BE710968A - - Google Patents

Description

  

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    Anthraquinone dyes, heavy preparation and their applications.



   The present invention relates to a process for the dyeing and printing of textile materials consisting of these polymers or copolymers of acrylonitrile or containing such polymers, with dyes of the anthraquinone series, a process according to which one uses to this end of the dyes corresponding to the formula
 EMI1.1
 wherein M was a bivalent bridging group, one. X represents a hydroxyl group, a nitro group or an optionally substituted amino group,

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 the antrum X represents a hydroxyl group or an optionally substituted amino group,

   T 'represents a nitro group or an optionally substituted amino group, A - represents an anion equivalent to the coloring cation and K represents a group corresponding to one or the other of formulas II and III
 EMI2.1
 formulas in which R1 denotes an alkyl or cyclo-alkyl residue optionally bearing substituents or forms, with R2 and the neighboring nitrogen atom, a heterocycle, R2 represents an alkyl or cyclo-alkyl residue optionally substituted or forms a heterocycle with R1 and the neighboring nitrogen atom, R3 and R4 represent hydrogen atoms or alkyl or cyclo-alkyl residues, identical or different, optionally carrying substituents,

   or representing back identical or different acyl remains,

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 R5 'R and R each represent hydrogen or an optionally substituted alkyl or cyclo-alkyl group, R1 can form with R3 and / or R2 can form with R and the atoms adjacent to these substituents $ and R5 and R6, or R5, R6 and R, with the neighboring nitrogen atom, can form heterocycles, the rings B and / or D being able to carry other substituents and the group - M - K # occupying one of the positions 2 'or 4' .



   Particularly good quality dyes can be obtained by using dyes of formula IV
 EMI3.1
 in which E denotes a remainder corresponding to one of the formulas V and VI
 EMI3.2
 

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 formulas in which Z denotes an oxygen or sulfur atom, Y represents the direct bond or an optionally substituted arylene residue, which residue is linked to V directly or through the intermediary of a hetero atom or of a hetero-atomic group, V denotes an optionally substituted arylene residue, residue which may be interrupted by heteroatoms or by hetero-atomic groups, V1 denotes a divalent group forming a bridge,

   group which is connected to K # by one. carbon atom, and R8 represents a hydrogen atom or an optionally substituted hydrocarbon residue, the rings B and / or D possibly having additional substituents and the group -ZYVK # or the group -Z-R8 occupying the one of the 2 'and 4' positions. ddd.



   The invention also relates to
1) basic anthraquinone dyes, group-free, sulphonic and corresponding to formula VII
 EMI4.1
 in which K1 represents a group of formula II or a group of formula VIII

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 EMI5.1
 in which R9 ′ R10 and R11 each represent an optionally substituted alkyl or cyclo-alkyl residue and R9 and R10, or R9, R10 and R11 may together form, with the neighboring nitrogen atom, a heterocycle, the rings B and / or D which may carry additional substituents
 EMI5.2
 and the group -Z - Y-.V-.Ki9 which can occupy one of the 2 'and 4' positions, 2) basic anthraquinone dyes lacking a sulfonic acid group and corresponding to formula IX
 EMI5.3
 in which the group -Z-R8 occupies the positian 2 'or the position 4', 3)

   Anthraquinone dyes lacking a sulfonic group and having the formula X
 EMI5.4
 

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 in which the -Z-R8 group occupies one of the @ and 4 'positions, 4) basic anthraquinone dyes devoid of
 EMI6.1
 (Jr () \ '(' sulfonic and r4poiidant with formula VII in laiuel1a at least one of the symbols X and W represented an alkyl-amino or aryl-amina optionally carrier r] (, '> 1.1: -: $ ti tUM ts.



   To prepare the dyes of formula VII it is possible: a) to react an anthraquinone compound
 EMI6.2
 ; r.i5:, or.r; c1nt formula XI
 EMI6.3
 
 EMI6.4
 in .'aulle A represents the acid residue of an estor, with a con> j, r6pl'mrla.'t the formula XII
 EMI6.5
 or with a compound of formula XIII
 EMI6.6
 b) reacting an anthraquinone compound corresponding to formula XIV
 EMI6.7
 

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 with a compound corresponding to the formula XV Halogen -. NH2 (XV) or with a compound of the formula XVI
 EMI7.1
 or transform an anthraquinone compound corresponding to the for-
 EMI7.2
 mule XVII -, \ / R P, 9 2 f x '10 2, 'B #.

   'R.10, by reaction with a quaternizing agent, to a compound of formula XVIII
 EMI7.3
 in which R12 represents an alkyl or cyclo-alkyl residue optionally bearing a substituent $, c) reacting a boric ester of an anthraquinone compound corresponding to formula XIX
 EMI7.4
 

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 with a compound of formula XX
 EMI8.1
 so as to obtain a boriquo ester of a compound corresponding to the formula XXI
 EMI8.2
 saponify the boric ester group and exchange the -SO3H group against a hydrogen atom or against a non-water-soluble group, d) reacting a compound of formula XXII
 EMI8.3
 in which R denotes hydrogen or an optionally substituted hydrocarbon residue,

   with a compound of formula XX, e) reacting a boric ester of a compound of formula XXIII
 EMI8.4
 

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 with a compound of formula XX, saponify the boric ester group and optionally reduce the nitro groups to thin groups.



   To prepare the dyes of formula IX it is possible: a) to react an anthraquinone compound of formula XXIV
 EMI9.1
 with a compound of formula XII or XII, b) reacting an anthraquinone compound of formula XXV
 EMI9.2
 with a compound of formula XV or XVI, or converting an anthraquinone compound of formula XXVI
 EMI9.3
 

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 EMI10.1
 r - '* or. avpc a quaternizing agent, to a compound 5n; -; n XXVII
 EMI10.2
 c) reacting a boric ester of a compound
 EMI10.3
 -, '1t': ri.r:

  U.1 noniqu "of formula XIX
 EMI10.4
 with a compound of formula XXVIII
 EMI10.5
 in order to obtain a boric ester of a compound of formula XXIX
 EMI10.6
 

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 saponify the boric ester group in this compound and exchange the -SOH group for a hydrogen atom or for a non-water-soluble group, d) reacting a compound of formula XXII with a compound of formula XXVIII or e) reacting a boric ester of a compound of formula XXIII with a compound of formula XXVIII, saponifying the boric ester group and optionally reducing the nitro groups to amino groups.

   ,
The dyes of formula X a) can be prepared by reacting an anthraquinone compound of formula XXIV with a compound of formula XXX
 EMI11.1
 b) reacting the boric ester of a compound of formula XIX with a compound of formula XXXI
 EMI11.2
 so as to obtain a boric ester of a compound of formula XXXII
 EMI11.3
 

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 then, in the latter, saponify the boric ester group and exchange, in the compound of formula XXXII, the -SE3H group against a hydrogen atom or against a non-group
 EMI12.1
 water-solubilizer.

   c) reacting a compound of formula XXII with, a compound of formula XXXI, d) reacting a boric ester of a compound of formula XXIII with, a compound of formula XXXI, saponifying, therein, the boric ester group and optionally reduces nitro groups to amino groups,
The dyes corresponding to formula VII in which at least one of the symbols X and W represents an optionally substituted alkylamino or arylamino group can be prepared by alkylation or arylation of an anthraquinone compound corresponding to formula VII in which at least the one of the symbols X and W represents a primary amino group.



   If it is desired to prepare anthraquinone dyes corresponding to the formula XXXIII
 EMI12.2
 a boric ester of an anthra-
 EMI12.3
 quin, onirjue'r4pondant to formula XIX with a compound of formula XXXIV

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 EMI13.1
 reaction which generates a boric ester of a compound of formula XXXV
 EMI13.2
 then saponify the boric acid rump and exchange the
 EMI13.3
 group -SO3H CCf \ trc a hydrogen atom or oontKya non-water-soluble group.
 EMI13.4
 1-e residue # (B 4y preferably occupies the ortho position with respect to the substituent W; but it can also be in the ortho position with respect to the hydroxyl group.



   The compounds corresponding to formula XI, in which A represents for example a halogen atom, can be prepared in accordance with the indications given in French patent No. 1,218,936.



   The compounds corresponding to the formula XIV or to the formula XVII can be prepared as described in the German patent application released for public inspection under No. 1,228,734.



   The compounds corresponding to formula XXIV in which A represents for example a halogen and

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 EMI14.1
 11 ,; 'nr <; vte alkyl, can be prepared by reaction of #rarst, described in the French patent Na 1,218,936,. ,, an .- ..; s ..- f, le with N-tiydroxy.-methyl -amide of acid h "2'1 ';, - :. i"' J.



  In the compounds of formulas I, VII and IX 4 ... ar roq, 11> ie to replace the anion AG by other anions,; .. 'i. ayE., tE7 using an ion exchanger.



  In all cases, the term “halogen” denotes -1; : ,, '' r (> r'1cû chlorine or bromine. An amino group dven-.:, 11r ...; rt u! Jstitu? is for example a group of formula ¯ \ '; ;-) 1 ..i, "$ ':" 1,!' ¯: ellE 'R can represent hydrogen or an rf "; 1y (r! c; rboné optionally substituted, for example. r't ilkyle .5vailable: r. ent substituted and containing by, ;;. # ..- .; 1? c 1 12 carbon atoms, such as a methyl residue,. "t \ '': ''.") r0 "'yh' or butyl optionally substituted, a;, =, t <: .rc.o-al% yl, permanently substituted, such as, .r: p tr lohexYl or methyl-cyc lohexy 1 e, an aralkyl residue. '.' " -rj '' 'substituted lltpnt, such as a benzyl residue, or an optionally substituted :: - :: r (-, ¯jsyie, such as a phenyl 0 nnnhtylc residue.

   When these residues bear substituents, it is more particularly a question of the hydroxylic group, of halogen atoms or of the cyano group. The aryl residue can thus carry an optionally substituted alkyl or alkoxy group. The residues R1 to R7 and the residues R9 to R12 represent, when the symbols R3 to R7 are not hydrogen atoms and that R3 and R4 do not each represent an acyl residue, alkyl residues optionally substituted, residues which contain for example 1 to 6 carbon atoms, preferably 1 to 4, such as residues

 <Desc / Clms Page number 15>

 
 EMI15.1
 methyl, ethyl, propyl or butyl are not substituted, cyclo-alkyl residues, such as the cyclohexyl residue.



   When these residues are substituted they contain in particular a hydroxyl group, a halogen atom or a cyano group. The alkyl residues can also bear an aryl residue, for example a phenyl residue, which amounts to saying that they can be aralkyl residues, for example a benzyl residue.



   The residues R1 and R2 can form together, with the neighboring nitrogen atom, a heterocycle, for example a pyrrolidine, piperazine, morpholine, aziridine or piperidine ring. The residue R1 can form with R3 and / or the residue R with R4, and the nitrogen atoms adjacent to these substituents, a saturated or unsaturated heterocycle, such as a ring of pyrazolidine, pyridazine or pyrazoline, for example trimethylene-pyrazolidine or tetrmethylenebyrazolidine.



   The acyl residues R3 or R4 are preferably
 EMI15.2
 residues of formulas R13 - SO2 - or R 14 - Co, -, O in which R, 3 is an aromatic residue, a saturated or unsaturated aliphatic residue or a cycloaliphatic residue and R14 denotes hydrogen or a residue R13. The two remains, acylated can force a nucleus with neighboring nitrogen. R3 or II 4 can be, for example, a formyl, acetyl, propionyl, butyroyl, acryloyl, cyanacetyl, benzoyl or methyl-sulfonyl residue or an optionally substituted phnyl-sulfonyl residue.



   The R5 and R5 residues, as well as the R9 and R10 residues, can form together, with the neighboring nitrogen atom, a heterocycle, for example a pyrrolidine ring,

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 of
 EMI16.1
 pip <ridine, / morpholine, aziridine or piperazine.



   The R5, R6 and R7 residues, as well as the R9, R19 and R11 residues, can form together, with the neighboring nitrogen atom, a heterocycle, for example a group corresponding to the formula
 EMI16.2
 or a pyridine nucleus.



   The symbol Y represents, in addition to the direct bond, preferably an optionally substituted phenylene residue. This residue can be linked to V directly or through a heteroatom or a heteroatomic group.



   The symbol V represents for example a linear or branched alkylene residue, optionally substituted, and containing for example from 1 to 12 carbon atoms, preferably from 1 to 4, which residue can be interrupted by hetero atoms. or by hetero-atomic groups, Heteroatoms or hetero-atomic groups are for example:
 EMI16.3
 
As V1 bridges we will mention: - (CH2) P- in which p denotes an integer from 1 to 6,
 EMI16.4
 -'.- (ï-C, 'H3, -0- (012) 1'- "- (Ci-t) p-0- (CHg..r in which nd {siqn (1 a number from e 1 to 6, -C-CH -a; 2- '- (CH2) ro-CO-CH2.'! "'. I")' - '; H- (Cj -, -CH-NH-CO-CH-.

   The alkyl residue contains

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 generally 1 to 6 carbon atoms, preferably 1 to 3, When R8 is not a hydrogen atom it can have the same meaning as R. '
The B and / or D rings can carry non-water-soluble substituents, and this is advantageous. They preferably contain halogen atoms, the hydroxyl group, low molecular weight alkyl or alkoxy groups, hydroxyaryl groups or alkoxy aryl groups.



   As acid residues A can preferably be considered those of hydrohalic acids; A is generally chlorine or bromine. Other residual A acids include for example those of sulfuric acid, a sulfonic acid or sulfhidriquo.Anions A # are organic ions as well as mineral ions, for example halide ions , such as chlorides, bromides or iodides, methyl-sulfates, .sulfates, disulfates, perchlorates, phosphates, phospho-tungsto-molybdates, benzene- or naphthalene-sulfonates, 4-chloro-benzene-sulfonates, oxalates. myates, acetates, propionates, methanesulphonates, chloracetates and benzoates or complex anions, such as for example that of double salts derived from zinc chloride.



   Belgian patent N 630. 895 describes an anthraquinone dye of formula
 EMI17.1
 

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 EMI18.1
 : r>.: - 2 el- N8 581.785 describes an anthraqui-.: a '! r :; "oP'1ule
 EMI18.2
 
 EMI18.3
 '.n;, 5 which are used * !, among other things, to roof the .., lvry10nltrllp. It is surprising that the dyes of ..;., I <> i, lJ ± s, which are also used to dye the i ':, ¯ =' 1.lonitrilo, have a much better rising power .y -, ...>. hn ,, ¯'Ulcul "'3 fastness to light.



  The reaction of a compound of formula XI or XXIV (> ': f> (. Ur. "' 0": 1rl) 56 of formula XII, XIII or XXX takes place of prf ::: '(' 1C in a solvent organic and at temperatures of - 0 "X +1? iiJ, preferably -10" +120.



  The reaction can also be carried out in medium, 1 Cl! "\ JX, optionally by adding an organic solvent, or a solvent at all, at the temperatures indicated.



   The reaction of a compound of formula XIV or XXV with a halogno-amine of formula XV is preferably carried out in an organic solvent and at temperatures from -50 to +80. The reaction can also be carried out in an aqueous medium, optionally by adding an organic solvent, at either the temperatures indicated: the halo-amine can then be used in the gaseous state, either in an organic solvent or in water. or in mixtures of organic solvents and water.



   The reaction of an amine of formula XIV or XXV with a hydroxylamine-O-sulfonic acid of formula XXVI is preferably carried out at temperatures of -10 to +100.

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   The reaction of an anthraquinone compound of formula XVII
 EMI19.1
 with a quaternizing agent, reaction which generates a compound of formula XVIII
 EMI19.2
 (XVIII) or an anthraquinone compound of formula XXVI
 EMI19.3
 with a quaternizing agent, generating a compound of formula XXVII
 EMI19.4
 

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 is preferably carried out in an inert solvent or optionally in aqueous suspension or else without solvent in an excess of the quaternization agent, at elevated temperature and in an optionally buffered medium.

   Quaternizing agents are, for example, alkyl halides, for example methyl or ethyl chloride, bromide or iodide, alkyl sulfates, such as dimethyl sulfate, mixtures of acrylic amides. and hydrohalic acids, for example a mixture of CH2 = CH-CO-NH2 and HCl etc.



   Reaction of an anthraquinone compound of formula XIX with a compound of formula XX or XXVIII or XXXI or XXXIV, reaction generating a boric ester of a compound of formula XXI or XXIX or XXXII or XXXV, and which is followed by saponification, in the compounds obtained, the boric ester group, then exchange of the -SOH- group against a hydrogen atom or against a non-water-soluble group, is carried out in a known manner, for example as described by
J. Houben "Das Anthracen und die Anthrachinone" 1929, page 449.



   The reaction of a compound of formula XXII with a compound of formula XX or XXVIII or XXXI can also be carried out by known methods, for example according to the German patent application placed under public inspection under No. 1,228,734.



   Reaction of a compound of formula XXIII with a compound of formula XX or XXVIII or XXXI, followed by 'Saponification of the boric ester group in the compounds

 <Desc / Clms Page number 21>

 obtained, then the possible reduction of the nitro groups into amino groups, can also be carried out according to known methods.



   To alkylate a compound corresponding to formula VII in which at least one of the symbol !. ' X and W represent an optionally substituted alkylamino or arylamino group, it is preferable to operate in an inert solvent or, optionally, in aqueous suspension or else sars solvent in an excess of the alkylating or arylating agent, at temperature high and in an optionally buffered medium. Alkylating agents are preferably
 EMI21.1
 - '' '' "c epoxies, eg propylene oxide, epichlorohydrin or ethylene oxide.

   But it is also possible to alkylate with usual known agents, for example with alkyl halides, such as methyl or ethyl chloride, bromide or iodide, with an alkyl sulfate, retort dimethyl sulfate. , or with acrylamide or acrylonitrile or with diviayl-sulfone, etc. The arylation is advantageously carried out with agents yielding optionally substituted phenyl residues, for example with halogeno-aryl compounds, such as halo-benzenes, for example a bromo-benzene.



   The novel dyes can be used for dyeing or printing fibers, yarns or textiles made from polymers or copolymers of acrylonitrile or containing such polymers.



   They are also used for dyeing plastic or leather masses and for coloring the

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 EMI22.1
 t, \ ", r .-;> ;, r 1 <" pste.



  I1 is particularly advantageous to dye:, -iliL; water, neutral or acidic, at boiling temperature.



  ': .. f .. d "<; temperatures greater than 100' 'under pressure.- ¯n 7;' tt then, m4ne without using a retarder, tv¯. nrs'-r'.t.nt a very good unison. We also paut '-.' 'e "r0!' 1 good dyes, with these dyes, on" ur "ixtc? containing a certain proportion of poly- - = r'¯;,; ¯r.lf 'P9 dyes, which have good organic solubility, are also suitable for the =' ":!", Of "'3'",. 'S natural plastics or materials' - "rv., , A ;, d (? Synthetic resins or natural resins ,, u 0U ncn. Some of the new dyes can ".'1; zr excr'nc Îi dye tanned cotton, cellulose prn: 01 0: synthetic polyamides, leather and paper.



  . L r;,;: '; tdt0 that it is also possible to use, with advantage, raises of two or more than two of !; new coierants.



   The dyes obtained have good light fastness and good wet fastness properties, for example good fastness to washing, to perspiration, to sublimation, to over dyeing, to decatising, to water, water. , ironing, bleach, dry cleaning and solvents. The dyes have good fastness in water, they have good stability at various pHs and good rising power. When mixed with other basic dyes they give excellent dyes; they combine well.

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   The following examples illustrate the present invention without in any way limiting its scope. The parts and percentages referred to in these examples are by weight. Temperatures are expressed in degrees centigrade.



    EXAMPLE 1 4.25 parts of a compound corresponding to the formula are heated to 60 in 20 parts of dimethylformamide.
 EMI23.1
 (compound described in French patent No. 1,218,936) and 3 parts of asymmetric dimethyl-hydrazino are added dropwise to this solution. The mixture is stirred for 18 hours at 60-65.

   Then 40 parts of chloro-benzene are added dropwise, at 60-66, which precipitates the dye corresponding to the following formula
 EMI23.2
 After drying, this dye is in the form of a crystalline purple powder, which dyes the polyacrylonitrile fibers in shades of pure blue having very good general fastness properties.

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  EXAMPLE 2:
4.25 parts of the offset body used in Example 1 are introduced into 20 parts of pyridine. The resulting mixture is boiled under reflux for 12 hours. After cooling to 60, 20 parts of chloro-benzene are added dropwise: the precipitation is then observed, in the crystallized state, of the colorant corresponding to the formula
 EMI24.1
 By recrystallization from dimethylformamide, the dye can be obtained in the pure state. It comes in the form of a purple powder that dyes the polyacrylonitrile fibers in shades of pure blue, very strong and very vivid.



  EXAMPLE 3:
4.25 parts of the starting material used in Example 1 are introduced into 22 parts of triethylamine. After editing 5 parts of dimethylformamide, the mixture obtained is heated for 36 hours at 120-1300 in an autoclave fitted with a stirring device. Then it is allowed to cool to room temperature and 30 parts of chloro-berzene are added dropwise to the dark blue suspension, which precipitates the dye corresponding to the following form.

 <Desc / Clms Page number 25>

 
 EMI25.1
 It can be recrystallized from dimethylformamide. It is obtained as a purple powder which dyes polyacrylonitrile fibers in solid shades of pure blue.



  EXAMPLE 4:
4.3 parts of an anthraquinone compound corresponding to the formula
 EMI25.2
 with 1.9 parts of boric acid. This mixture is introduced into 22 parts of 96% sulfuric acid, cooled 20, then introduced, at the temperature indicated, 2.5 parts of a compound corresponding to the formula
 EMI25.3
 operation at the heart of which it is necessary to cool the reaction mixture, the mass is then stirred for 12 hours at 20, then it is introduced into a solution of 11.5 parts of sodium sulfate in 100 parts of water.

   Using known methods, the first sulfonic group contained in the reaction product is removed and it is saponified by

 <Desc / Clms Page number 26>

 
 EMI26.1
 1. <; 2, qr "Uf) e of boric ester, then the" 1f'C; -. "} 3H is removed. A blue violet powder is obtained which 'r.",'.] U0 (J dl. Dye corresponding to the formula
 EMI26.2
 
 EMI26.3
 By das known dyeing methods it is possible to c. t '1Í!:, .tvc this dye, on polyacrylonitrile fibers, "s nuz ;; << deep pure blue. r! :: l'f' 1! ii 1> tr, dissolves 4.33 parts of the compound obtained z 1 <.: "" "., 1j le 4 in 40 parts of chloro-benzene, at temperature; 1 <ir <; 'r ,, al¯lition. To çetto 901utio1 we add drop to Y ',': t0. Ref: A little, a solution consisting of 1.38 parts of dimethyl ethyl and 4 parts of chloro-benzene.



  The mixture is refluxed for 3 hours and> 1 ri. rwniic the solid product is separated by filtration cl, iud 0t it is washed with hot chloro-benzôno until '"uc: .0 lir; uidc which flows is colorless. The dye has, r = xr>': 1w ^. Responds to the following formula
 EMI26.4
 It can be recrystallized from dimethylformamide. After drying it is in the form of a blue violet powder which dyes the polyacrylonitrile fibers in shades

 <Desc / Clms Page number 27>

 deep pure blue, having excellent strength.



  EXAMPLE 6:
If 4.33 parts of the compound obtained according to Example 4 are reacted, dissolved in 40 parts of
 EMI27.1
 nitro-benzene, a temperature of 60 to 10, ': ec, du'. Methyl chloride, until no more precipitate is formed, the same dye as in Example 5 is obtained.



  EXAMPLE 7:
4.3 parts of the starting material used in Example 4 are mixed with 1.9 parts of boric acid.This mixture is introduced into 22 parts of 96% sulfuric acid, cooled to 20, then introduced at this temperature, 3.2 parts of a compound corresponding to the following formula
 EMI27.2
 A compound which was prepared from ss-dimethylaminoethoxy-benzene by quaternization with dimethyl sulfate. The mixture is stirred at 20 for 12 hours and then added to a solution of 11.5 parts sodium sulfate in 100 parts water. After cola the reaction product is treated by known methods.



  The same dye is obtained as in Example 5., EXAMPLE 8a:
By operating in the manner described in Example 4, 4.3 parts of the starting materials used in this example 4 are reacted with an equivalent amount of a

 <Desc / Clms Page number 28>

   composed of formula
 EMI28.1
 Cn obtains the dye corresponding to the following formula
 EMI28.2
 
It is in the form of a blue violet powder which dyes the polyacrylonitrile fibers in deep shades of a pure blue having very good fastnesses.



  EXEMILE Pb:
The dye obtained according to excmple 8a can be reacted by the method described in example 5 or 6, in order to convert it into a dye corresponding to the following formula
 EMI28.3
 EXEMFLE 9a:
4.33 parts of a compound of formula
 EMI28.4
 

 <Desc / Clms Page number 29>

 one of sulfuric acid and in the presence of boric acid, it was felt to react, by known methods, with a compound, corresponding to the following formula
 EMI29.1
 
In the compound obtained, the notro croups are reduced by known methods. The colorant is obtained according to the formula
 EMI29.2
 which dyes the polyacrylcnitrile in shades of blue having; good solidities.



    EXAMPLE 9b):
The dye obtained according to Example 9a) is reacted by the method described in Example 5 or 6 in order to convert it into a dye corresponding to the following formula
 EMI29.3
 

 <Desc / Clms Page number 30>

 
 EMI30.1
 We put 15.4 parts of the compound obtained '' .'- ".. r5v: c 5.6 parts of sodium hydroxide, in - .--.,:" '2 parts of water at 0-50 and we introduce, ', -;' part? hydruxylamine -0-sulfolOn 1 ':' 1 anc for 1 hour at 0-5, then there. <..%;?. 1 '! E30, Cn filters the solution.

   We obtain, fl. '11 t ["'u'? ' Example 1. 15.4 parts of the compound obtained - - -ri, <4 are dissolved in dimethylformamide and '' ", '- -; - Lv tr. for 40 minutes, at a temperature. ".:> <., -.,., where a gas stream was chloramine, 1 ',.: -. r.',, ... nitrogen, gas stream that we can obtain r -r 0'q) ': \ ;, l (' cie! 'the strap described in "Inorganic Synthetics", -.fo i; r.'] 0 9Jé. The reaction solution is then concentrated. . of 4i'yo pous60, under reduced pressure; it is washed: r ";, rj]) 'VOS of chlonobenzene ju squ 1 so that the liquid which,.' is at: 3n,: :) it colorless. After that it is washed with nro10 pt ether and dried at 600 under reduced pressure.

   The dye thus obtained is identical to that of Example 1, EXTTLE 11 a):
If we replace, in Example 4, the 2.5 parts of the compound of formula
 EMI30.2
 by an equivalent amount of a compound of formula

 <Desc / Clms Page number 31>

 
 EMI31.1
 . and that we operate, for the rest, in accordance with the indi. cations given in the example in question, the dye corresponding to the following formula is obtained
 EMI31.2
 
This dye dyes polyacrylonitrile in shades of pure blue.



  EXAMPLE 11 b):
The dye obtained according to Example 11 a) can be converted, according to the indications given in Examples 5 and 6, with dimethyl sulfate or methyl chloride, by dye corresponding to the following formula
 EMI31.3
 It tints polyacrylonitrile in shades of pure blue.

 <Desc / Clms Page number 32>

 



   The following table I shows the structure of other dyes which can be obtained according to the indications given in Examples 1 to 11.



   The symbols K #, T, Z, W, X1 to X, in the formula
 EMI32.1
 have the meanings given in the table. As anions, one can consider those which are mentioned in the description.



  The symbol K + can represent any of the remainders mentioned in the following table A. These groups can be exchanged, without difficulty in each of the dyes, for another of the groups indicated.

 <Desc / Clms Page number 33>

 TABLE A
 EMI33.1
 'r S p, u +' represent the sycholoa K1 to K2? ' lao remained X1 at ::,: '7; isr; <gromt the following groups:
 EMI33.2
 roprôsonte µ5 J (i ') "? ¯. a- N (± 2ii) ¯ (? [rice)'" juf 2'5, -N (C2H5) 2 C41, "'µ2 1 -0 K5" -N ( C2H40H), Cii.J CH,, ;; 6, "-N (C2H, + OR) 2 CH s --CH20H C2H5 92H4-CONH2 8 es -N (CH3) 2 CH2 .--. # ..- CH2 ltf> Kn" 1 \ T ./ 2 2 'rJ .l9 -., "CH2 - CH2 /', J z '/) -re K10 #M \\ ss -N -1 1 \ 1 Et) K 11 Il -iI 1 C fl3 K12", .. N : J CH,

 <Desc / Clms Page number 34>

 
 EMI34.1
 7 "7.te - I X q 3 ..

   Or \ 4..corrx 2114-CON112 r j j \ -J 'c2H4-CONH2 l'il,) C ii -CoNil c2H4-CONH2 ::, -: // 0'. ..:, 8'1 \ l Ci) - (CH3) 2 i'TH2 ', ôz "(02H 5) 2 Je> 1 252 r ¯N (C40Fi) 2 Jazz llli2, 2 Il #J] IdH2

 <Desc / Clms Page number 35>

 
 EMI35.1
 K23 represents -N HO NH..¯2 z24. X24 -19 1 HD NH2 K25 -C2H4-CONH2) 2 z25 1. 24 '2 2 NH2 K 26 "-N (c2H4-CN) 2 NHg CXf çx' CH O H 2 - *, CH 2 CH2 K2" '' '"-N 2 N Cil2' 'CH2 CH 2

 <Desc / Clms Page number 36>

 TABLE 1
 EMI36.1
 "-. Shade of em la teine" 1 X2 3 X4 '5 turo on polyacry-.



  ######### -.... # ....-. ¯¯¯.¯¯¯¯¯¯¯¯¯¯¯¯¯ lonitr.lc -12 K2 n, 1! 4- 0 fijH 2 ÎiX "H eu 13 j, '3 m 0 (P do cf df d dP d dl 1:, j <f dl du d3 d3 dQ do (f 15 Xµ 0' do tf cf d fjp (pz 16 bzz d '0 d dO dp d dO d "cp 1 t> + do dl dl d dO dO dO' 1:, r, R" 0 e do do (f dO dP cr dl 19 0 dddddd cp r; .. ,, 1H-f -H dl dl bzz 21 2 Ù: iFi2 h'Fi4 ..,. / '. Cf d ci d blue 22 Il;, <bzz c' lOE- d cP d 'dd blue shooting CH rant on i; ..yj 5, -CH the green 14 "" '{D'3 dO dO dD r :.'? '-Pifi-f TOCH3 d' (f <y dP dP dP 1. '".-i3Fi.-. .r cP? o 'd' d blue F "> 1,"> id dl cf dO do Cr 17 J ',., d5 t1- id L1- CI- law 1> 1 q dl Q cP cr Q do "= r '(C # C) <' ¯ I ro 4 'di cP! 3 Crp de F.; .. C ll d dP cp dO r' <¯ CJ ..

    '1- <P 4 d d (f?> Μ' '1 d' (F cP dl 'do cf dP dP (P dl,'?? TP d dP (f

 <Desc / Clms Page number 37>

 VLAU I (Continued):
 EMI37.1
 '' ", X.) ,,, '\ 1 5. 6 Shade of" X the turkish them 1'0 1 ye.Cj (..



  ..¯. ",.. = ....,., ...,.,. W 1 oi t ri 1 e '." , I ",, - 2 -on H fI 11 H blue. Z 1 {J 1.1 '(-P # do dp llÙ r 1 ri' 1i d If dD cl 1" '. 1¯> ¯: "S da dl da ep do (fi de wJ .'...., riJ ES (1 '(P (P i Q d dl 0 4 S (p dP dO cI' CI d tp '"2' '' '3 G Gi # (i (fi dO (f cfJ fin a3 iô, z S do un el "(fi el" (fi do dO tes '3 l' S dO d 'c'1' i and 'iP d' dl 45 K7 S dl , 4i c'1 'cF d' d cf!, D 46 1 \ 18 v'fJ S duc do do dO (p dp (P H3 42 K ,, -C1I2-CII- 0 do du dO d 'd do do de 4th A2 0 d (f cP do dO (f 'dP 49 K ", 0 fil 0 dO U' rd vs d" tl- 4¯ # 50 'l'? 1, ls 0 dO C dd 'du (P cf F 51 K "'3 0 dl (pd du dc Cp 52 K7 -y 0 Ct' d <f dl dO cP 53 K18 0 de do d do d dO dO 5L K10 0 cP, cP cf cf dO d dO do 55 ri ^ n d1 o dc cP cI 'll- P c'1' c'1 'tu 56 KCJ c "0 4 it- d' d dO dD dO de 57 Y.:.4:

  "" 0 do # dP do CF + cP 58 K -C2-CH2-CH2- 0 dO Cr do d 'dO cf Cr 59 p 0 duo dd to d' dl Fa0 K "'9 0 dO fd 1 i cf dd 61 K23 0 dO Cr (pd cT ddd

 <Desc / Clms Page number 38>

 PLEAl I (continued
 EMI38.1
 X, X X X Xc X Shade of the dye on polyaory- - ¯..¯. lonitrile \ "C -Nli 2 - Nii 2 -0X 11 11 H rI blue iF d '(f cf zip dd' dl 0 lP cd ci 'cf fi d3 dl cPtPcPcPtf cp" "1 -j]" l'? l, "1 fF dl, dl 1 c" dm Cr 0 d 'd' ü- Ct 'U- 41' ti- 0 <f (fd <'(j (p (fcp (p Ocfcf <P (fcf'tf (p dl z.! tzar1 "" v "l, ^ 4." t "lez do W 4- U-" ü ü- 1 "<'Jlgi dl, ll- 1- ll' (pde î3 <3 d '( p (pid & i 1 7 "'" Cà "" ir dl d' (p -CE 3 (p '"' 3 dl> -CH 3 0 d 'Cr (f dl zur 77 h.1, s - .n-CH- 0 Cr O (ß 'Ci C Cl dO dl Cli,' '-4' due du -.Cx3 dO 0 dO dO d (f <p H 3 '3 r.,' $ fl, d dO -CH 3 Si 11, jQ 'Cjll:

  p duo (r dO dO dP H do d 82 '-2' 0 dO d d dl dO dD df <f 1 (,, d "dP dP Cr Cr dp dO 9 dO dl dl d" dl dl du dl

 <Desc / Clms Page number 39>

 TABLE 1 (Continued)
 EMI39.1
 Example- KTZW X1 XX ww X4 w vw X5 bzz Tint of pie dyeing on Nt 'polY8cry1enitrile 85 Ki ... cZH4 o -NH ::: H3 -NH-CH3 -0H HH -C) H blue fading green 86. .c! -L..cH- 0 dfi dC 'dd dO <JO dO dO CH 87 K10 -C2H4- 0 -: 1 .. dO cio dd ..CH¯ dd 88 K 11 d 0 d dO ddd dō3 dd 69 K13 d 0 dO d dO dO d "ddd 90 K 18 dO 0 dO dO dO dO d 'H - <X :: H 3 dO 91 K19 dO 0 dO dO dO dO dO da do 92 IL d 0 -NH -C III ..hH.-C2H dd 'do d dO d, MK dO 0 -N -N ddd Br H blue) 94 K10 d 0 ddd dO d H Cl de? K'2 dO 0 dddd dO Cl' -Cf "J d; / 6 K8 dO 0 d dO dd dO H (; 1 .., dO 37 Bzz dl '0 dddddd d') do: 18 K, d" 0 dO d é d.

   Br d H d) 0 -CfL? ... p- 0 dddd Cl Cl dd '7, (' JI 00 K -C "HA- 0 dddd Br Br d de ç 'K, Q" dc 0 d dO dO gy H dO dO do <t1 K10 dO 0 dd dO Cl d H dd - S3 -! O 0 to dd vr d Cl dd 'r Y'? - 4 d 0 d dO ddd H dd C- ii; di 0 dO -OH d HH ddd - () / 2'i-cy- 0 d dl) dddddd - "3 r'i '<, .... c" - 0 dO d dO Br d "13r dd

 <Desc / Clms Page number 40>

 TABLE 1 (Continued)
 EMI40.1
 pic V (z X 2 X3 X4 x5 X Shade of the f 'dye on polyacryloni- -17 tria: \ 4.' (: 21-: 4 -'H: 2 -OH -on HHHH blue 100 'g zur do do do do do do do 110 Y.9 dO 0 do do do do do dg do do 111 K 10 dO do dO do do do de do do 112 K11 dO 0 do do do do do ddd 113 12 j 0 dO dO do do do do do do 1 14 K13 d (\ 0 dO do dO do do do do do 1;

   !; ^ 4 '0 0 do do do do do do do do' do, 16 K-'5 do p do do do do do -CH3 do do 117: h '' 3 0 do do do dO do H, o do 11 ? 17 "" da de do do do do do do, 19 K; qr: \ 0 dO do do do do do -Ci: 3 do 1? C 1 <.1 ') rP do do do do do do H dO 121', n, ':' dO dO do., 'do do do do do '' 2! 0 d do do do do do do do f rO du do do do do do do do 12 <1 I:,) J '' "<1" l'jO do do do do do do do do 3 = 1 - ", 1 ù '"è" dO do do do do 00 dO .2 ". 'L' C dO do do do do do do do .- "" en do do d do do do '"0 dO d do (\ 0 do do do do do', ... C: ', -N!': 2 ¯Nf2 dO d do do do,. Rv '} "' - '"' dO dc do u do dg do do 'J (JO rie. D do, 1-10. R do do do' '' 'v ,. "" dC do do do dO do do 0 è "CO do do do da do do do do dO do do d do do

 <Desc / Clms Page number 41>

 
 EMI41.1
 J'M3LEN :! (Continuation and end)
 EMI41.2
 lx #, - - '' '1 1'! y y y v v rl;

   
 EMI41.3
 
<tb>
<tb> dye ';' ''
<tb>
 
 EMI41.4
 p1 :: 'ly! tGr' / Jn ...,, ... ##., .. ¯ .. .... ".., .....,., ....... ¯¯¯¯¯¯ nitrile '..., ¯ .. Ti ... r, ¯.: E .. # OH'1 HHH dlIVSJ â E'i., Ki'a "0 1-J d ^ - ,: 3 ", '' addc or 1 nt F ;?, 2Î K .." r- d dO <1 r1 dO dO ft,>. tio d J '"d ¯ d Or7' -" "'..,,; (.' 7 = dC> aa" "v H ..f'.U '' '' 3" ...., '" qd; 1 dn to do H d

 <Desc / Clms Page number 42>

 
 EMI42.1
 Gr; sscc has 1 ,,,, Idat) t albeit every day, on urm 'in #mosCy to the formula
 EMI42.2
 
 EMI42.3
 "': ê - \' <11'6 in .'ai; att react 36.9 parts ri ur6 r, acjir 36.9 parts
 EMI42.4
 itself described in French patent No. 1,218,936, with
 EMI42.5
 L ::,. 1 \ "'1:' tl .., of -hYdroxym6thYl-amido of the oxactic acid) a,. ',; r U :: Tli.itinn constitu60 do dimdthylamino ot de nitrohanzènc.



  After reacting, the filtrate is concentrated under reduced prossian and the dye of formula is precipitated.
 EMI42.6
 by addition of methyl alcohol. It dyes the fibers of

 <Desc / Clms Page number 43>

 polyacrylonitrile in blue shades having good fastnesses
 EMI43.1
 general. /,'.;/g .Il, 11 ';.,;. , l / '"Ù (EXAMPLE 142:') '.,' l, ¯ / [/ ¯; /)) = j
12.3 parts of a compound of formula are mixed,
 EMI43.2
 with 8 parts of boric acid. 22 parts of sulfuric acid are added to the mixture, cooled to 200, and 6 parts of N-N-dimethyl-3- are added dropwise at this temperature.
 EMI43.3
 methoxy-benzyhamine.

   The mixture is stirred for 5 heights. By known methods, the boric ester group is saponified in the reaction product and the second group, -SO3H, is removed.



   The dye obtained, which corresponds to the following formula
 EMI43.4
   Tints the polyacrylonitrile fibers in blue shades having good overall strengths.

 <Desc / Clms Page number 44>

 



  EXAMPLE 143:
Has 8 parts of a compound of the formula
 EMI44.1
 dissolved in 130 parts of sulfuric acid a drop is added
 EMI44.2
 At gOUtt0, A15, 8 parts of N-N-dimethyl-3-methoxy-benzylamine 5o! - ition in 90 parts of sulfuric acid at 96 x. We stirred 1 o rr ,. '? . :: - go ndsnt 1 hour at a temperature of -20 to -25. The nitro group is resolved by known methods and isolated
 EMI44.3
 the c010rant which, is identical to that of example 142, EXAMPLE 144:
A mixture consisting of 4.3 parts of 1.5-dihydroxy-4.8-dinitro-anthraquinone and 6.5 parts of boric acid is dissolved at a temperature of 25 to 30, in 110 parts
 EMI44.4
 ct 1 (1cid (concentrated sulfuric acid and cooled to, .. 5Q.

   To this temperature are added dropwise 3 parts of NN-dimethY1 3 .-, xy.-bnzylamine, Or) the mixture is stirred for 1 hour at this temperature, then the nitro groups are reduced by dosing. known methods and the dye, which is identical to that of Example 142, is isolated.



   By operating in the same way as for the preparation of the dyes of Examples 141 to 144, it is possible to prepare the dyes indicated in Table II below, They correspond to the formula

 <Desc / Clms Page number 45>

 
 EMI45.1
 
 EMI45.2
 'the,' '. in which X7P Y, 8, V21 'if Z, R and F have the meanings8 in which X7', V2 'W, Z, R and Font 1 & $, a: n1ficat, lon8; <> indicated and the core B occupa., on the nucleus anth to which i no nu 0 the positions indicated in this table II, The 'symbol, fez' can ",. represent any of the rastes Fl to F Cits tana ':.' '' ' -. ' :;. i ".-.:. Table B.

   These groupings can be exchanged? -. San $ jazz "diffiçul t, in each of the dyes, by another dQ8, qrou-ements cited,.) ..:"), "," .- '1: j'? " ". :. ; ' '..: -f., l: .. ": ..- .. i"; '' pemants c.tés, TABLE.AU AU, J: z '' '.i.v :,'., "The symbol F can represent .le ','. Y1nbo: le! '.



  F1 to F 13 'the latter designating las .gxaupemcanta.'suivarita s.' 'i. ; Av. ¯ ¯y: '1' ,, ..



  , '::,.' -., ':,; \; A:;:,.,: ": .. J ....
 EMI45.3
 



  CH ', ... # !: t -'--.'. '' ,. '..' y't, - #. ' represents represents - \. ;; r .'.... '/ .'.-....



  "" CH3 ". '.



  -.oN? 8., '2 cli'. "'..'. '' ?; ':' '.'., '' '"'% "...'- ';' '' '' ' t "'',.'..'- 'Thread'. ' C H, ",. ::.,;",: ,,,.:; 5 ,, CH '\. -. '..! "' '-.!:' -; i'j: '' '. * -.



  CH 31 ...; '.'...' t '";:" :: -' 'v ,,;,.: 1 ... -.



  F - ''.,.,.,. ";: ';'," ....,; :: '. "" LV ('Ir1;' .il ',' e ;;,.,.. ".F, i, .ze, il '' '.' ;, ::. ¯ -",., - ;; J1) (C 3 - ".'-, ..'.-.:; X: .fi ... r

 <Desc / Clms Page number 46>

 
 EMI46.1
 7 r4-i, present -NH-C3 H7 N,. CH2 'CH2 p. CH2 CH2 r 'a -NI-eCH2 - CH2 CH2 - CH 2 F ".rJ' '' GH2 CH2 ,, CH2 '0 GH2. GH2.' '2 H2" 11 F ..N ,,.

   CH3 CH4pH 13 ^ Iv 1/24 "OH C2H4 - OH

 <Desc / Clms Page number 47>

 TABLE II
 EMI47.1
 1: xem- Posi- v x x z fl, Îl '' Nancëàé lA ple tion x, z; Nuance ple tion>. '' "" '' taànture on "N of t * inture on jt, ¯ nucleus ¯¯¯¯¯¯¯¯¯¯ 'nitrile 145 F2 2 -CFt2- -NH2 -N1,. (f, 0 rCH3 vS blue ¯, 146 F22 do do do do 0 .5 'd 1 v 147 F3 2 dd do do 0 -CHg do 148 F4 2 do do do do 0 do do "Il 149 F do do do do de do' / fil) / , # 149 d? - 't-' ^!:: rv 150 F2 6 d * do do do 0 -W-0 do 151 F 2 do do -Cti..H do 0 -CH3 blue tiTlht e4tT the green 152 F8 2 do d -N "2 'de 0 4. Z blue 1 b3 F2 9 ddd do 0 d do 154 F2 10 do do do do 0 CIO do, ¯ ¯. ¯ .;, ll] 1 ;; = - 155 Fil2 d dO dd 0 do do .., x.



  156 F122 do do do do 0 do ',, do 157 F13 2 d do d d 0 dO; do, '. <'/ 1' '158 F3 1 dd de d 0 dd "y,' 't." ¯.¯ 159 F 1 3 dd zou d 0 do Violet 160 Fa 3 do do do d 0 dd 1 bowl F 2 -CH2 -NF4C-CH2m d -IVH-CI- (2..CFE..CFi3 d 0 of blue drawing on 0 OH 1 the green 162 Fic2 d do NH-CR2-CH-CH3 do 0 'of de. I # i. ..j;, J * OH ¯ '; $ j> ¯, 1;

   1 163 F1 2 ..C1- (2 .. do ± / H d 0 °, de 164 F22 dd "" .3d 0 dd '"/ 165 F 2 dd ¯ \ d 0 d .. d' i b6 F1 2 -0 <F-CHj- d -Nh 1 ... / d 0 d "s' blue:.

 <Desc / Clms Page number 48>

 TABLE II (Continued ot end)
 EMI48.1
 Ex; n1- F Posi- V2 W X7 X8 ZR Tint of the pie tior dyeing on NC 'of polyacryloroyl u nitrile Tu, ¯ ¯ ¯ 1 67 F 2 -cf-0 <H-CH- -NFh ..1IH: 2 -pHO -CHL blue 1 f.8 F ,? -C2H4- ddd 0 dd 1 F 2 ..0 - (;? C.-Cli. DO d N 0 dO d CFi3 170 F1 2 ¯Cl2-HN-O-CH ...... dO Î dd S dd "o

 <Desc / Clms Page number 49>

 EXAMPLE 171:
15 parts of the starting body a) used in Example 141 are introduced into 60 parts of asymmetric dimethylhydrazine, at 25-30.

   The suspension obtained is stirred for 18 hours at 25-30, After removing the excess of dimethylhydrazine under reduced pressure, the residue is extracted with nitrobenzene, the solid product is separated by filtration, washed with petroleum ether. and dried at 60 under reduced pressure, thus collecting 15 parts of the dye corresponding to the following formula
 EMI49.1
 
This dye is in the form of a violet powder which dyes the polyacrylonitrile in blue shades having good general fastnesses.



    EXAMPLE 172:
10 parts of the chloride of formula a), mentioned in Example 141, are shaken for 36 hours on a shaking machine with 40 parts of a 30% ethanolic solution of trimethylamine, the solution is evaporated to dryness, the residue is taken up again. the residue with nitro-benzine and stirred at 80.

   The dye is separated by filtration
 EMI49.2
 purified, it is washed with t.ol, u.ènJ: .- Ai "-..., .. t; -l.! - li! r: .. I \ 111!: 'o ---- - .... - -:. p --4 '-: - <. - 1 -, ¯uu ", lltIJIli, JII 11. reduced pressure. ol * omo

 <Desc / Clms Page number 50>

 
This dye, which meets the following formula
 EMI50.1
 
 EMI50.2
 this a violet rOUdN which dyes the polyacrylonitrile in blue shades having good general fastnesses.



    EXAMPLE 173:
10 parts of compound b) obtained according to Example 141, with 5 parts of sodium hydroxide, are suspended in 400 parts of water 0-5 and introduced, all
 EMI50.3
 by crushing, 12 parts of hydroxylamino-0-sulfoniqua acid. The mixture is stirred for 1 hour at 0-50 and slowly heated to 30. The solid product is filtered off and dried. By extraction with ethanol, the same dye is isolated as in Example 171, except that here the anion is the HSO4 # group.



   The same dye is obtained by reacting with chloramine 10 parts of compound b) obtained according to oxample 141, For this the compound of formula b) is dissolved in dimethylformamide and passed through this solution for 40 minutes, at about 30, a gas stream consisting of chloramine, ammonia and nitrogen.



   You can prepare the same dye as
 EMI50.4
 -44 #, qu.> S-ét ± Jb Tn'-y. o * kon -> 'where this # rRp &>. ii'-Qhr, di ù to 1 1.ru, t ###

 <Desc / Clms Page number 51>

 
 EMI51.1
 . ,, ... ,, - -. ..; . ,. j 10 parts of the compound of formula b), obtained according to Example 141, in 280 parts of nitrobenzene, add dropwise, at the temperature indicated, 7 parts of dimethyl sulfate and stirring the whole for 2 hours, the temperature then rising to 120.

   The. dye which precipitated, washed with nitrobenzene and toluene and dried, The anion then obtained is the group '
 EMI51.2
 CH3Sp4 Q, '<' -.....,. ¯ ::, ¯ - ¯..¯
 EMI51.3
 By operating as described in 198 "xej <., 171 to 173, the dyes mentioned in Table III below can be prepared. These colorants correspond to the formula
 EMI51.4
 
 EMI51.5
 in which the symbols K Q, p vlp Z, R, Xi at; 'ènt Àes j 4 y ¯ meanings given in Table III and the nucleus B occupies, on the anthraquinone nucleus, the position indicated in this table. As A # anions, it is possible to envisage those which have been mentioned in the description.

   The symbol K # can be any of the remainders K1 to K27 previously mentioned in Table A.

 <Desc / Clms Page number 52>

 



  TABLE III
 EMI52.1
 Exem- Bsi-. Hue of the ple K tion 'J1 ZR, X1 XXX tincture eur dia polyamloni-' 'of the poiyacryioniyau triie ¯¯¯¯¯¯¯¯¯¯3¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ## .. -... # ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ 174 2 -CI-'2- 0 -CH3 ¯H -NF -OH HH blue 175 K 2 d do -C2 H5 duo do di do do do 176 K4 2 do d -0 do do do do do do 177 K5 2 d do -CH d do do "1 do do 178 ç 2 do do do do do do dg do 179 K 2 ddddd do d do d 1SO K7 2 do d do dl do do do do do 181 Ka 2 do do do do do do do do do IE2 K 2 dddd do dn duo d do z 83 K10 2 dddddd dru dd 184 Kil 2 ddddd do d de z 1PI5 K12 2 ddddd do do do do do 1 Ph y13 2 ddddd du de d 1 Q7 K14 2 do do do do do do do do cio 1f'8 le 15 2 do do do do do do do du do 1 8, Q Yl 2 do do d * do du do do do do 1 -aU y17 2 dd do ddddd do 1 1? 1 Y18 2 d do do do do do do do do tu Ki f)

   2 ddddddddd 193 Y, 0 2 dddd do dddd 194 K '?. 1 2 ddddddddd' 9¯> .2 do do do do do do d do 19 K,., 7 2 dddddddddt g7 '4 2 dddddd dO dd <. > t> y, 2 do d do dd dO dO dd 199: ¯5 2 do do do do do do d do do

 <Desc / Clms Page number 53>

 TABLE III (Continued)
 EMI53.1
 ixem- @ Pos 1- "** '###" ----- ## ple K * tion Vl x X; 7t t.nc.d.



  NO of 1 X2 bzz; dyeing on poly4cxyl.on core, trile core B ........- ..,. .... .. pol yacrylonjtril "200 K27 2 -CH2- 0 -CE. NH2 NF, 2 -01 H Mhu 201 Kl 2" .0..0 (- ,. 0 do d- d- d- d- do 'do do 202 K2 2 de dO dO do do do, dO 1' d .de 203 Kl 0 2 d do df, do ci * do d "o ¯1 d 204 ((13 2 do CIO do do d 'do 'do>' de "" do, 205 Kl 2 do do do do do do do, ¯¯ "do, x.? /" ¯. '206 K20 2 do d de do do do - back de! "v .: j '".' '¯ (, 207 K23 2 do do do do do do -d" "- d' '; .'-.''- 208 Ki -Ci'.Nt'fC..C, dd 'd- d "d" 4b d9 ,,' '.



  0.;. . . '', l. ,. not a word; ¯; ¯; j,, 209 K2 2 d .dd, do d "duo dO ,,. do'- de 21 p K 10 2 d do do d do de, d,, j. ¯ dQ d 'A" Y'y', '' 5 '211 K2 do do do d do dd *' l dô 5.,;,. .i 'b,' a-'v.



  211 .....



  212 K20 2 d do do 'do do do de, -. R, â.J7 do 213 ff24 2 d d d d do d do', ¯¯df ,,. d; . ', = l' = ,. ¯; , "l 214 K -CH2- -CXj 0 dQ do do" 215 K2 2 d- ddd "do d * dr, do do /,'g¯;1¯,.g'/ ¯ 21 K 10 2 do do dO (JO, do, dO / die "'4f i) ¯], do' j9 '" 217 K1g back; ¯ ¯ ... ¯. Jj;. ¯¯., J.; #; J ,,,., >,.



  21 K 19 do d d do do du -d9 de 218 K23 do do du d d de 'do d du.,. 'Î ..> il J. ; 219 K1 2 -O-C't-CH- -CH3. do dO do d do ", doÀ CH3 sYj" '. ,, Â'r', # '.j, 1, 220 K2 dddd de d do ft do 220' de Ber '¯ d / q / 1, = .. ¯t, ry,:, 221 K10 2 do do d9 'd .d do J' do ', Iü =. 1 a: 222 K d d d d 'd .'d; ; df,,; . back ¯; ¯4 (<.. 1 (,,:,.; '] il; .. "." ,,, Î.; 222 K 12 2 do', 'do do .. ...-- I '.-... ";.;:;.;.", s, r, ririi --223- -'KQ 2. d -' ## - a 'd do' do

 <Desc / Clms Page number 54>

 TABLE III (Continuation and end)
 EMI54.1
 EX; - 1 <s 1- pl 'K r * ion V1 Z R W X Xr, X X4 Shade of n ¯> i; the tincture r,}. ,;

   on polyat <rylani xil 1> 0e4 x3? -O-CH-C- 0 -CH -NH. ... NH..2 -.3HH H blue 1 CH3 2 1 \, -Cfi-tlH-C-CH..2- dddd dO d "dO dO o 226 K 10 3 ddddd dl! D - dO dO 277 1 <'19 3 ddddddddd 22R 'S> 3 3 ddddddd dO dO.



  229! C? 2 -0-C ... c1.t2- dd -NH-C ... NH-CH3 d dO d greenish blue 230 2 dddd * ooNH- @ dddd 231 K4 2 ddd dO ooNH .... cH3 dO ddd 232 K'0 2 dddddd do dO dO t33 17 dO dO dO da dO da <> do dd 2.34 K 2 dd -CHg -NH ..NH .-- QCF da d dtl dO 235 1 \ 1 2 dd nC H - d NH - CH3 dddd C? - jH3

 <Desc / Clms Page number 55>

 
 EMI55.1
 - '' ':,; r; r, t, '"' '' 1, '1 l ....; \' .. t ,, - ':" ,; . "":

   EXAMPLE 236: ßr "., ... ',, yr" r; ,, "' é''r, ')'; ji,;." 1 "., {> ', In 227 PE # tf, S of Chlci: rqZ' <:: '9 :; r' ':, suspends, 70-80Ct, 22.7 parts'd'Hn tbpo. s (i6pÓn ':'. ': "put suspeflsi nS fÎ' '\'" "'' f ::". "'." - <>. ::'; i.-: ', .. {,, .t: L,}. l ,. before the formula. ''. ¯: '\; \ /' i: '::' '1' ', ..:' 'Îr' +;:, .Ii . ::;, \ t''1 ', 1 {) "$ 1 $; ..,
 EMI55.2
 
 EMI55.3
 compound which was prepared by the method described by J 'Houben'. "Das Anthracen und die Anthrachinone" 1929, page 449 / from 27., 5 parts of .I.S-diaminv-.8-dihydrox acid. srtthcacuinune-3.7-disulfonic acid and z.4.5 parts of Î-phenoxy4, aminoEben, zene and then removing the -SO H group by.) s known methods. 4 parts of pyridine are added to this mixture, then 6.2 parts of hho- 3 are added dropwise at 70--800. cliloracetyl ride.

   The mixture is stirred for. 3 hours at 70-80 and the product formed is isolated by evaporating the mixture under reduced pressure, by triturating the residue with de.'Ileeu ¯., J, "and by filtering. A compound is obtained responding to formula: 7 formula. ..1 next. ' ¯.ïï ..;,; ,, "', <, v., 4, 4. .4 "" r ;, r,,. ,, ¯: '' "f ±" H
 EMI55.4
 
 EMI55.5
 It is dissolved in 150 parts of dimethylformmldi at '90 "- and to this solution is added 6 parts of di! T1'-thÚ'Ctailn .:', '> L" ".; ..1' ::. .. i ', 1 ;.

 <Desc / Clms Page number 56>

 asymmetric. After stirring for 12 hours at 60, 300 parts of schlorobenzene are added dropwise to the mixture, which precipitates the dye corresponding to the formula shown below.
 EMI56.1
 



    Or) separates this dye by filtration, washed with tolun and dried at 60 under reduced pressure. The violet blue powder thus obtained dyes the polyacrylonitrile fibers in shades of pure blue.



    EXAMPLE 237:
If one reacts, as described in Example 236, equivalent amounts of a compound corresponding to the formula
 EMI56.2
 
 EMI56.3
 (prepared from, 5-diarnino-4 ..- di, hydxoxy-arthw = quinone-3, 'I-disulfonic acid and 1- (p-amino-phenoxy) n :: t al'ne ) a dye endowed with equally good properties is obtained. t (. '). It responds to the formula shown below,

 <Desc / Clms Page number 57>

 
 EMI57.1
 
 EMI57.2
 DanàJ, etablf1au "! Voo '. Donhà la, etr4ctùr', and other dyes. They can be prepared. ::! ...



  , "(: 'les, / .." - "0' \ '' :; ',! I, r' ;, indications given in / examples 236 and 237: and ilo correspond to the formula" ',', '.. iü; [g, $ r! t {t ': 2 ;;;' '
 EMI57.3
 
 EMI57.4
 where Mi represents one, of $: remainders; s: uifint'50.jr :::. iY:., - :: j /, j ...



  ", c. '!; t ;; {;!; h0, iW.: :(; t,;:?, ((
 EMI57.5
 
 EMI57.6
 and 'T and K' have the sirmo1: ficô'tion $ 'indim leéé' dam $ 'le'J' '.' board. As had env1sage 'exe:': L: '4t4J "t}; h :,'
 EMI57.7
 board. As anions we can consider -those
 EMI57.8
 ,>, r ", 0,1.,. \, .. jf- <. ,,., if; ' ',' ('cited in description. pour.1.a'si9nir1cn; YdJttfiQ ":? rr .. -.': -: ';.'? '' -.) i) '/;' .; ' see table A (see above). ';; Í' ;;; 1:, ';;:'; ';:,; \ ;;!' ';' <;:, 'i;.! /., ..:

   ... i ':.'. '

 <Desc / Clms Page number 58>

 TABLE IV
 EMI58.1
 l Ex (': pl.) 1 K' Nuanae of dye! I --4- on polyaorylonitrilej 2µ8 1 -NH-Co-CH2- K1 blue
 EMI58.2
 
<tb>
<tb> 239 <SEP> d <SEP> K2 <SEP> d
<tb> 240 <SEP> d <SEP>
<tb>
 
 EMI58.3
 241 of K 10 dO
 EMI58.4
 
<tb>
<tb> 242 <SEP> d <SEP> K11 <SEP> d
<tb> 233 <SEP> d <SEP> K12 <SEP> d
<tb> 234 <SEP> d <SEP> K13 <SEP> d
<tb> 235 <SEP> d <SEP> K17 <SEP> d
<tb> 236 <SEP> d <SEP> K18 <SEP> d
<tb> 237 <SEP> d <SEP> K9 <SEP> d
<tb> 238 <SEP> d <SEP> K19 <SEP> d
<tb>
 
 EMI58.5
 249 ..Cg2 .. g,. ",;" nF 250 cP K 2 1,. "Nù,, a, E 251 d '3 ..., Ci', 25é K10 'j,., - ..

   CF
 EMI58.6
 
<tb>
<tb> 253 <SEP> d <SEP> K11 <SEP> d
<tb> 254 <SEP> d <SEP> K12 <SEP> d
<tb>
 
 EMI58.7
 255 rP K'13,,. , 1.: \ ,. ,. cf
 EMI58.8
 
<tb>
<tb> 356 <SEP> d <SEP> K17 <SEP> d
<tb>
 
 EMI58.9
 57 and> K 18 Cr '' 1 '258 cf' K9 '"ri bzz3 d Klc.



  11 ", I

 <Desc / Clms Page number 59>

 
 EMI59.1
 EXAMPLE 260 5.6 parts of the compound obtained are dissolved,
 EMI59.2
 according to Example 5 in 56 parts of acid, acqu ', 91aci1,!;) ;, at 30. At this temperature we add little by little, bit; to drop 5.9 parts of propylene oxide and stir, ie mixture: Í; to i, 1 = i, .. i>; = ;; ¯, 30, until a layer chromatogram thin. \ 11ontte '/,,-.i that the starting body has reacted completely. After that the solution is concentrated under reduced pressure: the dye of
 EMI59.3
 formula formula.> ... ,, 'i. <= ",] é, .jlj, j .r" ii. <, j] ;; j: 11 ;, j
 EMI59.4
 then precipitates the crystallized state.

   After filtration, ravaging with petroleum ether and drying, a blue powder is obtained which dyes the polyacrylonitrile in deep shades, blue tending to green, having good solidities.
 EMI59.5
 EXAMPLE 261:
The same dye is obtained by dissolving 4.3 parts of the compound obtained according to Example 4 in 43 parts of glacial acetic acid, at 30, adding dropwise, - at this temperature, 5.9 parts of propylene oxide and in
 EMI59.6
 stirring the reaction mixture at 30 until a thin layer chromatogram indicates that all of the starting material has been consumed. 215 parts of water are then added and the mixture is slightly alkalized: it then forms an easy to filter precipitate.

   The product isolated and washed at

 <Desc / Clms Page number 60>

 neutrality appears, after drying, in the form of a blue powder, to which the formula c) corresponds
 EMI60.1
 
This dye gives, on polyacrylonitrile fibers, solid dyes of blue shades tending to green.



   If the dye of formula c) is dissolved at 80 in chlorobenzene and an equivalent quantity of dimethyl sulfate is added to the solution, after 12 hours of stirring at 80, the same dye as is obtained as to Example 260.



    EXAMPLE 261 a):
4.3 parts of the compound obtained according to Example 4 are heated 165 for -4 hours with 4.0 parts of potassium acetate and 18.7 parts of 1-bromo-4methoxy-benzene. After cooling, 160 parts of methanol are added and thus the dye of formula
 EMI60.2
 

 <Desc / Clms Page number 61>

 
 EMI61.1
 precipitates, It can be recried in dimethYlformantida, It dyes the acrylonitrile product in 'pure, greenish blue' shades. EXAMPLE 261 b):
 EMI61.2
 The dye obtained according to, 1! Axemp fil);

   can be transformed, according to the indications given in Examples 5 and 6, into a dye corresponding to the following formula.
 EMI61.3
 
 EMI61.4
 EXAMPLE 261 c) '' ''? 'H'. '' 'The same dye is obtained as
 EMI61.5
 Example 261 b) by reacting with 1-brorno ... 4êthxy ",:, benzene the dye obtained according to the axiseml ',.,;,.; y. z,':

  , '

 <Desc / Clms Page number 62>

 Color A 20 parts of the dye obtained according to Example d and corresponding to the following formula are mixed for 48 hours in a ball mill
 EMI62.1
 with 80 parts of dextrin, 1 part of the preparation thus obtained is impregnated with 1 part of a 40% solution of acetic acid, poured onto the slurry, while shaking, 400 parts of distilled water and made boil everything for a short time. Diluted with 7000 parts of distilled water, 2 parts of glacial acetic acid are added and the bath is introduced to 60, 100 parts of a polyacrylonitrile fabric.

   This commodity had previously been treated for 10 to 15 minutes, at 60, in a bath consisting of 8000 parts of water and 2 parts of glacial acetic acid.



     Heat to 100 in 20 minutes, boil for an hour and rinse. A deep, solid, pure blue dye was obtained which had good lightfastness and good wetfastness.



   By following the procedure for dyeing A, it is possible to dye with the dyes mentioned in Table V (see below). These dyes meet the formula

 <Desc / Clms Page number 63>

 
 EMI63.1
 
 EMI63.2
 r. , .. V ::: \ T!, I '' 0f} j. ' : \ gi? (1: j '\:;:' :;}.> ':.', 'where X 1 to x 4 Al'T2' W, Z tF:, Ól1t: J: 6 "" inittions ":;:" '<,' ', \. r>'.,!.: r, .f, - given in this table V. The symbol F can even override $ '.'; "-0.:" 1.1 :;, '=> 0 ¯ ¯ 0¯,.' Meanings other than those which have been formed..pcdmm nn;:; - "" in table, .... Ji 1; 'r, j ... . / µ .x .. ,, ¯st, H. ,,;: ..:. :: in table B. ¯ 'i; 1: 1' '.> ..'. "0'1 '' f '; -' J '.



  .; .. '' '! $:; ::;, f: 1>: 0 (,' :, '; YCcV' "àl'j 'TA BLE' A UV ''. '; \"'>, 11) ,, .-, '. i. <'' l; µ J. ' .9 1 "':". "1'" <'' "-10 1 / <'5 '01>" \? -: f:,:; +] rez '
 EMI63.3
 Example- ...,. ¯¯; Shade 'of' ,: 'ple NI AI Z T2 F X 1 X2 X3'} (4. Vzw the color- ..



  P; . ;, re% 9ur Pdly-, '.f'acryloni.tï'i- 262' 0! . ; 1. ' :: '1 "...", \>' IÎ4,: ..; ¯; , 262 - / "" \ - O.-NH-C-CH2. F -NH2 OR H: H N blue; ,, .., "". "', F:.



  ..! L ... f. 0.!. "',,' 263 d ù C2H4-0-C-ÇH2- d do d e.:t?" D: ,,, des, 'u,, 0:': è:}. ':: ;;: :.:, ',. 1, ..



  264 d d -C 6 H 12- d do do pi dit, - 'da .., ..



  CH '. ,,,, .. ¯, ;;;:. Ù, .. 'l "265 0 d CH2-CH-. D do dO de. D',. D" r'u. . # .. ¯ - '... j;'; / ;; ...>.



  CH 3. ';'! "-: '3 ¯,' ¯ - ,. * - '"' '' '- 266 d' do d F2 dO 'd do d8 ti. -:. ;.



  ¯ ¯. ; ¯ /, "J> .-.: ..



  267 0 dO -C2H4-, do do o Br :. ' d, j¯ .. '\ -.! ¯:; ;:; ', 3' ... µ 268 dddd dO dl, d Cl duo d ".:.;" :( '(' ". {,;::,>, - .¯. 'i; i". "¯ ..1' 269 du do dd OH duo f do,, .purple ;; 1+ ';; 270 N0z -N0z Ó, "1? 70 do do do do N0 do ci -02,:. rn9.>:" 1 ..' "".



  :. 'I':);>}; ¯. ''

 <Desc / Clms Page number 64>

 
 EMI64.1
 Exem- Nuance de nIe NI A T la tintu- '"" 1 T2 1 XXX w re on polyacrylonitri- ¯ 1271 1 -CH4' "] '1 blue 271 -1- -C i3 .- -M-I1-L 0 I -N "" 33 rant on #lovert 272 dOS --N 1 o èj, -NH2 blue 272 s dO -NH2 eO -W2 blue 273 1 B dO dO do dO d4 dO dO d
In the same way as for the dye of ', Example 4, the dyes mentioned in Table VI (see below) can be prenarated with this difference that by using phenyl ethers carrying substituents, for example ether phenyl next
 EMI64.2
 96% sulfuric acid is replaced by sulfuric acid with a concentration of between 70 and 80%. To dye with these dyes, the procedure of dye A can be followed.



   . The dyes meet the formula

 <Desc / Clms Page number 65>

 
 EMI65.1
 
 EMI65.2
 in which Al, Z, T "lp R15 'R 16 0 tF Ti * t.Ù, jflQÔ'l: ft7./ tions indicated in this Table I., t. symbol-.F can" $]; / .; l $
 EMI65.3
 have the meanings that were given 'previously
 EMI65.4
 in table B .. '.' .. '' ':; . ; ... / ¯ ...;. i) /. "/ .., l" Î; ./ jl '.,;., i "';.:.; i" #. z / t., Î.à,

 <Desc / Clms Page number 66>

 TABLE VI
 EMI66.1
 Excm- A.

   Z T2 F R15 R16 Shade beyond Pic: dyeing on ¯¯ polyacrylonitrile j1 ', 274 0 o -C2H4- F2 HH blue 75 cr d' 'cr #. "276 i de P4 # cr' # 277 (P # F5 cf # 278 cr '6 # cr 279 l' 1 cP F 7 cr "cr 280 d Fa à # + 2B1 cp d" cP F9 <f # ÊQ2 dr F10, tP d "263 tP i F11 tP (f tt '2e4 iF cr '12 cr cr 285 cP F1, cr + ep 286 0 11 do lP di OCfl3 'L-WS.7 / # \ 288 - S + (f.dP + (f 289 de 0 -CH2-CH- di cf! d cf! 'bzz 290, p -C2H4-0-C4- + cF' cr o 291 K If '-C2H4- ci' "':,' 1! ci 'ci' ## -. ç, '292 d '/ # 2 dd cf!'

 <Desc / Clms Page number 67>

 
 EMI67.1
 T A B L E A U, i v: t (Sui teei1 fin) '> H ::' i <';; 1.;.' L
 EMI67.2
 Exem- A. ¯. '¯l' ';. / .. '". / j /)"' ''.? / Î.], illl /, 1 /).:.: .. ÉùrdsÀ $ pleN on. ' .: ..: .jl ".:.:,.;", .i .'ij :, ".:", l: 1 ..: .. "i., 11'à: '. i.;

   poiyacnylo # "...... ràïtrile 29j 0 -C xg-, '.F ..... H' .. H # - '' {: J ':,;".' 294 - <- <'d,, "',", ''. + ... ..I '' "" '"' / Q '1.1; 1" ":.' ,,, ... '' +, '.



  295 dl dO,. ' not a word:.' OQH 3 "'j ..' '..' / :." '; "," j.,:: '. "': '.' ,, ', l-" t <:. '..' 296 <fi o. : d '"' '' M '' -% <P '. \' 'dP' ''. '". '297 0 Cr CH 3 CH' blue .10 green

 

Claims (1)

ABSTRACT The present invention comprises in particular: (1) A process for dyeing or printing textile materials consisting of or containing acrylonitrile polymers or copolymers, with dyes of the anthraquinone series, which process is used for this purpose. corresponding to formula I EMI68.1 in which M represents a bivalent group forming a bridge, one of X represents a hydroxylic or nitro group or an optionally substituted amino group, the other X represents a hydroxyl group or an optionally substituted amino group, W represents the nitro group or an optionally substituted amino group, A # represents an anion equivalent to the coloring cation and A # represents a group corresponding to either of the formulas II and III EMI68.2 <Desc / Clms Page number 69> EMI69.1 foxmul.as in l.esquells-s, y '1' jf.j>. ':'? -.'- \ '.'..-'..-' 'formulas in which w:;': '= - .; ,:, '; '; a: R1 represents an alkyl or cyë..ioalkyi..sv.n ": ',! 1 ::",' 'residue. , tally substituted or form heterotyl910: ', 9 @, "11À"; with R2 and the neighboring nitrogen atom,.:. ', .'f' '!' ..: .. '' i, '. ; ..: .. "/ Î ;,);. The R represents an alkyl or cyclo-alkyl residue which is also subat1tué or forrnerGn h4téoeocYclé with. '.,' :: ', <, ..' R and the nitrogen atom volai n,,. ::: "" ,, ", /": ':', i <'', ..; R3 and R represent de8'atoms.d'hydrOo &. 'U "dti8 eat4 y T. Alkyls or cyclo-alkyled den11.:' Or different, possibly 8ubsti killed, or reprl'nt.f \ (d,> t ;, possibly substituted, ".. => 'j "- ,,.' "', /. - ;: '"...' '" "identical acyl residues. or.' d.1ftrent, '' ,,"., \ !.} ;; ': "R, R6 and R7 each represent hydrogen ** or a residue -: alkyl or cycl.o-rlkyle.vertue, i, emerït sub.t1t \: l4 ',:;.') :: aSBOCG. ..., l \, - '\ J', 1 "'-: <' 'I4'!. H, '. ,,:. J \, 1! Jr., R, associates Rg and / or .¯. l,.; .: l '/. Il = 1 / .j] / "1: 1' / Î" ÎiÙl'llÎ1..1 '/ 1)> 1' R associated with R4t, 'vec 1'8' tos t o ' , "V'1,? Í: ':; <p these substituents, and.'. '"', "'..' ':'. '' .Î; b 'li' 'i'é. $ Ô / "<, ...,:,:,. '' ¯; T, .-. , j; 1.: ':.: ..' 1. 1. '.. ". R, f, with:. ' ,;,:. 'tt'., :: "" ',:.! - ::': J,;: ';.:' and R., R j, R .. and with the atom d ' aé $ t9,,. Voia i $ i '; Ôµ' ".; 0" ": '', with atom, a% t!", S1H ",;,:,". '; ,,,;.]; ; flj '<"\., .i'", '4 !. ..- can form µ "'.' Î; 'fÔ5 -4; 1>, :(;",:, -: ,, "', t; .... ¯ - <., 1": i ':;'! ':; "'. '.:: ft,!. \;".' j ';! <kernels B and / or D could carry 8utX'é', "'9irff: c, ::, group '' '' n '' "''" 'f'urrf rié;' pQ.iôné -; r ":; 3 and the group -M - K can occupy the uQ9", # éµ ).; 2'and 4, .. "'" i ",' ... J .-. Jl; f '"',:;. Ij "Y-; .." An execution mode of the following procedure '! 80U' -. ,,; " I ,. ; ':. \.) ,,' .rt; '.' "\." rJ =, 1, according to which we use 'Qoran: t8>, # ép4nd, at, l't ::, ::' "',: formula,. ° .., yâï¯;. ,, ';,. n. x, .. 5: = 'a.:':r' ,. formula IV ..]. ? ;;: '"\: i' <:::: c <, (',' ..: h:, t}; Ji :::: t ;;, EMI69.2 <Desc / Clms Page number 70> EMI70.1 d; -r1 1 <'Irjuelle E represents a residue of formula V EMI70.2 or formula VI EMI70.3 formulas in which Z denotes a hydrogen or sulfur atom, Y represents the direct bond or an optionally substituted alkylene residue, which residue is linked to V directly or via a hetero atom or a hetero-atomic group, V represents an optionally substituted alkylene residue which may be interrupted by heteroatoms or by heteroatomic groups, V1 represents a bivalent bridge linked to K # by a carbon atom and R8 represents a hydrogen atom or an optionally substituted hydrocarbon residue, the rings B and / or D possibly bearing additional substituents and the group - 2 - Y - V - K # or the group - Z - R8 being able to bear. occupy one of the 2 'and 4' positions. 3) As new industrial products: <Desc / Clms Page number 71> EMI71.1 a) the s c ol o ran t s ..a n th 1 * 4À> $ 1 '±% àijii'Éé9 bÉài qgec ilµ) l "" "/ j"' - ".. 'without ..." i. '; "/..1;,;?1 1 ...,. / ;. l'll; 11:" :: ;;. 1 ..?) I "'; '".;. L .. ...>.;., ', <"a ... $ -" :. i .->: " EMI71.2 EMI71.3 where K represents '' un- ,, dana rpr; e {:; uÎ '; IJl11iJi1 a group answering the formu19-: 1M}, ;;' f \, i \ / j,: J ,, {;;; :: t'è> '} \ ti :;' "responding group. . '.:. <:' -: '"; ¯t ..,: .- .. 0:'.:;,};:,. :: ':.: - ;; - <'.: t -.,.: <",': '.: ->"'.: 'j: ,,' :: ";;; EMI71.4 EMI71.5 formula in which EMI71.6 R91 Rio and Ri, represent ChÇyi \ ;, 'u:.' ReW (8,1, kYle 9iJ '/}.', '"> ,,. Cyclo-alkylent subatu 10' or R9 # Rio and Rjjt po. ., r! '? J;' tT'r: eeem:, t1 ", ':",' heterocycle with atoniti, '(i'% Qteàvoi8in ./"-: the nuclei B and / or D. possibly and the group 7 - Y V-K cicçù, Pan, t-1 <un * ades, Positions, ',, 2' and 41; . "',:," l {L:';? Y0 \: <, ";;,; /" I,. ;; 'i;:;'; G,; t '; ", t!"' / '::,?, b) dyes. seen as a sulfonic group and responding to, la, fo EMI71.7 <Desc / Clms Page number 72> EMI72.1 ...,. {, ";,.: j in which.-ZRR," '/ l .. "..' ds 'Ié. ¯';> in which the group -" Z-Ro opcises one of the two pa.si -. 't 1 o n 2' and 4 '; ;.: .s ,,. ,,; , J <', 1 c) the anthraquinoniqtjeis dyes dpourVu8 of. "¯, .J sulfonic group and corresponding to the formula X. ..': 1 EMI72.2 wherein the group -Z-R8 occupies either of the two positions 2 'and 4'; d) basic anthraquinone dyes do not EMI72.3 containing no sulfonic acid group and corresponding to formula VII, represented and defined under 3 a), formula in which at least one of the symbols X and? represents an optionally substituted alkylamino or arylamino group. 4) A process for the preparation of the anthraquinone dyes of formula VII, specified under 3 a), process according to which: a) an anthraquinone compound of formula XI is reacted EMI72.4 in which A represents the acid residue of an ester, with a compound corresponding to the formula XII <Desc / Clms Page number 73> EMI73.1 EMI73.2 -. ' ..: ..., ..., ......, ¯ .. ,, .....,. ,,, ,, ¯ ,,,,, ,, ¯, or with an oompoaé ' r'éµôn4ààéé '; làf ià] Qo' & ùié "? Qi.z)", l ±; 1:)% El. ... "..;.:. ' .. "1" ... "=.: '/. 3': J '. &. 'l? Mi;. "i; Ôl ... j. / .. l' µj.g; .- .." <:]. to.J "j .Ç: (j., ii {G :: : <:;!. :: "t EMI73.3 EMI73.4 a9i à Un I ÉbùPÉ% À 'à6ÙàÉ% µli non'i Qµà) / ¯'11)) ") corresponding to the formula XI', 'i 5f (<$, i",. " EMI73.5 EMI73.6 with a composition: '8P0ndary: f' 'ne or with ut' ç. '? 1. EMI73.7 EMI73.8 -. v pt d .t e? ". ' .i, T t, 'x, i' pJta .. .1 or one traneformaun formula XVII t "" 4 ".tx", bzz ¯..L EMI73.9 <Desc / Clms Page number 74> EMI74.1 by reaction with an agent t dE. that a compound of formula XVIII.: ..¯; ("... '.", j' "" 1..8i. EMI74.2 EMI74.3 ô.-ns which R 12 represented a xeee, krle or .., .... bzz c5r: lo-al.kyle optionally t (/. l "., c) a boric ester is reacted anddl4n 'anthraquinone compound. formula XIX ..1; ". EMI74.4 EMI74.5 with a compound of formula XX .. ("., i:: r ..Ai;, 7,,,, L t, '' -, ..,. 1! r ... EMI74.6 EMI74.7 reaction which gives naisaarec, -. à}, ln 'at..r, ..: He. '.F];.> .. i; .., yl. ii.?>; ' .: <. # of a compound of formula XX, .r.,; ¯ 4 = ', a'; , '-; . # 1.;,. ' ';' "S" ... -. ¯ '.: 1: " EMI74.8 <Desc / Clms Page number 75> EMI75.1 "'' 1 <: IapvlI.I, .4..LtiI .La yr: UVpe ffS1j, er DOr.qwr: ,,", "Qr \" eç "8nq.d:; ';, :: r:' ii ,,,, r :: ',:'} f: ';':: (1j:, ") ':; ... ::. \ :; i' /; EMI75.2 the -SU3M- group against a ja'nyarogenic atom or% 'group -8 311- at "m -.'.; '' * '- P' 'against a non-hdxv'solubi group. d) a component p6hant .. Formula XXII. ".". "'S EMI75.3 EMI75.4 . .- .. '' 'r. in which R represents hydrogen or an optionally substituted hydrocarbon, with a, cpmpQ-7. s of formula XX, ':; ) .il ,; "] Î,?" .. "..; ii ,,;, j ';.':. formula ', i' ...:, {,;, Y; ':: {! JlI e) a boric ester of a., Cm $ os4 .. / ::. 'L;,.' Is reacted. ";,) ./" '¯ # j = ..,:' 1 '¯. /.,;,:, Formula XXII ..' ':.:;:. I]),':, ',. . "". "" '1' '!: F? R'i, Ij; \': ";, ::,: ', -.: EMI75.5 EMI75.6 with a compound of formula XX, ÓÍ1 :, apont (iQ le .. "q :(.)]. , -l. "." .. "" "'::.') fi" "IE":. ".: <,. r /. ' boric estur group and we reduce vef) tU: e1ieU \ erl't :::: ;; ' . ', nitro groups in amin'o ""% 1,1'; .- ''; ... '.' '- 5) A preparation process of,' 9oQrans anthr - 'basic quinonics not bearing no sulphonic acid g'rupeacid and corresponding to formula six, dyes which have been defined under 3'b), process according to which 1 ':'. '<. . ":: . "# <" ./ .. '"" .li; =, a) an anthraquinone compound ";: ± é.¯ of formula XXIV -,' ;. ',' ,,, ..; ';,;' ... '. <Desc / Clms Page number 76> EMI76.1 with a compound of formula XII or XIII, b) is done. act an anthraquinone compound of formula XXV EMI76.2 with a compound of formula XV or XVI, or converting an anthraquinone compound of formula XXVI EMI76.3 by reaction with a quaternizing agent, to a compound of formula XXVII EMI76.4 <Desc / Clms Page number 77> EMI77.1 c) reacting a 'boric ester of a' ceo84 ""; ' . "anthraquinone of formula Xi, '.?; ..,; ..' J ..... l EMI77.2 EMI77.3 with a composition of f ormu the XXVII.J. EMI77.4 EMI77.5 so as to obtain an 'ester bp r 1 that Ù of a cor1pO s4' 1 /). j of formula r. ,. ...; the f; ./.;l "(.> / .. EMI77.6 EMI77.7 ': .- f ,,' ..... ,, "1 ... :( ,: '.: ..- EMI77.8 then, in this compound, we saponify the 'ester group' EMI77.9 .. 'c, boric and we exchange! leHgrop "' S03:,. for n", ",, H ';" "': .. '.' /, '., ... i, .... . hydrogen atom or against a non-hyroeo3 group. =, bilising, ". l ": 1 ..:" ',. : 'J .. ";;.,;" "; ..: .I.) .." I'>: j ...:; . ':; d) we make rp'ôg1r 'a' COtfipt) s: 'ëjoxmui. x.xII "" é'è a compound of formula xlm I.ol; t, i.t ";:>; 41N", 1:,;. e) a boric ester dt, n'CÓmP9Ilt:.:, :: formul.e XXÎIX is reacted with; "<'.' /.',r '!:"' <; '' {: "', <, t. "<',', <" :: ": '. ,,;' i,: \ of formula XXIII with a compound of" lti4l formul.0 X <i .. "'..... ,> ..l; . .:::: " ..he " <Desc / Clms Page number 78> the boric ester group is saponified and the nitro groups are optionally reduced to amino groups. 6) A process for the preparation of anthraquinone dyes of formula X, specified under 3 c), proceeds according to which t a) an anthraquinone compound of formula XXIV is reacted with a compound of formula XXX EMI78.1 b) the boric ester of a compound of formula XIX is reacted with a compound of formula XXXI EMI78.2 reaction which generates a boric ester of a compound of formula XXXII EMI78.3 the boric ester group is saponified in this compound and the -SOH group is exchanged in the compound of formula XXXII against a hydrogen atom or against a non-water-soluble group, <Desc / Clms Page number 79> c) reacting a compound of formula XXII with a compound of formula XXXI, or d) a boric ester of a compound of formula XXIII is reacted with a compound of formula XXXI, then the boric ester group is saponified in the latter and the nitro groups are optionally reduced to amino groups, ' 7) A preparation precedent for the compounds of formula VII specified under 3 d), a process according to which an anthraquinone compound corresponding to formula VII is alkylated or arylated in which at least one of the symbols X and W represent a primary amino group. 8) A process for preparing anthraquinone dyes corresponding to formula XXXIII EMI79.1 process according to which a boric ester of an anthraquinone compound of formula XIX is reacted with a compound of formula XXXIV EMI79.2 so as to obtain a boric ester of a compound corresponding to the formula XXXV <Desc / Clms Page number 80> EMI80.1 then the boric ester group is saconified and the -SO3H group is exchanged against a hydrogen atom or against a non-water-soluble group. 9) The application of dyes corresponding to formulas VII, IX, X and XXXIII to the dyeing or printing of fibers, threads or textiles made from acrylonitrile polymers or containing such polymers. 10) The application of the dyes corresponding to formulas VII, IX, X and XXXIII to the dyeing of plastic or leather masses. 11) Application of dyes corresponding to formulas VII, IX, X and XXXIII to the coloring of the paper. 12) Processes and products in substance as described above with reference to the examples cited above.