BE558390A - - Google Patents

Description

       

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  The present invention relates to novel dyes
 EMI1.1
 ; 15; Lio and more particularly to new nitro dyes containing a 1: 3: 5-triazinyl- (2) -aino group.



   The present invention provides novel nitro dyes of the formula:
 EMI1.2
 
 EMI1.3
 oÉi 1> represents a naplltal ': llÍlue or bcn :: 6nic nucleus which can be substituted for & j, where the ato1.1e <:' s.> .; ote N is in position ortho p., r relation to the group ni \ :; 1'0, X r;: r, esemte of izydro "en or fine hydrocarbon radical:

   Which can be substituted, R rc.,. PY, feels:. '1 </ - j: r'0bmG or an organic r.rdic ^ 1 attached to nitrogen by an atony

 <Desc / Clms Page number 2>

 
 EMI2.1
 of Cfrbonej and where R can be re-read: l X when X rep. feels a iiyé.rocarbon4 radial; or to D, in position ortho with respect to 1-latoae nitrogen 1.i, to force a htcrocyclic ring, new nitro dyes which are further characterized by the fact that they contain
 EMI2.2
 at least once the group:
 EMI2.3
 
 EMI2.4
 ') 1, Po. Rt: ycr'sente of 118.10.,;,:; Ne., B represents an aryl or alkyl group. of mloene, alcm: y, aryloy, alkyltl1io, a :). "yltllio .., lxy- -ïrr, ¯yj l8rcapto, amino or G ::. 11Íno substituted and Z is hy- < .r,> gene or a hydrocarbon radical which can be substituted.



  Co. The examples of substituents which, inter alia, may be present in the phnyl or naphthyl nuclei D, the substituents of the. for-mile aryl-Y- where the group ary-
 EMI2.5
 le may contain substituents and where-Y- represents a bond
 EMI2.6
 :! üecte or a divalent linking group for example -NR'-, -SO2-, -.3- -0-, -80ZNR '-, -NR' SO2-, -C0îlR'-, -IIR'-C0- , -CO-, -CH2-, or -CI, T = CïT-, where R 'represents üyurogen or. a hydrocarbon radical which can be substituted.



  Coolie radicals or [;, ['niquE's represented in .i. formula cidozi - .. i2s by R, we can c'es rnclienu ,,, 81: yl, E'r1l1;: yl, cycloalkylc, aryl and heterocyclic which can be substituted by
 EMI2.7
 the substituents defined below.
 EMI2.8
 



  Co :: ie radicals il.jT; 'OC, n'bOl1r: s que rerr (sc-r.Ltent R', X and Z in the following formulas: above, we can cite the alkyl radicals, ' 1rl ', lkyle, cycloéllkyle and;: r yl which can be substituted by the substituents defined below.



  There may be in the phenyl or naphthyl nucleus D, in any acrylic nucleus, a group represented by ttryl-Y-, or clan :; any aryl ring present in an rf1d.ical 01'GD111.

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 that or. in a hydrocarbon radical represented by X, Z, R or R ', substituents such as alkyl groups, for example methyl and
 EMI3.1
 ethyl, -S03H,. -COOH, -CON (Rit) 2y = CN, -COOR "., -S0il (Ri '), -GpR'1, -CF 3, halogen, eg chlorine and bromine, -S020R" ; I -I \ 10 21 -S02RII -ORT ', -OH, -N (R ") 2' -NR" COR ", and -NR" So2R "where R" represents an alkyl group, cycloa.L¯ú 1 e, aralkyl or aryl, and it is evident that more than one such substituent may be present;

   and that when Rn occurs more than once in any substituent, the groups represented by R "may, in this definition, be the same or different, or alkyl or all-yl groups substituted: s, united so as to form "with the a.to: ze ci 'nitrogen, Him heterrocyclic nucleus.



  Coiiflue examples of substituents which may contain the alkyl radicals present in an organic radical or. in a hydrocarbon radical represented by X, Z, R or R ', there may be mentioned
 EMI3.2
 hyciraxy, cyano and halocun groups, for example fluorine and chlorine.



   In the new nitro dyes of the present invention in which R is connected to X or to D in position ortho to
 EMI3.3
 at e.t #, the nitrogen N to force a heterocyclic ring, the radical R can be such that the heterocyclic ring thus formed can con-
 EMI3.4
 hold more than one heteroatollle, for example one or more nitrogen atoms ;, sulfur and / or oxygen, besides the nitrogen atom Nd 1? As examples of heterocyclic nuclear systems which can be thus formed by the attachment of R to X, mention may be made of
 EMI3.5
 morpholine and piperazine, and as examples of heterocyclic nuclear systems which can be formed by attachment of II to D, there may be mentioned ph-lioxaziric-, phenothiazine and acridone.



   Thus, by way of examples of alkyl and substituted alkyl radicals which may be represented by X, Z, R and R ', it is possible
 EMI3.6
 mentioning i; i ± tliyl, ethyl, p-hydroxycthylj -c'1lor-ethyl, and P-cyano6tliyl groups; as examples of aralkyl radicals and rr = éiic <7.iaJn armlicyle substituted represented by X, Z, R and 11. ', we

 <Desc / Clms Page number 4>

 
 EMI4.1
 may contain benzyl and t radicals; .Q.-chloroben; yl; As examples of substituted cycloalkyl and cycloalkyl radicals which may be represented by X, Z, R and R ', there may be mentioned cyclohexyl and 2a6thylcycloheÀ71e radicals;

   as examples
 EMI4.2
 substituted aryl and aryl radicals which may be represented
 EMI4.3
 where X, Z, R, R 'or C1j pt- <' may be present in the group represented by aryl-Y-, there may be mentioned phenyl,? -ai.¯inopiinyl,: 2-aainophenyl, .-- groups. :, ijüzo-3-: ulfo.Iu.n; le, 3-a..¯ino -.- sc: lfbpiienyl and l - :. lahyl.üno-3-sul fophc: nyl; and as examples of r'1: hétsrocyclir) ues which may be represented by R, there may be mentioned radicals 2; ± -d 1. eiiloz o-1 t 3: 5 -t.ri azinyl, 2-, 'C! L170 tl1i?', Zolyl e, and 2 - benzoxazolyl e.



  As- "-'m: .3, .. ples <i 'ato - es c' nc..lo; ene which can be present by A and B in the above formula, we can,. lentiol1- -; '> 2Y the c1; the e and the r) I'0: .1e. ß. .title el' exel1ples S of LltreS rOLl¯7e8 which ¯ ¯ wind to be represented by we can mention groups al - :: c: ys 7ui.'Lho.-iy and til0XY; as examples of aryl radicals, it is possible to use phûnyl and -: iethylphFnyle radicals; as <1 '<Jxia Alkylthio groups may be mentioned. .hy lthio and laut3rl tizic; as an example of groups ε <1: = ino substituted, we can ... 1entiolm the group 3-hydroxyfthyla.rÜno; as an example of arylthio groups, we can ... may mention the group n-tolyltn.io, and as examples of arylo2: Y groups, there may be mentioned phenoxy and .Q.-chloroph {noxy.
 EMI4.4
 



  The present invention, in another of its aspects, is
 EMI4.5
 The characteristics provide a process for the manufacture of the new colors nitro # = '1ts, process in which a 1: 3: 5tri.r zine of the formula is reacted:
 EMI4.6
 
 EMI4.7
 or A and B have In signif lesion c, ui their e ::: t Cionn, e plus hlLlt "êvac

 <Desc / Clms Page number 5>

 
 EMI5.1
 x a nlbro compound of the formula NU2-D-l.-R, where D, l'f, X and R have], is meaning given to them plus ¯ '??. L2't; which contains at --c'ins a group 2 :: 13.i10 of 12 formula -lll-I <. Z where. Z s. the meaning r;
 EMI5.2
 it is given above.
 EMI5.3
 



  As examples of nitro compounds which can be used in the above isrcL.éd4, there may be 1, mentionJ. "1.er the 2: / clinitro-3'- and 4 '-alllinoc'i.iph311yle' , ines, IIa 2-ni tro -! + '-al.lino-L.acétylc1iphenyl &! l1ne: 1 la 2-ni tI? o -1 "-miiino -lé- sv, lioned.iiiE tii% la.:; -iil.odi iJhiÀnj7l xiine, 2-nitro--. ' -a.lino-t, .- ca.r'ballanil idociiph nyla.; ihe, la 2-nitro-L'-sy'lino -.-- carbonec; Tcloheayla: lidoc), '¯chén.lat.lirle9 la 2I? .3.-lr OJ. ' -8. '. ¯1.210 -...-- Cyc ^ .110C210i1: llylc ::. 1.12-G' la 2-ni tro-4 '-, 1ino-4-sulf'one- µ-igd.roJ # j7étliyrlxniàoàipl.ié; lyla = nine and 2-ni tro-4 '-B.:lino-4-trifluù::'o.



  ; ... 'ti, ylé.ipl1 / nylC: -. line. These nitro compounds can be obtained by reacting 2-nitro-chlorobenzene appropriately substituted with α- or .12-phenylenedianline in alcoholic nilieux by eē.lal in the. ethanol or j3-ethoxythanolj, in the presence of an acid scavenger, for example sodium bicarbonate or sodium carbonate Co; .riie other examples of nitro compounds which can be used in the process of 111 ' VE. ':. ltlOCl, one can.! Le :: ltionl1.er the sulfonic acid derivatives, llh6nylll. & Phtylar.lines and substituted dii) hnylaÜ110s, for example acic3e 2 :. -din: i'tro -.'- 1¯1110d1.JAlC'.11y18i1.Yle- 3 '-sulfonicaue, 1, j¯ eid 2 - n.ïtro-3'-¯; iuo -:' - cai ' borlwiphnyl: line -; .- :: nÜfoni (lUe, lucid e -nitro- / '- (n - :. lino.11i1ilio-) ë1i hc¯n% 1.üls-?': 4- <1 sultoni,. juc, l 'f <, c1ri, e 2-nitro-l ,.' -: 1¯'ti; flC:

  ¯.¯1.11UCI7.31'Yljr1: 1122G'- ': 4Cl7.: Iu.if'OYll.rLlC, 2-Yl.ltZ'O -.'-:.! C'ttl, z,' ', .. û.11.î10 -.- SLILÏOlle - il, y': ï'O¯STi: tiiyl ai.iido di jp 1-Enjli a:, i irie -3 '- su 1 oni q ue, lucid 2-ns.tro-Ir '-:.: Ctyla = .liiio -lé- ci, rb.JxyéJ iph6nylājaine -3' - suiòni <j1Je, l 'aci'Ô -i5.tro-l. '-;,: lisol .'- ns; j> htylj> iifiiyla- <iin <u-416' - <: iiulÔoniLjue and the 1: 5- (Jilli tro-2:

   6- (i- (le - a iii iio -3 - 1; ul i'o s, ni l.iiio -) xia plit ai éii e Ces (iL'ivJ: s de l ', lcicL0 8'cl11 The reaction of ortllonitrocnloro-benzcnG or -naphthpicne SLL5tltLiC appropriately with the appropriately substituted diaisine can be co.rj.tOd'.cnt obbonus., (At least one of the ingredients of r, 5: 1ctlon r.Ull't # a1t'llt ufi 8ulfonicluc acid group) in

 <Desc / Clms Page number 6>

 
 EMI6.1
 aqueous media or alcohol;, ues "in the presence of an 8: er1t fixer salt '<' c1de, for example. cn'bol1p. te of Cz, .Cil:.: l, temperature raised by GXhjiple to a tet .: -r.ture of lc0 C.



  Other examples of nitro compounds which can be used in the process of the present invention "are 2-nitro-4 '-! 3-tJ.minoE: thylsulfol1J l,). L. 11fnylEmline, 2-n .tro -! - a .. = ¯inrr Lh;, rls1Jlfona; ôâoôiphényli: iine, 2-nitro - G ..:. ano-I-eyclo'rïev; rlanüine, 3-nitro-t ,. - :. ïorpïlolinoeniline, 3-nitrohnarazine, 1-nitro-3-aainoacridone and 5-a ï: iro-iT-2'-n. troia: nylen¯, ī.; ina.zoie. fi bitre ( 1 '.c: el) le.:; =:' Il2.loimo-1: 3: 5-tri2.zines r ui ^ ewvnt :: ': 1' <. ' .e ', ili: e: d: ". l1.s the j> roeid16 of the invention, one can ..¯éntloI1Il8r cyanuric chloride, 2: 1-: icnloro-6-: n - ïcy- 1: 3: 5-tri2zine, 2:; .- c chI Gx'O -.- jÎ1,110 J-1 ::: 5-triaziï e, la 2: L;, - ': ic:' coro-6 -plîtnyl- .ri ê: 3Îlw, la :. ; 1.-Giclaro-6 - ((3-Yl;, r.? Rosyw'tll = v.II110) -1: 3: 5-tr.iazine .. la.: -CicnLoro-C - :. c ' thylthi o-1: 3: 5-triazine.



  The reaction between 1'lloïlo-1: 3: 5-tria.üiïle and eo:. = Posed nLt''0 is preferably carried out in a solvent of the nitro compound, ¯'1 ',: f (.rence l' water, ..; eis in the case had the nitro compound used is not 1 "iyc'rosoluble, one can use a gold solvent; a.ic.ue, by 8ye ,,) the 1 ': =. cctone or dioxane, which is a solvent for both.; É.; ¯; Gs> 1 ni-tro and halabmo-1: 3: 5¯triczirm, or a ,,: '1c: n2e of such a solvent with ee, u.



  The reetion is preferably carried out at. a low te # ra.ture which will be: 9rlnci) ele.aent depending on the environment and the iialocàno-l: 3: 5-trié1.zine used. When cyanuric chloride is used in an aqueous medium, it is 1 rrf rāhle to carry out the reaction at I) the te ;; p / r: 'ture infrieurG at 15 C, ¯.12is fel: 3 of the media anhydrous, -Jp.E tp.,: / ré tu1 '\': S .Jlus é1ciT <'ec can be used. To; z: make, with a di-halogeno-1: 3: 5-triazine it is) 1 'reole to perform 10 r,: r, ction 8. a tc¯ ..: rc.;, UrE. < 'l] -, the ::. wus é.e 85 C in aqueous media,
 EMI6.2
 although higher temperatures can be used in anhydrous media.

 <Desc / Clms Page number 7>

 
 EMI7.1
 



  If it is el: sire, we can add to the ¯.: Medium C-titS fixing Ci'2.acid, for example carbonate of SOC? IU !, sodium bicarbonaGe or i.cé.ta. you of potassium.
 EMI7.2
 



  The reaction products can still be reacted
 EMI7.3
 nitro compounds with the h.loc, eliu-res cYBl1uriques with d.es 8111n8s, for example with 1.ro: l.¯.aine or with the olali metal salts of phenols, for example socli1.J1 phenate. l, in aqueous or acet # lque medium at temperatures 1,100SrteS, by eX6.Jlple at .0 C to ob-
 EMI7.4
 keep products identical to those obtained by the reaction of
 EMI7.5
 nitro compounds with the s di -halogéno -1 t 3; 5 - sorting a zine which is obtained by reacting cyanuric halides with the corresponding 21 :: ine or with the alkaline N / 'tal salt of the phenol cor: cespol1.ctant, for example with the: la.- cliehloro-6 (J'-hrc¯roa; J tliTlē: .ir¯o-) 1: 3:

   5E: 1; #ziiie or: '. Vec la 2: L, .-;:, icllJ..oro-6-pilcllo = ¯y-1r3: 5-triazineo It is <; en, 1a: lc; ient src : f.rt iïle, in order to r,: c1.1.Üre au the secondary reactionsj for example the i1.yc.rolysis of 1 to., ie or these li'halog = ene atoms which remain attached to the tria- nucleus 0 to. during the manufacture and storage, to isolii% the new nitro dyes from the media in which they are forced to a;> 1.I of 6 ii 8, and to dry the dye pastes obtained with this to.1pr'1'E.tures rclativG.::el1ts low, for example between 20 rt 40oC, of trî -rence in the presence of tr.ùl110ns for: .. ailïto.ir le; H une value of about 6.5. Examples of buffers of this type are des, l (lc ', n; c eixodiqae phosphate and phosphate: upïtOsOC' =. Que or disodium phosphate and monopotascic phosphate.
 EMI7.6
 



  The dyes of the present invention which contain
 EMI7.7
 dcf. ; ... J.'or: Js: "suitable sulfonic acid,: ¯ r-ticuli :: r E: icil't 2. 1> a> ,; i # -
 EMI7.8
 cation on cellulosic textile materials, for example cost,
 EMI7.9
 lit and rayon Ge viscose, by dus i roc. : this dye in which we apply the dye 811. solubiun ElLJ.l1Utli.G on los atië- 1 '<"' ,; t -tile;:, opijiication associated with a ti? i; 1.The,:. ent by an i.¯ent fixative û 'ELC1C) .G, by li soda Ci', LI :: ': tick or carbonate of CiOUIIlI:!, the tr.'ait; e., icut by the 1., cnt fixer and '[' J.cicie being performed rnT!, nt, [1cl1 (Ùnt or (.Íir) S le ctra 1..t e..i in .l;

   piu, the dye solubion.

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 The dyes of the invention can also be used
 EMI8.1
 for the 1-.ipression this F. cellulosic textiles by a process in which one applies to these. materials a printing paste containing the dye and a substance which on heating or vaporizing releases a diacid fixing agent, for example bicarbonate
 EMI8.2
 sodium, and in which the textile uatiëre is then subjected to the action of heat or water vapor.

   The dyes of the invention can also be used to print the. wool and silk
 EMI8.3
 and regenerated protein fibers, coi; k.ie casein and 3rdein They can also be used for the dyeing of silk, wool and polyid textiles, for example of -i% tiéi? es textiles. - 11211.t of the pol: 'T:' 1E> Xéllllsthylène aéipéJ1.; Làe or the polymer obtained from r?, I ,, - ,.: 2012cta..le.



  The colarmts of the present invention which are insoluble or soluble in water can be used in the form of a finely u-ivisce icer for dyeing and icing. ... pres- :: lon 1 ;; 1n (:, silk and textile materials containing ¯rificiel fibers.:, eg fibers made ee,) 01Y8.i (Îes'; 0:. J: read the olyl1e} a ', / ti1ylè: lf. :: Er1 ip & JlÍ6.e and the poly.Liere obtained from = .u ca3-ralactone,:, from esters cellulosi <1.aes, for example c: cellulose acetate and tl'ircate, c, polyurethane eb cse polyester (: r: .ro ", 1HtÜUGS lin, a.ire, including polyethylene terephthalate.



   By the above processes, colorations are obtained
 EMI8.4
 yellow, gold;. streaked and reddish-brown of high light fastness, light and reddish very: itejLients by way <Him.ii <. "e.



  The invcl1tlon is illustrated, ..1:, i8 not îi..iit> 'e, by the following examples in which the parts and proportions are crpripées by weight:
 EMI8.5
 j;, / "j.Ll 1 ... :: ....., On <1 1 r zout à9,! 5 É i ;; ieN '..1' 'Cicle 2-> ii. tro -! '- # uiino-di:> iié nylDl! liüe-3': 4-Ó.isulfonlt ';. ue in 300 parts of water coltuüfmt 50 parts c!' umu solution of c;> ri> oLi ;;

   ta ne roeliii; 1 2if, and one intl'oë: uLt la

 <Desc / Clms Page number 9>

 solution obtained in a stirred suspension of cyanuric chloride (prepared by dissolving 9.25 parts of the latter in 40 parts
 EMI9.1
 acetone and pouring the. solution in 150 parts Ct (water).) The mixture is stirred at a temperature between 0 C and 5 C and adjusted to pH 7 at short intervals by the addition of 2N sodium carbonate solution. The reaction is complete when a clear solution forms. 100 parts of a solution containing 6 parts of disodium phosphate and 12 parts are added.
 EMI9.2
 of micronutrient phosphate in 82 parts of water.

   100 parts of sodium chloride are added and the mixture is stirred for a short time, filtered and the residue is dried at room temperature. The product contains 41% inorganic matter and 7.27% organically combined chlorine (the derivative of dichlorotriazi-
 EMI9.3
 nyl of the raw material - at 59% purity - contains 7,21) .é binds chlo- II (,). The orange-red product dyes wool and cotton orange with high fastness to light and to water treatments.
 EMI9.4
 



  The 2-.nitro- / '-a1: 11.210Cilphéllyla.itle-3' 4-di sulfonitlue acid used as starting material in the above example can be obtained by reacting equimolar amounts of ll-pheny 7 diacid. ¯ènedia ^ alain-2-sulfonic acid and 4-chloro-3-nitrobenzenesulfonic acid in aqueous solution at the boiling point in the presence of calcium carbonate. The mixture obtained is made alkaline with sunflower with sodium carbonate, it is filtered and the filtrate is made acidic to Congo red by means of a 35% aqueous solution of hydrochloric acid. The greenish-yellow precipitate is filtered off, washed with 2N hydrochloric acid and dried.
 EMI9.5
 



  Instead of the 19.4.5 parts of 2-ni.tro- ± -a-ninodiplzônôrl, a.iine-3 ': 4-fii, sulfuric acid used in this example, 19.45 parts of 2-nitro-3'-alsinodilhcnyla.nine-.s, .'- cl: isulfonic acid, 17.1> 2-nitro-3'-aniino -.'- carboxyydiphenylauine- 4-snifonic acid, or 17 , 8 parts of 2-nitro-3'-amino-5'-carboxy-.iphnylnine-4-sulfonic acid. All these raw materials can be obtained by the general method described above starting from

 <Desc / Clms Page number 10>

 
 EMI10.1
 lucid.-eirloro-3-n z tr oben, mesulfonic and p: 'üényI8. ± 1E: suitably substituted diamine.
 EMI10.2
 



  Evi.PLL '2.-10 parts of 2-nitro-! R' -. Ethylāainoeiiphenylamine-3 ': .- c'; isuifonic; ue are dissolved in 400 parts of water containing 25 parts of a sodium carbonate solution, 2N and sufficient piled ice is added to lower the temperature below 5 C. The solution is stirred and a solution is added. of 4.6 parts of cyanuric chloride in 25 parts of acetone by adjusting the mixture to pH 7 at short intervals by the addition of a 2N aqueous sodium carbonate solution. When a clear solution has been obtained and the pH remains constant, laying a few
 EMI10.3
 12 parts of ion-potassium phosphate and 6 parts of 4-sol phosphate are added.

   Then added 100 parts of chlorine> ssiu = li and 50 parts of sodium chloride and we have you 1; .u'l3.ne for a few minutes, it is filtered and the solid residue is dried at room temperature. The product thus obtained contains 28.8; S of .1 [lti3re inor, -7-i-liiue and 7.95 of chlorine or 2nic ;, uement: co-sbin6 (the dichlorotriazinyl derivative of the Liatière pre-iliè- re, at 71.2% purity, contains 8.5% chlorine). The product
 EMI10.4
 dyes wool and cotton in yellows of high strength, both luxiiére and trp..i tē: ¯ents by hl..1laicle way.



  The 2-nitro-l, .'-: r.ét.lylaninodiph ^ nylmine-3 ':! R -;' isulfanic acid used in this exc. 1, ole can be obtained by dissolving quantities of 6cuiiuol, - ' Culeircs diacid! .- ¯rtl.ylaai.noaiziline-3-sulfonic acid and 4-cllloro-3-nitrobenzenesulfonic acid in water and boiling the solution in the presence of calcium carbonate. When the reaction is complete, the mixture is made alkaline with
 EMI10.5
 ù.oycn carbonate of soditba., it is filtered and the filtrate is strongly acidified with ciilorhy acid. concentrated risk. The crystalline precipitate is filtered off by filtration, washed with 4N hydrochloric acid and dried.

 <Desc / Clms Page number 11>

 
 EMI11.1
 



  Instead of the 10 parts diacid 2-21i tro-! ' -iW thyla: ninodipilcnyla: al¯11e-3 ': 1 ..- d1st11fOn11L1G used in this es.eaiple, one can use 9.2 parts eP acid 2-nitro-L' -? u: thyla.lino-l, .-Carboxy-di plnylamine-3'-sulfonic acid, which is obtained by reacting 4-m.ethyl .linoaniline-.3-sulfonic acid and 4-chloro-.3-11itrobenzoic acid.



  EXlli, IPLE .3.OLE 3. In 600 parts of ice and water, 8.2 parts of 2: lp-d: l.nl.tr0 -., .'- a: .i.nodiphenylaßnine- are stirred. Sodium 3'-sulfonate (prepared by reacting 2: j4-dinitrochlorobenzene with j3 "phcnylenediamine-o-sulfonic acid in aqueous ethanol in the presence of calcium carbonate) and adding a solution of 4, 5 parts: .es of?: /.-- dichloro-6-unethoxy-1: 3: 5-triazine in acetone The mixture is heated to 35 ° C. and the pH is adjusted to 7 at intervals by l Addition of 2N sodium carbonate until the lane of the suspended dye changes from orange-red to orange-yellow and until the pH remains constant for 15 minutes.

   Add 6 parts of disodium phosphate and 12 parts of phosphate
 EMI11.2
 ": lonOJ9tassiCJ.ue and the mixture is filtered and the residue dried at room temperature. The product obtained in this way contains 35% of inorganic material and 5.0% of combined chlorine Gold; a111qL1L'Mient (the dichlorotriazinyl derivative starting material - 65% purity - contains 4.5% chlorine.) The product dyes wool and cotton orange with high fastness to light and wet treatments.
 EMI11.3
 tr 1.P: GlS 4. 6.85 parts of 1,111110-2: l.-dinitrodiphenylamino is dissolved in 150 parts of acetone and a solution of 3.0 parts of acetate is added. of potassium in 5.0 parts of water.

   The mixture was stirred at 20 ° C. and a solution of 4.7 parts of cyanuric chloride in 25 parts of acetone was added. The product separates quickly
 EMI11.4
 yi..ēnent of the solution. After 18 hours, the product is filtered off, washed with acetone, then with water and dried.

 <Desc / Clms Page number 12>

 
 EMI12.1
 che at room temperature .. The product thus obtained contains 16, S5 / chlorine (la .'- f'ïichLorotriai.ylaraino) -2: .- c'3¯nitroc.ilhcnyla ... 1ine contains 16.82, '7 of c1110ro}. Dispersed in water under the form of a finely divided suspension, it dyes the nylon orange
 EMI12.2
 solid in washing and light.
 EMI12.3
 



  Instead of the 4 '- &; lino-2: 4-dinitrodiphény1w1ine used in this example, 2-ni tro- ±' -aôilino- ± -ac ± tyldiph8nyla., Llne, 2-nitro- ± can be used. '-rmiino- ± -cyanodipheizylaaiine, 2-nitro- 4' -éUllino-4-s1l1fonediIJ1 {tnylamidodiphenyla., J.ine, 2-ni tro - ± '-aLlino-4. s1Jlfone-f3-hyc1roxyétylar: lidodi;> hényl & iline, 4'-aino-2-nitro-, i1 - ethanesulfonyldiphenylejaine or ± '-a # iino-2-nitro-4-trifluoroni, thyldipli6nylanine. These compounds can all be prepared at p -> shooting at 2-nitrochlorobenzene substituted with an appropriate nanisre a position 4 and p-ph6nylanediline in othanol in the presence of anhydrous sodium carbonate.

   For example, .'- aclino-2: / - (; Íli trodiphenylar.1ine can be prepared as: .t,: e follows:
 EMI12.4
 Aite and boil under a reflux condenser
 EMI12.5
 for 3 hours, 20 parts of 2: 4- <1initroclilorobenzene, 1a, 8 parts of 12-phenylenediar, line, 1a, 6 parts of anhydrous sodium carbonate and 250 parts of 6thallOl. The mixture is cooled and
 EMI12.6
 The orange crystals which separate are collected by filtration, washed with ethanol and with water and dried.
 EMI12.7
 



  ± / l,> -., PLC 5. 8.7 parts of 2-nitro -! .'- anino -, - carbonanilidodipht5nyla.nine are dissolved in 150 parts of c! Io = ane j the solution is stirred and cooled to 20 ° C., and a mixture is added. solution of 3 parts of potassilli net in 5 parts of water. 4.7 parts of cyanuric chloride <! 25 parts of dioxane are dissolved and the solution is added to the mixture. When the reaction has cured, 200 parts of water are added and the mixture is filtered off and the residue is washed with water and dried at ordinary temperature. The product thus obtained contains 13.25%. chlorine (la /'--ichlorotriazinTla.zino-2nitro-4-carbonanilidodiphcnylaj:iine contains 1.31, chlorine).

   The

 <Desc / Clms Page number 13>

 
 EMI13.1
 product dyed nylon from an aqueous dispersion in oraii>; 1.s <? ' good fastness to light and to llu ,, 11ide treatments, Instead of L, .'- al: iino-2-nitro-l-ca.rl7on: xlil3.couiph.nyla- = iine, we can use t, .'- a.laino-2-nitro - / - ca; .rbonecyclohexyl-a: mi do-rliphc'nylë '.. JILine, and one obtains' Him similar product.

   These coi.ijpos4s) E; UVl2l1t be prepared 3 ;: silencing r8 & .ir rospectivei.lent 2-nitro-4-carbonanilidoc111oro benzene and 2-nitro-4-carbonecyclohexylaiiiidocl11orobenzene with 2.-phenylenedialiline in f3-ethoX " .f8thanol boiling in the presence of anhydrous carbonate of soCiuLi. l: 11-, -:> L: 1 6.-. 6.85 parts of 2: 4-di: litro-3 - aniinodiphenyl- to-: in 150 parts CJ'a.CetOlle and add a solution of 3 parts of ingredient (potassiuxl in 5 parts of water. We stir the u- 1; D., e and add 4, parts of cyanuric acid and the following is continued: for 18 hours 200 parts of water are then added, the residue is filtered and the residue is washed with water and se-
 EMI13.2
 che at room temperature.

   The product thus obtained contains
 EMI13.3
 Chlorine 11r965i (the 3'-C.'l.Cillox'Otrr11.a27..i1yla.rz11.110-2: L, .- dinitroâiplW: -. NylJj.line COl1tielt 16.82, '. Of chlorine). The product dyes nylon from the aqueous dispersion to oral solids washing and drying. r ... G. . , 7.We dissolve 6.85 parts of 2: / - cci! Litro-t'-a? .Lixloâipncnyla, .. ine in 150 parts CI 'acetone and we add a solution of 3 t': itl.f3S G 'c..CCt = aE' 'from i70ta..1.S1.L1-.i in 5 parts CY'eilu. We add 4.5 parts of 2: /.- c.ic111oro-Ermét! Oicy-1: 3: 5-trir.zi! Ze and heat the ..i-mixture to 30-35 C ju, -. U ', 3.u .O, Ilent oL1 la. reaction is complete. We add 200 parts key.'e [11.l, we filter it: a. 1a11; e, the residue is washed with or'u and S3C: le at 13. ordinary tc-iperature.

   The product thus obtained contains C11 t 8.1, j of chlorine (10 / ,. '-¯.! Ti: o, j ^ Ci110I'OtricZnWrl 2tlll0contains c3.5, of chlorine). The product dyes the nylon from a squishy solution orange.

 <Desc / Clms Page number 14>

 
 EMI14.1
 c #. # = .- PLiù 8.We dissolve b, S5 parts of 2: .- Cail t7: 'O -'- 2:' ¯7.i2ocJiÎ1¯ t1'1- 1: '- .: 111th in 150 parts ï = 'cwtone and on. add a solution (you 3 parts of pc {t ['te of potassiul.1 in 5 parts el' 881.1 .. We add 6.05 .9 'rtie'S of 2: 1-riczor. -: 3 -, -! , '. nory-1: 3: 5-triazi.ne and the mixture is stirred at 25 ° C. for 18 hours. 200 parts of water are added and the mixture is stirred until the mixture is stirred. The oily precipitate solidifies, then the precipitate is filtered off and dried at room temperature.

   The product thus obtained contains 6;, 4- of chlorine (la .'- phenoxychLorotriaziliylasislo-2: /.-- nii trodipiiiny1a iise contains 7.47 {, of chlorine). The product dyes the nylon from a rough dispersion to laT solid oranges: xire and 1.leave.



  ¯¯. '¯i'Lt'¯ 9.On p:.; I teach you..i \'. Le:) el1. <Пnt 3 hours [40G, L,., 2 pi'rtie;:, ru? O- main uit (ce 1 ':: 1-ei # .¯> 4 100 parts cl' ,,:. c {toL'le and 1¯, 20 prj-tie to 'thf'l101s.,: in0. We filter the solution obtained and 1 - <,>. J parts of water are added to the filtrate. The i, r (el11be is filtered, the resioll is washed with water and hidden at room temperature. obtained contains 8,1 / b of chlorine (the 4 '- ([3-l1yclroxyétllylp.ninoc. ilo ro - Lri a zinyl x - .; ino) -2: 4- <ii => 1 ti? c ili = oh4njrla ., iine contains 8.1 l of chlorine). The product dyes the nylon from then an aqueous dispersion in orwlt'.s of a high solicit 'in washing and: 1 lttire.



  Instead (the 1.20 prrtip, - "'éihanoL1;.; Ine used in this a :: ... plc, we can use the quantities;: ioLéc1Jlaire..ient / quiv? Lentes o'r.:. TOniauue , of cthylar.d.ne dcthylpline of ÜiJ; tl1ylE'l.lil1e, of "1 th, ylRü1ine, of 11-LtîtIl;, T1ca1111o.ī <: ine, of c1ieth81101Pc'üil1e 'or of 0 1.ydrozY- [3-Lthoxy (thylDHlil1e. Ruins which have these the ace points of 6bl.'Ù. Li.ti.on are, .V 'ilt [1Leusc..1811t intI'o <> aites in the inketon8 under the for-: .ic-, 1'Ull (: solution: 'q1.l0Uf.C concentrated. i': 7) PijM 10.



  Dissolve 6 "H5 parts ne 2: .- dinitro-l, .'- m: inotliphenyl- ..; in." 'Years 150 parts ii'ac4tone and add a solution of 3 par-

 <Desc / Clms Page number 15>

 
 EMI15.1
 ties cl'ac: wt. potassium in 5 parts O. ' water. 5.9 parts of 2: / - cie111oro - phcnyl¯1: 3: 5-tria.zīne are dissolved in 50 parts of actone and the solution is added to:. ::.: La.nbe ci -above at 3. C. Then stirred on 1 (12 nGe pen (ant 1 hour at a temperature between 35 and 405 C and the product is precipitated from the solution by adding 20U parts thereof. The orange product is filtered off, washed with water and dried. It contains 6.9% chlorine (4 '-. ohénylc11lorotriazinylaOE1ino-2: 4-ciinitroéLiphenyla1nine contains
 EMI15.2
 '7.65% chlorine). It dyes nylon from an aqueous dispersion orange.



  EXAMPLE 11.-
 EMI15.3
 4.95 parts of 2-ni tro -.- tri.fluoro: .rcthyl-3'-.: 'No; :) jl) 11.'nylaflil1.e and 4; 3 parts of 2: 4-dlchloro are dissolved -6-phenoxy-1: 3: 5is., .Z-ine aiis 50 parts of a.cetone and a solution of J losses of [t.cte.te of iJot, xsilz, 1 in 3. Water is stirred for 2 hours at 25 ° C. 200 parts of water are added, the product is filtered off and washed at 23 ° C. then to ¯.¯Ltha.nol. The product thus obtained contains 6S% of chlorine (3 '- (:; IlénoJ: y-chloro-triE zinylmJ.ino) -2-ni tro-4-trifluoroII ± tllyldi-) 11. {lly12.:¯ine contains 6, 65i (chlorine).

   It dyes nylon from an aqueous ersior¯ ..i.s solid yellows in wash and wash. the light. jì 1- iPLî ± 12.On (lssout 3.61 parts of 2'-nitro - / '¯t ..: aülo-ivt - pîu.7.y1- ..¯o: .ß: oline and 4, 0 parts of 2: .- e: icllloro-6-; hénoh.y-1: 3: 5-'triazii7.e in 50 parts of acctone and we:. Add a solution of 1.5 parts, 1? ' re lt; = te this potassium in 3 parts of water. The - :: liange {: n.: nt is stirred for 2 hours at tc "r;,:> Ordinary Cr2turG. 100 prrt.7.U are added. 3 of water and an oil separates from the solution. The mixture is left on 1: 1 (left for another 16 hours and this oil solidifies and is filtered off and washed with water. product? if obtained contains 8.35; 'Z' of chlorine (4'- (phenoxycliloro.triazioyl) -2'-nitrol'f-ph8nyLnor'pholine contains 8.29% of chlorine).

   It holds the nylon of then 1Jn <: aqueous dispersion in yellows of good solidity.

 <Desc / Clms Page number 16>

 
 EMI16.1
 



  The 2 '-ni tro -4' -anii, iJ o - ± 1 - phìJ.yLnor 1> iioline can be obtained by reacting the 4-chloro-3-ni troacetanilirle with 1; orpiloline, this reaction (both followed by treatment of the product with an aqueous alcoholic solution of clilorayriic acid to hydrolyze the acctyl group It melts at 131 - 132 C.



  F: = :. iPLE 1, 10 parts of 1-nitro-to-xdinoacridone (obtained COke it is described in the Journcl of the Che.aical Society, pages 595 to 597, 1947) are dissolved in 200 parts of di = ié .thylforiaié- ± de. The solution is stirred at 90 ° C. and a solution at 90 ° C. of 20 'rties ce 2: .- Clsoro-6-plnoy-1: 3: 5-triazine in 100 parts is added thereto. tlqlfor.:.2iê?¯Üc.:e. The tei;:;: <r '"'. Ture amounts to 110 C and the product., ¯ ¯." -, lliwe c: e 1 = Solution still hot-. The l6liaic was cooled to 60 ° C. and the product which had separated out was collected by filtration, lifted with Ll8thylfolyl, then with water. The obtained: .roc "lÜt? Insti contains 7S of chlorine (l-nitro-8- (chloro-:; .. r ::. J1ozytric.zinylē'J.ino) ecidone contains 77 of chlorine). nylon from an aqueous dispersion into oranges.



  --b'LE 14.- 4.15 parts of 6-bro.ol are dissolved: 5-dinitro-2- (4- ê ... "inornilino) n ±" pht81ene 0 '? ns 50 parts at' ac6 .tone and we ... <318on56 la
 EMI16.2
 solution a solution of 3, 7 parts of cyanuric chloride in
 EMI16.3
 20 parts of acetone, the mixture is stirred at 10 ° C. and a solution of 2.5 parts 4'i.cétc, te of Package 4 parts dee to U.



  The mixture is stirred for 30 minutes and then poured into 200 parts of water. The resulting precipitate is filtered off, washed with u and a, u 2.thpnol and dried by exposure to ir. Then 5.5 p. Of this product is dissolved in. 100 parts dc <tonej as well as 1.9 parts Li '(tl1ano13 ... ine and the solution is nitrogenated for 2 hours at 40 C. Or add 100 parts of water and the. B-bro = .¯o- 1: 5-d.irLi-tro-2- /.'-(/.,r-chloJo-ç'r-hyc,rozyctn.yla.iino-lrr-3"-5'ri:ri zinyl-2 " -nino) an: Llino> na, lztalime) r: ci1Jite, and it is separated by filti ,, -tioii, washed with er.u and dried by exposure

 <Desc / Clms Page number 17>

 in the air. The product thus obtained contains 13.1% halogen (expressed as chlorine), while the calculated figure is 13.2%.

   The product dyes nylon from an aqueous dispersion in solid orange-brown shades.
 EMI17.1
 



  6-broino-1: 5-c.nit-ro-2- (Lh '.- 2, iuinoanilino) napiita.lêne can be obtained as follows !. Stir together in 20 parts of boiling alcohol for 4 hours., 1.88 parts of 2: 6-di--
 EMI17.2
 broino-1: 5-dinitronaphthalene obtained as described in Journal of the chemical Society, 1952, page 259, 1.1 part of p-
 EMI17.3
 phenylenedia: Line and 1.8 parts of sodium carbonate. The mixture is cooled and the brown crystals which separate out are filtered off and washed with alcohol, then with water and dried. the pure substance obtained by crystallization from benzene forms hexagonal plates melting at 198 - 200 C.
 EMI17.4
 



  1; .. ¯¯, ¯¯PL. lO. 5.6 parts of 2-nitro-diphenylamine-4-sulfone-Ünothylaülic1e are dissolved in 50 parts of acetone and mixed with a solution of 2.25 parts of potassium acetate in 3 parts of water. . A solution of 3.08 parts of cyanuric chloride in 40 parts of acetone is added and the mixture is stirred at 20 ° C. for 2 hours. The mixture is then poured into 100 parts of water and the product which separates is filtered, washed with water and dried at room temperature. The product thus obtained contains
 EMI17.5
 13.6% chlorine (2-ni trodiphenylf) wool-4-Rulfone- [3- (dichlorotriazinylc.ulino) ethylB: Jlir; e contains 1,., '7; chlorine). It dyes nylon from an aqueous dispersion to solid yellows.



  The 2-nitro-diphcnyl, xine -.- sulfone- (i-aia.inocthyla ::. Ic? E used in the above example can be obtained by reacting this 3-nitro-4- sulfochloride. chlorobenzcno with p-chlorethylfU1ÍrW, condensing 3-nitro-4-chlorobenzene .sulfone-f3-chloétl1Yl a ::. e rNult, nt nt nvec 11I1l1inG to obtain 2-rU trodiphenylf.) nÜ) Jü-Lf -sulJ.'o! 1o-D-chlorethyln ;, lic1c and then realizing the product with phthalmide and then with L'1iyr <]> ir # iixc *

 <Desc / Clms Page number 18>

 
 EMI18.1
 i; ii? LT 16.We dissolve II, 2 parts oxacid 2-nitro -.- sulzone-3-ô.rc xyethyl <¯, iic: o-4 .'- É.t'tlji 1] .i "10 -G''ißh.: Nl ür¯e-3'-sulfonicue (obtained from acid / - .:

   thyls.ainoaniline-3-sulfoniclue and 4-chlorine-3-nitrobenzenesulfone - hydrosythyl? ide) in 400 parts:! 'water containing 12 parts of a 2N sodium carbonate solution and the temperature is lowered to below 5 C. A solution of 4.75 parts of cyanuric chloride in 25 parts of acetone is added and
 EMI18.2
 the pH is adjusted to 7 at short intervals by 1-lac, adding a 2N sodium carbonate solution. After about 20 minutes, a clear solution is obtained and the pH remains constant. We dissolve
 EMI18.3
 in the solution 12 parts of Lionopotassium phosphate and 6 parts I cisodium phosphate and 80 parts of chloride of;:; O (111.1.l and the product is pr # = ci = 0iti ..

   The mixture is stirred for a few hours, filtered and the remaining product is dried on the filter at room temperature. The product thus obtained contains
 EMI18.4
 nj, 5 (lë of inorganic material and 10,1, 'of combined organic chlorine-., ¯c: izt (the dichlorotriazinyl derivative of the pr e: ire. uatisre, at a purity of '78.5, contains 9 0.05 chlorine).



  In r ':' 61a, nt the reaction conditions, om can make r '<j <1 r 1' a.c id. e 2-ni tro-4-f3-hydroxyûthylsulf'ona-.üco-4 '- :; ié th3rlziaino d.ihé.nglc¯aine-3'-sulfoninue with the triazines mentioned below. All products can be used to dye cotton and wool yellows, high fastness 3. to light and to wet treatments.
 EMI18.5
 
<tb>
<tb>



  1: 3: 5-Triazine <SEP> Temperature <SEP> Duration
<tb>
 
 EMI18.6
 : 1-ü3.csloro-6-.¯ftnoy- 35 C 1 hour 2: / - t.ichloro-6-pl = c.-nucle 35 to 40 C 3 hours 2: Hc: 1 cl-iloro-6- ph {nyl 65 at '70 C II hour 2: /: 6-trihro.o- 5 to look l'l. hour 2: 1-ciciloro - 6-thiocrGsoî: y 80 to 85 C 3U minutes 2: 4-c7ichloro-C-nhi nylauino 5 C 30 minutes

 <Desc / Clms Page number 19>

 
 EMI19.1
 ...: L3 17 ..- ¯.
 EMI19.2
 



  9.73 parts 2-nitro - / '- to :: inodüariêizylaaine-3': .- d.sulionicue are dissolved in 400 parts of water containing 12.5 parts in a 2N sodium carbonate solution and one Add to the solution a solution of 4.5 parts of 2:.-cichloro-6-thoxy-1: 3: 5-triazine in 25 parts of 8 ketone. The mixture was stirred for 30 minutes at 34-37 C, during which time the pH was adjusted to 7 at short intervals by the addition of 2N sodium carbonate solution. The reaction is complete when no further pH change occurs for about 5 minutes. 6 parts of disodium phosphate and 12 parts of monopotassium phosphate are added and when these products have dissolved, the product is precipitated by the addition of 100 parts of salt.

   After filtration, the solid residue is che. ordinary temperature. The product as well
 EMI19.3
 it was. contains 51.8% of inorganic matter and ?.7Jll of chlorine com- 3ii.i organically. (The chloro-methoxytriazinyl derivative of the = ii; 1: 1st proi (1st, at a purity of 48j2% contains 2.76; b of chlorine).



  The product dyes cotton and wool very light orange in washing and light. One can get breast products
 EMI19.4
 bla.bles by using instead of 6-raethoxy-2: L, -d.chloro-1: 3: 5-triazine used in this example a molecularly equivalent amount of the compounds mentioned below:
 EMI19.5
 
<tb>
<tb> Temperature <SEP> of <SEP> Duration <SEP> of
<tb> 1: 3: 5-Triazine <SEP> reaction <SEP> reaction
<tb>
 
 EMI19.6
 6-uthoxy-2: 4.-dichloro- 35 C 30 minutes -6-buLoxy-2: 4-dl.chloro-, .0 C 90 minutes 6- (beta-ethoxy & thoxy) -2: 4- 35 C 30 minutes līchloro- 6-phnoxy-2: 4-c! ichloro- 80 C 2 hours 6-thiocr & soy-2: 4-dichloro- 80 to 85 C 30 minutes
 EMI19.7
 1> X '' 1;

  BATTERY 18. 12.9 parts diacid 2-nitro-t, .- trifluoroacthyl- /, e-viiiinodiphc'nylaj, line-3e-sulfonic (obtained from l, .- chloro-3-) are dissolved.

 <Desc / Clms Page number 20>

 
 EMI20.1
 nitroiaen otrifluoride and (; c.eice n- pii <Fn yl ane <1 i n .., 'inc single tallow) in 400' parts ci. ' 0: 11 containing 20 parts. '. - Carbonate of s & dim :.



  2N and the solution is heated to 80 C. A solution is added cc 9j5 parts cie 6-iJizénox> .- 2: 4-f # icl loro-1¯: 3: 5-tJ'ia; xiize r, m3 50 parts f'e dioxane and the ', H is adjusted to 7 at short intervals by the [' (.:. i t10n -de solution of carbonate ie sodiUi.1 2N. The reaction proceeds, i1.?; ve in about 10 - 15 minutes and then 12 parts 0 r.onopotassiuue phosphate and 6 parts disodium phosphate are added. When these are dissolved, the product is precipitated by precipitation. It is made up of 100 parts of chloride of oc = iua, it is separated by tr1tion and dried at room temperature. The product thus obtained contains 14% of ..1 etire inor, <nirue and 5.9 ) 1 of combined chlorine gold. ^ RziLe..¯crzt.



  The <, lriv ± of c.iÜorOj21: no7tria.zinyle of 18. material .e ': .p -rt,: z a purity of 36 ,, contains 6.1.;. 8 / :; of chlorine. The proauit dyes cotton and wool solid oranges. Instead of lucid 2-r¯itro-t; -triîlLOro ..-; l ti: yl -4 '- # -; iic oc. iplzényis <. ia # -3 '- sv 1.ioni <¯ue use in this t Ù:; - <;; .. 1-: le, we can use a slow c1..v: ntit / c: c¯u.iv (:: "2.cic.e 2- = zà. Tro-4'G¯v ir: o - sulfone-ph; c. Ro: ¯yétFrJlo-.¯idodip'rnrla.line-3 '- =: uli Gni:; yue, i 'act e -nltrG-l; .'- c': ¯.! 1I10 - r'-SLlii Gile-i-: f 'i Of =;

   Ct: .lj lv ':: i C, .G :: L3it 1? Tj'1r.; Ine-4-sulfoniru (:, diacid 2--2litrG-' -ét'¯l, rao -.-., Llli Glle- -'ri;% CiI'O '; ß: tiJl .... ic; ocliphnylr: ine-4' --- suf'oniaue, 'cïc: ¯e 2-r = 1 tro-4' - e- # ino-4cerox fû inh njrlc¯.alle-? '-SL11: L Gnic; lie, diacid e 2-nitro-4'- iYiG-d.ïz nylE'¯,: ine-4-sulfonirlu e or ce e -ni tro-4 '-8 ... irè.orÜ) h (n ::, rlL' - ",. ine-.3 ': 4- his (sulfone-p-rJcro ;; .tiyl ¯i' e). All these inter: ¯f: ¯ia.ircs are easily obtained by reacting a drift iJ'ortlio-c2 # lcx o - = - 1itrol; .eiizi; ne with a!: J! lfnylènecJi8,: 1ine aü.; çLl, te..¯ent substituted.



  [.Zj, = I, LL 19.We dissolve 45 parts of 2-nitro-4 - sulfonc-f-hydroz; 4 tiiyla.; I <oi> '- (A. "- a.- .: i = ioiniliso) à.iphênjri * - .. ii = e-3 '-sxiîo.ziiL = e' '' -1 '<' 1500 parts water containing 4. parts of soul; olution of c eo :! te of G.! 11.t¯.¯ 2il. On 1 ", f :: 'ol'; it 1D solution to utlG 'te:., y'rC.tl..r0 below 5 C and we add a solution e 17, parts C8 c.iloride c '] anuriyve d'ns 200 pr-ti'2 sd' afé Gm. It ::.; 'En.:.u1'; a r: c tiGm fast

 <Desc / Clms Page number 21>

 
 EMI21.1
 and the effect is 5% (the liquid is neutralized by the addition of a 2N sodium carbonate solution.

   After about 10 minutes there is
 EMI21.2
 no new prI chaDgilent and the solution is buffered by the addition of 50 parts of nonopotssic phosphate and 25 parts of disodium phosphate. 100 parts of sodium chloride are added and when all the salts have dissolved, the product which separates is filtered off and dried at room temperature.



  The product thus obtained contains 13.9% of inorganic matter and
 EMI21.3
 8> 8li7 'of combined organic chlorine (the dichlorotriazinyl derivative of the raw material contains 9, Zi of chlorine). The product dyes cotton solid browns with slow water and light treatments.



  2-Nitro -.- sulfone- (3-hycTro, cyûthylamicto-t, .'- (h.1 - inoanilino) diphenylaa.ine-3'-sulfonic acid used as material of ", ': -, art in the above example can be obtained by reacting equimolar amounts of 4 - chloro-3-nitrobenzem-p-hydroxy- -chylsulfonaulde and 4-a.Liino-il.3-ac- acid. , thylaxiiinodiphc-'nylajuiiie-3sulfonique in aqueous solution to the Di-illition in the presence of calcium carbonate. The mixture obtained is made alkaline with sunflower with filtered sodium carbonate, and the filtrate is acidified. in Congo red by hydrochloric acid, a brown tarry solid precipitates and the aqueous liquor is separated by decantation.

   The solid is dissolved in 1000 parts of water, 125 parts of 35% aqueous hydrochloric acid are added and the mixture is made.
 EMI21.4
 boil the - ,. c '; lan, -, e for hour. The brown solid material is then filtered off, washed with water and dried.



  Instead of lucid 2-nitro-L, .- sulfone- (3-hydrocytthyl: .idol .'-. (L.tT - s ::,. InoG.nïlïno) dipht: nyla.uine-3'-sulroniue used in the example one can use an equivalent amount of the compound which carries in position 4 instead of the group ,, ulfonc - P-1-iycro, -cy-, thyl, -L-iiico, an acid group SLtl .: e0ill.ciue, sulione -bi s (hjriLro> iyé tlzyl) a1: ii do, sulfone (.N-Iil6thyl-hyà.ro: X.Y '(thYl) (J, i.lido sulf'oizeGiui; ltizylawié.o , sulfonel.J.orpholido, rmlf'one (Jil-sulfoanilido) -,:; 1 <ltii <..; zesulonyl or carboxy.


    

Claims (1)

EMI22.1 1:: .. v 1 ..; N DIe. 8. T ION s. ----------------------------., .- Nitro dyes of the formula: EMI22.2 EMI22.3 oâ D rcpr sente vs .z <.y. * ul "'1ilt? 1 nique or benzene (.:. u: 1 ...: it can be further substituted or the to.:er' 8-zote N is in ortho position by r :: ';') J: "ort to the nitro group, X r '.' rdsej.ite Ge Z'ryc = rone or a 1.YL.rocF.rboné radical (it can be zu5rtLtu6, R represents a <.to:,: e 0 'llYdrogsne or an orbr¯lic rpdicri; ue rattz> ci14 to nitrogen by a 8.tO ... Le of c ['. R;) one, and where R i eüt be linked to X when X rt: has a radical Aß'rOC: ^ l '!? 01TC or to Du in position ortno with respect to L E't #, 18,:>. 30 te N to force a 110Y ±, u i2 t'¯rOC ',, TClICßuC, new nitro dyes: ¯ui are also cprF.ctrisé in that they contain at least once the group: EMI22.4 EMI22.5 where A 2, 'c.pr,' feel?: 1¯'m.Lo; ne, B represents a, ryle, a, lEi3le, halogen, alco: y, r..rylo: y, alayltnio, 8ryl thio, nr, ro, r, lercÇ \ J? to, a. '. ino or amino substitutes and Z represents hydrogen or a hydrocarbon radical which may be substituted. 2.- Manufacturing process of new .iitro dyes, EMI22.6 cf-rrct'risú in that we fnit r ': é1.; ir a halo' no-l: 3: 5-briazine in the formula EMI22.7 EMI22.8 or. A and B have the position: llfle'tiol1 given Ô; #iis claim 1, and <Desc / Clms Page number 23> a nitro compound of the formula: EMI23.1 where D, N, X and R have the meaning given to them in the EMI23.2 claim 1 which contains at least one 8lûino group of the E) formula -lm.Z where Z has the S1.gîll .rlcs.ti.on given in claim 1. 3.- Manufacturing process of new izitro eoloran41s, characterized in that the oiz fe.i t react a dye lli tro de la. Îor¯..ul data, -J.a: ns resell tion l, where D, N, X and R have the meaning. donnve in the. claim 1, said nitro dye containing at least one group of the formula EMI23.3 EMI23.4 wherein Z and A have the sincificntion given to them in claim 1, with an a-line or an alkaline ta.1 salt of a phenol. 4. A method according to claim 2 or 3, characterized in that the nitro dye is isolated at a pH of 6 to 8. 5.- A method according to either of claims 2 to 4, characterized in that the nitro dye is scné at a tempé EMI23.5 r turn CO.:1IJrÜ:e between 20 and. 40 c. 6. - Process according to one or the other of the claims EMI23.6 ; :: il 5, because: ctéiiisé in that the iiitro dye is dried in the presence of an IHrl.lett8.Ilt buffer as'jnt to maintain a PiI of approximately 6.5. 7.-. New combinations of dyes characterized in ce ', t-'C11.G'S e'Jmpr,: Ll.l18ll t; a nitro dye according to claim ly and; A buffer according to claim 6. J.- -ecJ ^ C (2 do manufacture of color :, l1t ::; ni '1:; 1'0, in partC¯! L; Lt.'? ': FariYiïf'. DëcrLL Cl - '} l: J: .H.1S! "VC'C special reference to the examples cited.