino-phenyl., diphenyl- or -naphthyl-diazotques compounds optionally

 <Desc / Clms Page number 6>

 
 EMI6.1
 8u1fon & 8 ou dos composas nltroaryldltzotqu8 "therefore for example one coupling the diadic of a ge4tyl. Amino-aniline, of a 4-acetylAmino-4'-bm1no-1.1 '- diphenylo or of a nitranilinee ccraposantos which little. Will 4vontuol1tmnt carry tulfonic acid groups, nvoc de * fompooantQ * do nppwlattnn UIUtl1 ..



  Oorftblo1 do oopulor on a vnla1nQ poottlon of a hydroxyl group or nmino # for example with copu back. lante of the bontènoo series of mothballs, of pyrazolongo of pyraxolone-imine or of aceto-oc'tylanilide, ot then saponifying the acylamino group or reducing the nitro group or amino group, or pulping a diazotque compound with uno
 EMI6.2
 coupling component containing amino groups
 EMI6.3
 acylabloop for example with an aminobonzene, an amino-
 EMI6.4
 naphthalene or an amino-naphthol coupling in a neighboring position with respect to the amino group, also with
 EMI6.5
 an aminoaryl-pyraxolone, an aminoâryl-pyrazolonolmine or an acetoacdtylamînoaryl.ide, or with their sulfonîquoa acids.



  Metallized andno-azofc dyes; corresponding to formula V
 EMI6.6
 
 EMI6.7
 are also interesting starting bodies.
 EMI6.8
 In this formula t
 EMI6.9
 A represents a residue of the benzene or naphthalene series optionally carrying other substituents,

 <Desc / Clms Page number 7>

 
B represents the remainder of a component capable of co- pulorization in a position close to a hydroxyl group,
Designates me a heavy metal with atomic number 24 'h
29, a metal which can still be linked by coordination to other complexing agents,
Y represents oxygen or the COO- group, and n has the meaning given in connection with the formula I.



   This amino-azo dye preferably contains at least two sulfonic acid groups.



     Such omino dyes can be obtained. azotquos metallized for example by coupling acylamino- or nltrophenyl- or -naphthyl-diazo compounds optionally sulphonated and advantageously bearing, in position ortho relative to the diazo group, a hydroxyl, alkoxy or carboxyl group, with coupling components usual, coupling by position close to a hydroxylo group, for example with dos phenols, naphthols, pyrazolonoq or dos acdtoacétylarylides, as well as the sulfonic acids of your compounds, or one coupling dosed with usual aromatic diazo compounds, more particularly dos compound. , its o-hydroxy-,

       optionally sulphonated o-alkoxy- or o-carboxy-aryldiazo, with coupling components coupling in a position adjacent to a hydroxyl group and containing an amine group no optionally acyl, for example with an amino- or acylamino-naphthol . - or an amino acid. or acylamino-naphthol-sulfonic acid.



  After hydrolysis of the acylamino group or reduction of the nitro group to an amino group, the amino-azo compounds obtained are transformed into their complexed using compounds capable of yielding chromium,

 <Desc / Clms Page number 8>

 cobalt or, preferably, copper as a pre-ounce need for an oxidizing agent. To saturate this possible co-ordinating valences, the metal can be attached to other compounds, possibly compounds having the character of a dye, for example water, certain tertiary amines, such as here.
 EMI8.1
 pyridino # or another otot-dihydroxy dye. or o-hydroxy-o'-carboxy-azo! quQ.



  As compounds which can be used according to the
 EMI8.2
 vention and which are able to introduce the remainder corresponding to formula II
 EMI8.3
 one can consider above all the acid halides,. for example chlorides or bromides, such as
 EMI8.4
 chlorides or bromides of 2- or 4¯fluoro-5-sulfamyl-bonzoyles, do 2 ... fluoro-4-ohloro- or 4 ... fluoro- '2-chloro-5-sulfamyl' <bonzoyles optionally substituted - killed with nitrogen, chlorides' or bromides of 2 * or 4-fluoro - alkY18ulfonyl-bohzoYle., chlorides. or 2 'fluoro-4'-chloro- or 4-fluoro- bromides.

   ohloro - alky18ulfonYl..bonzoylo8, They are obtained by reacting the corresponding fluoro- or fluoro-chloto-bonzolques acids with chloro-sulfonic acid and by transforming the acido-sulfonic chloride thus obtained into the desired sulfonamide , or reducing the sulfonic acid chloruro to sulfiniquo acid and alkylating

 <Desc / Clms Page number 9>

 
 EMI9.1
 this last counted alkylxulfonyliquo sought, and finally by transforming Io group QQrboxyl1quQ on croups hêlôgdno-carbonylo, by 0) (011'11'1 p with the starter of an ohQ .. rum of phosphorus or chloride of th1nnyl0.



  The side faction mina1 avoo having ¯nylntlon .4pto to introduce the r $ t & du to1'- muh 11, Ionic laws reitetite Aont lioluhha d ni Ilonui Ott ettactudu on OQIlitton 4qi4atinoe 4yontu () Uo. Mounted in the presence of (e.). 9 buffers As for the water soluble or insoluble compounds, it is advantageous to react them in organic solvents. Inertot, for example in lower alcnnols, of ketone. lnferences or lower fatty acid amides), if necessary, prescribe atot bases of tortiaircep like dialkylnilinot, which play the role of acid acceptors. In order to develop a premature change of reactive fluorine, we gave the preferred do $ condi- tiont douco4f to a pi-1 which could bind from 4 to 10 at most, and at temperatures as low as possible.

   For the isolation and for the exchange of reaction products It is also indicated
 EMI9.2
 ror under gifted conditions.



  The operating variant conforming to the definition, according to which the dye of do
 EMI9.3
 formult III by reaction of components of which at least one contains the resto of formula II, can be envi.



  "6.u, r.t ... o.'tJ: I ag6ef for the synthesis of azolquos dyes by cc-
 EMI9.4
 pulation of an aromatic diazo compound with a coupling component.



  To obtain reactive dyes in accordance with the invention in this way, a compound

 <Desc / Clms Page number 10>

 
 EMI10.1
 diazo answers, \ ot 14 formula 9! Sndr '"llt VI
 EMI10.2
   (as long as
 EMI10.3
 A fQpr4a'mtq un renie do In <5rio du btnxttno, end of ph6nvl0 or naphthalene, which may possibly rOf "other beginners and XI # X and R have the meanings indicated above, with regard to formula II , with a component capable of copulating in a neighboring position with respect to a hydroxyl or amine group,

   copulation which leads to an azo dye corresponding to the
 EMI10.4
 formula çM $ n <5ralo VII
 EMI10.5
 in which 8 represents the remainder of the coupling component in a position adjacent to a hydroxyl or amino group,
 EMI10.6
 ot optionally transforming the dye obtained into a metallized complex by ovoc treatment of $ agents capable of yielding heavy metals,
As disazo compounds of formula VI, which can be used in this variant, diazotized condensation products can be used.
 EMI10.7
 obtained from an optionally sulfonated aryUne-diamino and a halogenuro ùh f luoroaulfamyl-bonzoyl

 <Desc / Clms Page number 11>

 optionally substituted% nitrogen or a halide
 EMI11.1
 fluaro-alkylsulfonyl-benzoylo,

   bodies which have been described above, so for example fluorosulfamyl- or fluoro-alkylsulfonyl-benzoylamino-phenyl-f -diphenyl- or -naphthyl-diazo compounds The components to be copulated with these diazo compounds can be copulation components customary in azole dyes, for example glues of the benzene series, such as phenols or phenol ethers, of the naphthalene series, such as naphthols and amino-naphthols
 EMI11.2
 èveuollemont'sulfonéàp also pyrinzolono4 and pyrazolono-Imines as well as dos actoa atyl arylides,
Another embodiment of the process according to the invention consists in coupling a diazo compound A-N2 + optionally carrying a '-' very substituent.

   with a coupling component corresponding to general formula VIII
 EMI11.3
 in which
 EMI11.4
 X, 3 and R have the meanings 1diqu8 for formula II and B represents the remainder of a suitable component.
 EMI11.5
 h copia on fonitlor 11nu from a hydroxylo or amlno group,, tto utonir a dye corresponding to the general formula IX

 <Desc / Clms Page number 12>

 
 EMI12.1
 in which 8 has the meaning indicated in connection with formula VIII, and '
 EMI12.2
 A represents a remainder of the bonz4niquop / diphé series.

   nyl or naphthalene, optionally carrying other substituents., and optionally converting the dye obtained into a metallized complex by treatment with an agent capable of yielding a heavy metal *
As a diazo compound, it is then possible to use diazoteos aromatic amines customary in azo dyes, for example phenyl- compounds,
 EMI12.3
 d, phn- au raphtyl.diaxaruos possibly sulfonated,
In formula VIII the benzoyl residue is linked by an amino group to the component of copula-
 EMI12.4
 tion, for example to an am1nonaphthol-eulfon1quo acid, such as 1.am acid, ra.

    hydxaxynapttainu..6 eu '*' 4t6 d, aui'aniqu, mira.hydraxynaphthalna6 acid. oulfonique or 2-amino-'5-'hydroxynaphthalene '<' 7'-8Ul "tonic acid, or an optionally sulfonated am1nQaryl.pyrazolone or -pyrazolone-imine or an acoaatyl-amina-arylide.



  Another form of r <'' H.6.) Tlon of the px-
 EMI12.5
 <nt!.! uCt "d. ' r; onû1t.t.t. to copultr a C (tfl \ r) (! j 111-10 \ '; 1 \ 111 r! ait., 1 ir.rf;: a ,. VI
 EMI12.6
 

 <Desc / Clms Page number 13>

 with a copulation component responding% to formula VIII
 EMI13.1
 to obtain a nitrogenous dye correspond to the general formula x
 EMI13.2
 and optionally converting azo co-dye into one of the metallized complexes by treating with agents capable of ceding heavy metals. The meaning of the symbols contained in these three formulas will be found, as well as the examples of the components corresponding to formulas VI ot VIII, in the description of the previous operating variants.



   In the last three modes of operation described, the coupling is carried out in a slightly acidic to slightly alkaline medium, by the conventional methods.



   When the azo dyes prepared in the operating variants in question are metal ** readable, they are transformed by known methods, with agents capable of yielding a metal (by oxomplo 'chroma, cobalt or, preferably, copper) , optionally in the presence of an oxidizing agent, in the corresponding metal complex 1 the metal can then fix other complexing agents, for example those of the type mentioned above

 <Desc / Clms Page number 14>

 
It is necessary to carry out the copulation as well as the metallization in soft conditions, that is
 EMI14.1
 that is to say by avoiding high pH * and at such low tompératur * s back,

  as possible
As other amino coluiants * used according to the invention, mention will be made, for example, of amino-
 EMI14.2
 anthraquinonao as doo 1 amino-4 <(tn- or p - amino- ph4nylamino) -anthtoqulnonQ8 and their sulfonic acids, dos minophthalocyon1quo ', as dot produced from conden.

   sation obtained from phthalocyanine-sullochloruro and dt nlkyUmo-diam1nl) $ or atylene-diamitios 4von- tually sulphonated
The dyes in accordance with the invention which are insoluble in water may find
 EMI14.3
 For use as dispersion pigments or dyes, however, preferred are dyes containing water-solubilizing groups, more particularly those which have two to five sulfonic acid groups. These dyes dissolve very well in water in the form of their alkaline acids. They are suitable for
 EMI14.4
 dyeing of ceUuloxic matter, such as cotton, regenerated cellulose, jute, ramie and hemp, or also of fibrous materials containing polyamides.

   by oxomplo natural polyamides t comma la
 EMI14.5
 141ne or solot or palym1dG.ynth6tiquo., Conimes Nylon * These materials are tointed with the dyes according to the invention by known methods; collas which contain * hydroxylic groups are tointow for example by foulardago with an aleauno telution of dye, followed by a vaporisago or by drying by
 EMI14.6
 dry heat or by prolonged storage60 at room temperature

 <Desc / Clms Page number 15>

 
The fibers of natural polyamides are dyed in a hot slightly acidic bath, for example acidified with acetic acid, in the presence. adjuvants improving the unison of the dye and possibly in the presence of salts, such as sodium chloride or sulphate.

   Suitable adjuvants are, for example, condensation products which are obtained by heating acidos grains containing at least 8 carbon atoms with 1 to 3 moles of lower alkanolamines containing together at least 3 alkanol groups per fatty acid, which condensation occurs. done with removal of about 1 mol of water per mol of alkanolamine. In the case of synthetic polyamide fibers, it is advisable to carry out the dyeing in a hot acid bath, then to rinse and to treat subsequently in a boiling alkaline bath.



   The dyestuffs according to the invention have a relatively high reactivity; nevertheless, for technical applications, they are sufficiently stable in printing pastes or alkaline dye baths. Realistic dyes with these dyes are very pure and have good light fastness as well as excellent wet fastness properties. They are very resistant to alkaline or acid hydrolysing agents.



   The following examples illustrate the present invention without in any way limiting its scope, EXAMPLE 1:
 EMI15.1
 

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 EMI16.1
 18p8 parts of Act 1 3¯diaminobenzene-4¯sulfonic acid with sodium carbonate are dissolved in 400 parts of water, pH 4.0-4.5, and the solution cooled to 0-5. C. At this temperature, 25.0 parts of sodium chloride are added dropwise over 1 hour.
 EMI16.2
 2-Fluoro-5-methylsulfonyl-1-benzoylo is dissolved in 100 parts of acetone and the pH of the reaction mixture is maintained at 4.0-4.5 by simultaneous addition of a sodium carbonate solution.

   As soon as the reaction is
 EMI16.3
 When finished, the reaction product is precipitated by adding hydrochloric acid (30%), it is separated by filtration, it is dissolved again in 300 parts of water
 EMI16.4
 and diazotized to b 5-10 ° C with 25 parts of chlo acid. 30% hydrochloric acid and 6.9 parts sodium nitrite. The suspension of the diazo compound is poured into a solution.
 EMI16.5
 tion of such sodium 28 # 9 parts of 1- (2'-chloro-5 - sulFophenyl) .- 3-methyl5-pyxazolona in 200 parts of water and 40 parts of sodium acetate * When coupling is complete, the new dye with sodium chloride, separated by filtration, washed with dilute sodium chloride solution and dried at 50-60 C under reduced pressure.

   It comes in the form of a yellow powder which dissolves in water with a yellowish green color.



   The new dye dyes cotton, regenerated cellulose, jute, ramie, hemp, wool, silk and nylon, by the usual processes for reactive dyes, in pure shades, yellow, wet solids and soidos in the light.



   2-fluoro-5- chloride is obtained.

 <Desc / Clms Page number 17>

 
 EMI17.1
 mdthyllulfonyl - '. bonzoyl0 by reacting 2-tluorQ -'- bantOqu ,. with the acid chloro8ulfon1quQ pjur obtain the chloride of the acid -fluora1 crrbaxy.nxrc tesulfonic, n transforming this dorniot on ot1do aul- f.niqua by reaction with the sulfito do sodium and ntdthylant the 8ulfinic acid with the 1oduro do methylot the carboxylic group and then converted to the chloro "arbonyl group with the aid of thonyl chloride.



  81, at the halter of the 2 *, 0 portat of chloturu dp hfduca: methyl, euifanyl 1hcnxoya, dosages dquivatontos of 2 fiuoro 5> -ethyl sulfonyl-1-bonzoylet of 2-fluoro.-d1hyl chloride are used. minoeulfonyl-1-bonzoylo, do 2-fluoro-diethylaminosulfonyl-1-benzoylo chloruro or do 2- f.uaxa-5-rnthyi-thylaminasulfanyl.-1.-benxay.v chloride, we obtain
 EMI17.2
 analogous coloring backs endowed with omblabloa cleanliness.



  Acylation agony containing back
 EMI17.3
 sulfamylos groups are prepared from acid chloride 2.f, uaxa1 caxbaxybonzinc..aul'aniqua with dot solution. dot alkylammonium chloride corrospondanta
 EMI17.4
 fatty acid salts of alkali metals are present.
 EMI17.5
 The following table 1 contains other
 EMI17.6
 dyes which have been prepared according to the instructions of
 EMI17.7
 Example 1, as well as the dos tolntu shades;

  ea on coDuloie r6ftl, .de with these co} o! '.') nt6,

 <Desc / Clms Page number 18>

 
 EMI18.1
 BOARD!
 EMI18.2
 * "*" ** hmm iinwo l'iètn i mm * mm ** # -> tt n r-.rc a iiiiJ .jjiin-ninmiiii riiiiijii'miji * .ii) i]) iiiniij (wt | j j. ii | mi iiji.in .1,1 #kiji | h..i * i ii'iruiitmi.iiicijiiiiiiliiii.im.ctiiii-
 EMI18.3
 
<tb> Nuance <SEP> on
<tb>
 
 EMI18.4
 N "Free collulotic constitution '! M m! Jt)' n)) <) j) j !! <!) T <nt! '' !! <!! mw)! H '!!'!) X ! [MftM U!) U !! 'W' !!!! <WM << t'M) 'WWMMtW) t <) MM) tMMM * M << MMM <MtMMMWM <M, * - \ - 803H CH WC * 1 N w N 3, ce '-% 03H Yellow CL 2 ci CCNHSOgH CH3-C S03H yellow 8t> 2, CaHft M w N ffl cw C "* 1 .CO.MH-rSO Lil r Cl S? N% N yellow SOa, vH3 N a N .. e Co - ± ¯r J, aun ÔH F- * CO.NH-r.SO-H flS.f. / 4) F <> 3 S03H CH3-C N \ N jn.



  Cil N * N # C m C 'y-77' Yellow 3 C CO.NH''O.W CH M, 1. Su3 uno 50, fti 3 H CHqwç # ci qq 903H 'so2, ai3 n * n # # c' ci
 EMI18.5
 
<tb> F
<tb>
 
 EMI18.6
 6) ci 4NH-CD- $ 03H CH3.C 1 SCLH, * unrr $ 02, N c, li5 N "A tolu

 <Desc / Clms Page number 19>

    EXAMPLE 2:
 EMI19.1
   18.8 parts of acid 1.3- are dissolved
 EMI19.2
 di.:Jlninoben:;t>n(t-4...,ulfoniquo with aodium carbonate in 200 parts of caut at a pH of 4.0-4.5. To the solution. rofroidio at 0 5 * C 29.2 parts of 2.fluoro-5-dim & thYlaminosulfonyl-bon = oylo chloride dissolved in 100 parts of acetone are added over 1 hour, while sodium carbonate solution is added dropwise in order to maintain the pH of the solution. reaction mixture b 4.0-4.5.



  As soon as the reaction is complete the condensation product is precipitated by the addition of 30% hydrochloric acid, it is separated by filtration and again dissolved in 300 parts of water. The solution was cooled to 10 ° C. and 6.9 parts of sodium nitrito and 25 parts of hydrochloric acid were successively added thereto, while the temperature was maintained at 10-15 ° C. by addition of gJaco. When the diazotization is completed, the suspension is
 EMI19.3
 pension of the diazorquo compound at pH 1.8-2.0 using a sodium carbonate solution and then poured into a solution consisting of 42,

  3 parts of salt
 EMI19.4
 1-Benzoylamino-8-hydroxy-nFaphthaleno-3.6-disulfanic acid sodium in 200 parts of water and 40 parts of sodium carbonate. When coupling is complete, the new dye is precipitated with sodium chloride, filtered off, washed with dilute sodium chloride solution and dried.

 <Desc / Clms Page number 20>

 
 EMI20.1
 il e, O ... 60'C 6t> u praotion r .. 'ldui h. It tlouoof'jc) I1d the formula given rather hiui ut it <e taking 4 included fottno of a dark red powder which ae dissolved in water with a red coloring tending to blue.



   The cellulose or polyamide fibers can be dyed with the new dye,
 EMI20.2
 by the methods commonly applied for reactive coloring idea, in shades ($) red # wet solids? The chloride of 2, uoro. d, mGthy. amino8uXfonyl-1 bon! soyle is obtained from 2-fluorō-1-bonzo! ocido, by anointing with chlorosulfonic acid resulting in 2-fluorō 1-carboxy-5 acid chloride -sulfoniquo, reaction do co last avoc dimthylam9.na and conversion of the carboxylic group to a chloro-carbonyl group with the aid of thionyl chloride,
If we ophro do the same way we use, instead of 29,

  2 parts of chloride
 EMI20.3
 2-fluoro-5-dimethylaminosulfony1-1-bonzoyl, the equivalent amounts of 2-fluoro-5-di 5-ylaminosulfonyl-1-bonzoylop de 2-fluoro-5-methyl "dthyleminosuifonyl-1-bonzoyl chloride , 2-fluoro chloride.



  5-, m thylsuifanyl-.1.-bcnxayla or 2-fluoro-5-6thyxsulfanyJ, -1-bcnzoylcchloride, corresponding dyes are obtained, preceding analogous properties.



   The following Table 2 shows other dyes which were prepared according to the indications of Example 2, as well as the shades of the cellulose dyes produced with these dyes.

 <Desc / Clms Page number 21>

 
 EMI21.1
 TABLE 2
 EMI21.2
 n4lo $ tir NO Coostt tuHM fibers ce! - .. luloaiquew rr ............- ---.......-............ ....... "" '*' ......................, ....-- IJ 1 * 'rotjtqt Ç' <D ''. 0 & aeriata ¯, 3 JLjj 4cnlah.



  .2 "('H / \'" '' 3- '0 JH r-lm.NU. (") ... S03H' '0 rOU9tt y I. --T4N. 1J, * 1 shell) - f .: OI3 N '.'1, 4carlate 60 2ON HO; 5 03H ci) PN! IqS03H' CO-0 S02.C13 NAN red H03S 5f3H 4) F Co qo3H (i Ini-CO-0 red 4) F .. (') -, tlHqo3H -4, A .'rOUQI SU (CH3 ICIf! ah Mo 0 3 H) ci OH aa pt Ci' 1 N. N ... fl 'IQ onnQ' re.wrrt rer, a wa m , t fi a ins.a. * rsw.r 1 -.-? -----'- "'' '. 1 -.

 <Desc / Clms Page number 22>

 
 EMI22.1
 TABL8AU2 (tultf).
 EMI22.2
 



  ..-... ------ .- '-; 1iij) C'.ïùt' Nt Constitution fibers col "Iulos \ (t1lQI ................ .... "............................ JI" ..., ......, .... ...., f ..., ............................



  03H 'yellow pulling Co "' .tiOH H4 - f Oi on the M" "N. N -:> rQugl 802.N << Li SOqtN r.1 \ ï HC3â Co NH .L .. orange '. H032S oranCJê CO . ... s 3H S03B pulling on 2'C2 '"N. () the young p 803H r-lco. NH 503H). S03H orange ICH3 N shooting yes, S02, N, - 1 1f young
 EMI22.3
 
<tb> Cl
<tb>
 
 EMI22.4
 9) F..WySO.H orange S621S '-'. N '"N" "'" .lS03H Qr'nQft s03H H03S in) 141 :: so3H H03S "GG" 12.Gli, .tXH oranpa '0) sn rx <: z ... s 3H' S OtAn; t t'-fi! N '"N t' M) lill'7f.;! 'Rkr1-ro. S t.! I t -He, .. t.,.) H) r!' '* M Mt <M wr Vrwtt .1 'in, s wrx' t 11 "'' '' '' ......... aL J1A 1 1

 <Desc / Clms Page number 23>

 
 EMI23.1
 , TA S LE AU, 2 (continued)
 EMI23.2
 
<tb> Nuance <SEP> on
<tb>
 
 EMI23.3
 No Constitution free cel ... lulQa1ques ....., ....., ......,.,. r, ... ".,.", ..,! Wt "!! '"' "* l JI J 1 rr Ji ......-...........



  H03S 1 \) Aco. OR-! .c03H NH, co.cHàrcH orange $ 0 CH, M.M Ijj S02 'H ;, OH COOL
 EMI23.4
 
<tb>
<tb>
 
 EMI23.5
 ci i 2) F -.) - <X) .NH-SO.H OH COCH * CH .CH NH.CO.CHH carlete '12) ëO ,,. CH. NH .. () - S03H & 1 H.CO.CHeCH deaflet.



  H03 N se 140aSI S02,, CH3 13) CO.Nti -, - * O \ -Qo3FI OHNH.CO-P eclt 13) (D - '' <13) -; - CO.NH <: <: 3 JA 4Qarhtt SO2 "CH3 H0 3H C3 SO2" <CH '14) CO. IH OH NH.CO. 'H3 4e.rl.te 02.N / CH3 "" "" N. N 'cH3 HO., ST H03S-' SO 3

 <Desc / Clms Page number 24>

 EXAMPLE 3:
 EMI24.1
 Can this example start from the dye
 EMI24.2
 * minommoozoequo copper answering the following formula
 EMI24.3
 colorant obtained by coupling in an alkaline medium
 EMI24.4
 2 amino.1-hydxaxybanxne.4b disulfonic acid dlazotque with 2¯amino-5-hydroxynaphthal & no <7 <i sulfonic acid and treating the obtained am1nomonoazolquo dye with a copper release agent *
51.7 parts of the preceding copper aminomonoazole dye are dissolved in the form of its sodium sol,

   in 500 parts of water. At 20-25 C we add a
 EMI24.5
 solution of 29.2 parts of 2.fJ.uoxa-5thy chloride,., aulfony ,. 1 bonxpyla in 150 parts of acetone and the pH of the reaction solution is maintained * at 6.5-7.5 by adding sodium carbonate solution * As soon as free amino groups can no longer be detected the new dye is completely precipitated by the addition of sodium chloride, separated by filtration and dried at

 <Desc / Clms Page number 25>

 
50-60 C under reduced pressure. It is in the form of a dark powder which dissolves in water with a ruby red color.



   It dyes cotton, regenerated cellulose, jute, ramie, hemp, wool, silk and nylon, by the usual procedures for reactive dyes, in pure shades, rubid red, which are wet solid. .



     Lo 2-fluoro-3-ethylsulfonyl- chloride
1-Benzoyl is obtained by ethylation of 2-fluoro- acid.



   1-carboxybenzene-5-sulfinic with ethyl ioduro and conversion of the carboxylic group to a chlorocarbonyl group using thionyl chloride,
In the following Table 3, other dyes which were prepared by the procedure of Example 3 were indicated, as well as the shades of the taintues on cellulose produced in the case of dyes.
 EMI25.1
 

 <Desc / Clms Page number 26>

 
 EMI26.1
 TABLE 3 il.
 EMI26.2
 



  '- * "" "'" "" "" '"'" ## "" 'M' / 1 "" "H ..., n ......-...." .- '. .-L ... L '- ## .. wsrrrwrrlwW lJ.1l L "Grade N. Constitution JI" "fibers col- Hutn .. tur pww1w14YP HO S lul., Lquo' 1) p .. Ctu 0 NH Co o, .CHS purple Np vloltt S03H. S4.Gt NH .C .C / JF purple 2) N 2 SO 2 'HO 3 OH "3? 33) CH3 black Jr' draw HO-S 3'JffNH. S CO .p 2. on the YY / green N kill 2 N rr 4, .z. "ç 1J, vort" 0 03H in r Htà 8 r .t "f" 1 black 0035 / \ ti black H03S .. o, "9 0 CoV2JJj. NH 4 -! '2. Black 1 ""' walnut m 8 brown 503H NC? <Se.CH .MCOf-Ci brown ts 1H. Brown HO 3 NNC CH3 yellow to 3H.

 <Desc / Clms Page number 27>

 



  EXAMPLE 4:
 EMI27.1
 
A solution of the diazo salt prepared by diazotization of 24.6 parts of 2-amine-4- acid
 EMI27.2
 acetylamino-1-hydroxybonzene-6-sulfonic acid with 6.9 parts of sodium nitrite in the presence of hydrochloric acid is mixed with a solution of 30 parts of sodium carbonate and 31.7 parts of 1- acid. amine-8-
 EMI27.3
 hydroxynaphthalene <-2.4-di8Ulfonic acid in 200 parts of water. As soon as coupling is complete, the dye is precipitated with sodium chloride, filtered off, washed with dilute sodium chloride solution, and again dissolved in 500 parts of sodium chloride.
 EMI27.4
 Sudokaustic detergent at 5.

   The mixture was stirred for one hour at 9Q.950C until the oedtylamino group was saponified. Then, at 60-65 C, the pH of the solution is brought to 4.5-5.0 with acetic acid, then 25 parts of copper sulphate crystallized in 100 parts of water are added to the solution.

   We shake
 EMI27.5
 laying for 1 hour at 60-.65 C, then precipitated the dye, am1nomonoazotquQ copper with sodium chloride, it is separated by filtration. then washed with sodium chloride solution * The wet dye is dissolved

 <Desc / Clms Page number 28>

 in 500 parts of water and added!) the solution, at 20-25 ° C in one hour, 30.7 parts of 2-fluoro- chloride
 EMI28.1
 5Hnethylethylaainosulfonyl -1 benzQ.yle By the simultaneous dropwise addition of a sodium carbonate option the pH of the reaction mixture is maintained at 6.5-7.0. As soon as the reaction is completed, the product is precipitated. by condensation / sodium chloride,

   we separate it by
 EMI28.2
 filtration and dried b 6O-7O C under reduced pressure.
 EMI28.3
 The new colorant, which corresponds to the formula given above, is in the form of a dark powder which dissolves in water with a dark blue coloration. It dyes cotton, regenerated cellulose, jute, ramie, hemp, wool, silk and nylon, by the usual processes for reactive dyes, in wet solid navy blue shades.



   This gives 2-fluoro-5- chloride.
 EMI28.4
 Methylethylam1n08ulfonyl ... 1 ... bonzoylo on condensing the acid chloride 2.fluara1 carbaxybanxbna..sulfo. nicely with methylethylamine ot by transforming on-
 EMI28.5
 following the carboxylic group into a chlorocarbonyl group by means of thionl chloride.



     If, instead of the 30.7 parts of chlo-
 EMI28.6
 2fhuaxo..5 m6thy ride, thyxami: nasulfonyl-1bpnxay.o, equivalent amounts of
 EMI28.7
  fluara ad, methylgu, fony.arrr, now1.banxay, a, do 2-fJ.uaxa dimthyi.uxfonyl chloride, amina 1 .bnzay.o, do 2-fiuoro-5-methylsulfonyl-1-bonzoyl chloride or do chloride of .fhuaxa.5 dthylau, fanyl..1..banzaylsr, analogous dyes are obtained with samblabl s opr16w tees
In Table 4 below are indicated other dyes which were prepared by the procedure of Example 4, as well as the shades of cellulose dyes produced with these dyes.

 <Desc / Clms Page number 29>

 
 EMI29.1
 TABLE 4 ¯OL .. ". - '
 EMI29.2
 iiuoie% lw eu & Ne Comtttution fibers ce) 1 luloalqu ..



  .......... \ .. !!!!! <! <tum <. <, rtt <Tt W-TM !!! HJ! '...' T j '- "o:" 'T.mM.l!' L-.n; r) tnrMM! Mr-T'T1 "t MM * <" <* '<<< *' * "- **" 0 Cu- F HD N .N rw kltt H03S .. o reads N qu; "N .. '-" blue,), H 8 mina Fi E H03 03M l'nul Co Wb1,21CH3 02.CH3
 EMI29.3
 
<tb>
<tb>
 
 EMI29.4
 CI / "'" 0, HN N QI.! . violet CI 3C'IJ. 'Y': '11 vlOI.t $ 02-N S 3H 03H S02.N, CH 3 5 3 "W N w (90H 1 3 3) J-CO. 5 3" blue JO C2 0- H03S. . ' SC H violft S03H violet '0 "pulling 1 $ 03H on the red COF SIC2H CH 112 0 cq 0. H 2 CH: s, 02 \ .... HC \ t ... H viciât i .'N vol.t S03H 3H

 <Desc / Clms Page number 30>

 
 EMI30.1
 EXAMPLE 5 NH2 "628424 H03S 0: 3 H H03S" YY 03H NIHI 02 # CH3 'ONH.

   NH t co <; 50: 2tCH3 03H
 EMI30.2
 We dissolve under forma do se 8od1quo, in 1000 part * of water, 56 # 9 part * dtnoido 1-ornino- 4 (('ul'a' -aminophenylaminora anthraquinonc2 7.di sultonique (obtained by sulfonation of acid 1 -amino.



  4- (4t-am1nopnylamlno) anthraquinone-2.7-disulfon1quQ in Itoidum at 30%), To this solution is added dropwise at 0 <"'" C, a solution of 25.0 parts of chloride of 2 -fluoro-5-methylsulfonyl-1-bonzoylo in 100 parts of acdtonop while maintaining the fold at 5.0 - 5.5 pnr addition of sodium carbonate solution * When the reaction is finished, the new dye is precipitated (corresponding to the formula given below) by addition of sodium chloride, it was separated by filtration, washed with a solution of sodium chloride and dried at 50-600C under reduced pressure. It dissolves in water with a blue coloring and it dyes cotton, regenerated cellulose, jute, ramie, hemp,

   wool, silk and nylon, by the processes
 EMI30.3
 064 commonly applied for the reactive dyes, we nuance biou which are solIdQ # to mutlt4o Si, instead of 25.0 parts of 2-fS chloride, uaro -. Methylsulfcnyl1-banxaylc, 1 equivalent amount of 2-chloride was used. -fluoro-5'-cthyl "Gulfonyl-1-boozoylo, 2-fluoxa - dimcthyl chloride.

 <Desc / Clms Page number 31>

 
 EMI31.1
 amino8ultonyl-1-benzoyl $ or 2-fluoto .. 5-methyltSthylamino8ulfonyl '; 1 ... benzoYl chloride, corresponding dyes are obtained which have similar properties.



   In the following table 5, other dyes which were prepared by the procedure of Example 5 are indicated, as well as the nuances of the cellulose dyes obtained with these dyes.
 EMI31.2
 

 <Desc / Clms Page number 32>

 
 EMI32.1
 PAINTINGS
 EMI32.2
 "..., .. T ...." ",., ¯ Nuanct tut No Constitution fibers ckl .. lulogiquoi il 0 H S03H NH 803H CO -1: OC20CH3 1 blue 4 H 3H a # CH3 SH H038 TT co --02 p - / CH3 blue OV3 H% 3 Hp NH2 $ a3H le3 # NHH2 '' "Jk Nose. NH. GH drank.



  4) 003H / fr t N1 NH CK) blue .¯¯¯ 10 3H '\, month f, 1 UJJ' 3 0 NMNH .03-'P blue S'0''H, Cl '. '#' '#' # 3S NH 02 blue
 EMI32.3
 
<tb> NH <SEP> 00 <SEP> P <SEP>
<tb>
 

 <Desc / Clms Page number 33>

 EXAMPLE 6
 EMI33.1
 57.6 parts of cuivra-prktai.a- cyanineetetraoulfochloride are suspended in 500 parts of water and 300 parts of ice, stirred with 15 parts of m-aminoacetanilid * and brought to pH b 7 'by addition of an aqueous ammonia solution. The temperature is then allowed to rise slowly to 40-5O G, while constantly maintaining the pH of the suspension at 7.0-7.5 by the dropwise addition of an ammoniacal solution As soon as no more can be detected. amine
 EMI33.2
 Primary 270 parts of 30% hydrochloric acid are added and the mixture is heated for 3 hours at 3a90 C.



  This treatment has the effect of saponifying the acetylamine group. The dye is then isolated by filtration, it is
 EMI33.3
 mat h again in suspension in 1000 parts of water at 10 C and the pH of the suspension is brought to 8.5 with dilute caustic soda lye, A solution of 29.2 parts of 2- chloride is poured into this suspension.
 EMI33.4
 fluoro-5-dimethylaaminosulfonyl-1.benzoyl in 100 parts of acetone. Condensed while stirring well 10-15 C ot neutralized the hydrochloric acid liberated by adding dropwise a dilute solution of sodium carbonate * When the reaction is complete, rolargue com-
 EMI33.5
 plot the new dye,

   lo separated by filtration and dried at 50-600C under reduced pressure It corresponds to the following schematic formula
 EMI33.6
 

 <Desc / Clms Page number 34>

 in which
 EMI34.1
 Pc represented 1% 6quelotte of the phthalocyanino, @t X represents one left the groupa Nl-1 and partly lo group .GNr or ... Ct-SH4.



   It dyes cellulose or polyamide fibers in pure turquoise blue shades which are solid in the wet.
If we operate in the same way but
 EMI34.2
 that instead of 2-fluoro-5-diroé "thyleminosulfonyi-1-bonzoyloé chloride, the equivalent amount of 2-fluoro-5-dimethylaminoeulfonyl-1-bono zoyl chloride of 2.tluoro.- chloride is used. m'th16thyl'no.

   sulfonyl-1-bonzoylet of 2-fluoro-5-methyl sulfonyl-1-bonzoyl chloride or of 2-fluoro-5-ethyl sulfonyl-1-bonzoylo chloride, we obtain corrosive dyes endowed with similar properties,
The following Table 6 contains other dyes which were prepared by the procedure of Example 6, as well as the shades of the pulp dyes made with these dyes.



   TABLE 6
 EMI34.3
 
<tb> N <SEP> Constitution <SEP> Nuance
<tb> fibers <SEP> cal-
<tb>
 
 EMI34.4
 lulosquo :.



  J # (SOgH) * blue 1) Cu Po turquoise S% * NHè% * CH2 * NH.C (-02-CH3 Cu Pa .j3 a 4A ^ Y i H Lrf7A i VH 1ü7 i 3) Cu Pc- S03H> 3, 502. / 3 4) Cu Pc (SO26r%) 3 A 'rf. 9 bm OMMS02 9 NH-C * -> S02 s N X.CO-Cj # F ######### ### - ###################

 <Desc / Clms Page number 35>

 
 EMI35.1
 EXAMPLE 7 so 3 H j- # '6jS03H N. N' \ # / 4; rt 11, L f Y i Y J CH ...... H3.



  \ / \ ./ t SO a H
 EMI35.2
 In this example, we start with the aminamn4azauo dye corresponding to the following formula
 EMI35.3
 dye which is prepared by diazotizing ziamino acid
 EMI35.4
 naphtholéno-4 * e-dieulfonique ot by coupling the diazotquo with the 1mno3môthybnxno one presence of either al- cids of cid # gru.



  In 400 parts of water we dissolve
 EMI35.5
 form of the sodium sol # 42.1 parts of the above amino-monoazorque dye * At 20-25 C, 29t2 parts of 2-llworo- -d1m & thylominosulfonyl-1-bcnzoylà dissolved in 100 parts of chloride were added dropwise in one hour. acetone, while maintaining the pH of the reaction mixture 6.5-7.0 by adding sodium carbonate solution. As soon as no free amino groups are detected, the reaction product is precipitated by the addition of sodium chloride, filtered off and washed with dilute sodium chloride solution. The new dye is dried at 50-60 C under reduced pressure * It is in the form of a yellow powder which dissolves in water with a yellow color.



  It dyes cellulose and polyamide fibers by the processes commonly applied for dyes

 <Desc / Clms Page number 36>

 reactive, pure shades / yellows having good light fastness and good wet fastness properties.



   If we proceeded in the same way but we used, instead of the 29.2 parts of
 EMI36.1
 a..fluaxor5-.dimthylaminosulonyl lbenxayl equivalent quands / titde of chlorurofluoro-5-di4thylamlnosulfonyl-1.benzoylo, of 2-fluor-5-methyl-ethylaminosultonyl-1-bonzoylet of 2-fluor-5 chloride -methyl8ulfonyl-1-bonzoyl or 2-fluoro-ethyliulfonyl-1-bonzoyl chloride, corresponding dyestuffs endowed with similar properties are obtained.
The following Table 7 contains other dyes which were prepared according to the directions of Example 7, as well as batch shades dot dyes on.

   cellulose made with these dyes
 EMI36.2
 

 <Desc / Clms Page number 37>

 
 EMI37.1
 T A B! .S A U 7 M¯. "'" 1 1
 EMI37.2
 # '- ###### itnco on constitution flbroà ot1 ..



  Con.Ututlon lU1QI1quu S03H -g Rune / il .. N-Q-NH. 2.CH3.,, J'tun.



  H03AY 0, cl S 3 Q, CH3 p junr 3H N .. N NH. co jiune k T -'- "- <s02.C2H oH ai s03H" 'Ntf. t .. 'yellow r, "H03 $ SO 3 802. <:: H3 4) N. N-QN. N0-NH. C i3 young H03S S03H jun%) SoH N N1 NH. CdF S03H sa 3 H CH3 2 # C "3 H03S-C> N -. J," - ') CH3 or.nQ.



  $ 03H CH3 S02 'CH3 SO-H "S0 -.! F * CHg 7) HOQ-N" NN .. N-0-NH ..



  3H SCH3


    

Claims (1)

ABSTRACT The present invention includes in particular 1) As new industrial products, the dyes corresponding to the formula generated? III EMI38.1 in which at least one of the symbols X1 and X2 represents a fluorine atom and the other hydrogen or any substituent except the nitro group, R. Represents an optionally substituted amino group or a lower alkyl residue R 'represents hydrogen or a lower alkyl residue, D represents the residue of an organic dye, and n denotes a positive integer at most equal to 2. 2) Varieties of coloring. specified under 1, having the following features: a) in the dye formula, the symbol D represents the residue of a sulfonated and optionally metallized amino-mono- or -polyazoic dye; b) in the dyestuff formula, the symbol D represents the residue of a sulfenated anthraquinone dye; c) in the dye formula, symbol D represents the reate of a sulfonated phthalocyanic dye bearing amino groups. <Desc / Clms Page number 39> 3) A process for the preparation of the dyes specified under 1 and 2, a process according to which 1 mole of an organic dye of formula 1 is reacted EMI39.1 in which the symbols D, R4 and n have the meanings indicated under 1, with n moles of a compound capable of introducing the residue corresponding to formula II EMI39.2 in which the symbols X1, X2 and R have the meanings indicated under 1, or these dyes are synthesized from components at least one of which contains the residue of formula II linked by means of a amino group. 4) Embodiments of the process specified under 3, having the following features taken separately or according to the various possible combinations ta) D represents the residue of a sulfonated and optionally metallized aminomono- or -polyazoic dye b) one makes react 1 mole of an aminomonoazo dye corresponding to the general formula IV (H2N) n AN = N - B) (IV) in which <Desc / Clms Page number 40> A represents a residue from the series of benzone, di-phenyl or naphthalene, optionally bearing other substituents, B represents the residue of a commpoastane coupling at a position close to a hydroxyl group. lic or amino, and n has the meaning given under 1, with n mixes of a compound capable of introducing the remainder of formula II, reaction which results in a dye corresponding to the general formula EMI40.1 in which A and B have the meanings given under formula IV, and the symbols X1 'X2' R and n have the meanings given under 1; c) reacting t mole of a metallized aminoazo dye corresponding to the general formula V EMI40.2 in which A represents a residue of the benzene or naphtha series - ' Ionic optionally carrying other substituents, B represents the remainder of a component coupling in a position close to a hydroxyl group, Me indicates a heavy metal of atomic number 24 to 29, a metal which can still be linked to other complexing agents by coordination, Y represents oxygen or the COO- group, and <Desc / Clms Page number 41> EMI41.1 n a 1..10n1t1Óation indicated 4 under Ibo With n molot of a compound mpte b introduce lu re4t *. of formula Ilt reaction which leads to a dye corresponding to the general formula EMI41.2 EMI41.3 in which the symbols $ A, of Mo and Y have 108 lignification! indicated all the formula V, and X1 'X2' EMI41.4 ot n have the signitiontiome Indicated under 1 * jd) the symbol D fopr6otntQ J., r9tt <of an amino-anthraqu1noniquo sulfonated dye i) the eymbqle P repeats * the remainder of a phttlocyanic dye. ) one copulates a diazo compound corresponding to the general formula VI EMI41.5 in which A represents a residue of the series of benzene, di-phenyl or naphthalene, optionally carrying other substituents, and, X1'X2 and R have the * meanings indicated cous1, with the components copulating in a neighboring position EMI41.6 a hydroxyl group u amino, to obtain an azo dye corresponding to the general formula VII EMI41.7 <Desc / Clms Page number 42> where it represents the route of a component coupling at a position adjacent to a hydroxyl or amino group, EMI42.1 X1 'X2 and R have the .1001fioat1n. 1nd1queou. 10p and A 1. lignification indicated * bous Iti tnrmula VI # and the resulting colouration was transformed optionally into one of its m6t.lli complexes. By troitomont -vue of agents encoding heavy metals; EMI42.2 o) one copulates a diexoic compound A-N2 + which is evontutllomont portour other #ubatituantot with a component of copulation corresponding to the general formula VIII EMI42.3 in which X1 'X2 and R have the meanings * indicated * under 1, and B represents the residue of a component coupling in a position close to a hydroxylic or amine group, coupling which results in a dye corresponding to the general formula IX EMI42.4 in which X1 'X2 and R have the meanings indicated under 1c, B has the meaning index under formula VIII, and EMI42.5 A represents a residue of 1¯) series of bonzèno, diphd nyle or naphthalene, 'vauol1omont pote tour dtaurec subotttuantet <Desc / Clms Page number 43> and optionally converting the dye obtained 'into one of its metallized complexes by treatment with heavy metal releasing agents; h) a drazo compound corresponding to the general formula VI is copulated EMI43.1 in which A represents a residue from the series of benzene, di-phenyl or naphthalene, optionally bearing other substituents, and X1 'X2 and R have the meanings indicated under 1, with a coupling component corresponding to the general formula VIII EMI43.2 in which X1 'X2 and R have the meanings indicated under 1, ot B represents the residue of a component coupling at a position close to a hydroxyl or amino group, coupling which results in a dye corresponding to the general formula X EMI43.3 in which X1 'X2 and R have the meanings indicated as soue 1, <Desc / Clms Page number 44> A represents a remainder of) the series of benzene, di- or / phenyl / naphthalene, optionally carrying other substituents, and B represents the remainder of the coupling component in a position near a hydroxy or amino group and the dye obtained is optionally converted into The en of its complexes metallized by treatment with agents encoding metals.