BE622565A - - Google Patents

Description

       

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  "NEW BAIC DYES AND METHODS FOR THEIR
MANUFACTURING AND THEIR APPLICATION. "
The present invention relates to novel basic dyes, corresponding! to the general formula (I) of the appended table; it also relates to manufacturing processes for these dyes,
In this formula (I), R1 signifies an alkyl, cycloalkyl, aryl or aralkyl residue.

   Ar is an aromatic residue and R2 and R3 is hydrogen or alkyl, aralkyl, cycloalkyl or alkyl residues which can also together constitute elements

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 EMI2.1
 of a heterocyclic ring and the aromatic residues such as the residues R1a t H * which can bear dee tton-ionoene substituents, and eâ in particular halogens or .es alkyl groups. alexoxy acyl, acylaminot dialkylamino and / or allam1no;

   X repv feels an anionic residue *
The dyes of formula (I) can be made by various processes. Thus, dyes can be obtained having fabula (II) of the appended table, (in which R4 is an alkyl residue and preferably an alkyl residue. inferior,
 EMI2.2
 Re represents hydrogen or an alkyl or cycloalkyl residue, R6 is hydrogen or an alkyl or aryl residue and in which the aroma-
 EMI2.3
 ticks may present non-ionic bubstituantz * - genes, and X has the siit1cat1on indicated above),

   There are treated with alkylating agents of the dyes of formula 1 (III) in Table a = e to xed.



   The dyes of the invention can ren
 EMI2.4
 close as non-"iunogenous" substituents in alkyl residues, for example halogen atoms, such as chlorine, bromine and fluorine further
 EMI2.5
 hydro groups:

  Ky, aieeàfcy, ester of carbo "xylic acid, amide decides Óarbo11que, arylato or cyano, and the nuclei a2ôiuàtiuèg can enclose it * the same atoms or groups as well as of the remains.
 EMI2.6
 lower alkyl and âuifônamidei groups

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 EMI3.1
 Colorants corresponding to formula (1)
 EMI3.2
 and which may be suitable are those represented by formulas (A) to (R) included in the appended table,
 EMI3.3
 These dyes can be made by ezel pie by laying naphtholacte- <1tG) possible lemont substituted with the aromatic amines apl propriees 4uns an inert solvent, by ejîe y? Le * Un, 3 du oW, or9bens5è, ne, <a l ' helps 'oxyctlorup of pps' phore or thionyl chloride, t by putting in ber4et to:

  !, 'using an alkaline substance, the corresponding ba.ae from the product of ooa4ensa-
 EMI3.4
 tipn obtained in the form of salt,
 EMI3.5
 Co 4e PPQ alkylatin agents, 1és, it jp for example the esters of alipietic alcohols 1m. (Er1eus and mineral acids 0 '.), Sulfonic acids as well as alkyl halides. among others, climtly01 sulphate, didtnyl sulphate, ethyl ester 4th and 4th atonic alcohol, ester aêtbj / liquô ie 3, ** W itcluene sulfonic acid, methyl chloride, methyl braze, ylef iodide $ 1s) ylef 3.0 OhT. pure ethyl, eth11e bromide 11104gpq 4 'et + was n-propylop bromide 04 = 0 at' BP-p butele and n bromide -butyl.



  TI ent recozaand to proceed to ÎU'aky * ç4on in a solvent or diluent j, ne9 e 4 twin pe1: 'tl.pr 4Xv <îe ,. preferably between o0 'and 1, ooQ., Solvents or inert diluents apr> ropt': fté acnt onive other benzene, toluene, ch.1oobengbno

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 dichlorobenzene, nitrobenzene, dimethylformiamide, dimethyl sulfoxide, acetone, chloroform and carbon tetrachloride. Alkylations can be carried out with alkyl halides also in alcohols, for example in methanol and ethanol, if necessary under pressure; it is then advisable to use the alcohol corresponding to the alkyl halide used.



   Among the dyes corresponding to formula I, it is possible to manufacture those which have the formula (IV of the appended table -in which Rn represents an alkyl, cycloalkyl, aryl or aralkyl residue and in which the aromatic rings as well as the alkyl ester or cycloalkyl may bear as a substituent halogens or aleoxy, acyl, acylamiao, dialkylamino and / or alkylarylamino groups;

     the aromatic rings may additionally have alkyl and / or aryl groups as substituents, Q represents an aromatic residue and R8 and R9 mean alkyl, cycloalkyl, aryl or aralkyl, the alkyl groups can also constitute together the elements of a saturated heterocyclic ring system and the aromatic residues as well as the alkyl and cycloalkyl radicals may bear as halogen substituents and / or alooxy, acyl, dialkylamino and / or alkyl groups. arylamaino, the aromatic rings may also bear alkyl and / or aryl groups as substituents,

     and in which X represents an anio-

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 EMI5.1
 nique,., 7 also I after another process, and co.laîén cheuffant compounds of general formula (V) of the appended table with amines having the formula (VI) of the table, in the presence of agents dehydrating conm densation s <For this process it is necessary for "example to cite -. as naphtholactamez corresponding to the totffiule V and which may be suitable -0 the H-taéthyi nâïJhtolaôtaiùô 1 8} the .. 'r" ethyl-'napht'3lactaae' * 1)! 5, In "pyopyl * napho" -lactams-1,8; K-'iso'propyl-naphthola <: tamu * '1.8; 'N-n-buty ... naphtho.actamel, 8, I'lac'xwhxh tolactam-1 $ 8; the NoycloheXyinaphtolac'ta & 6 '!, 8; the:; bsnzyL3aph'Cb.aCt, nte'iy8;

   7.e N-2t.4phétiyl4thyl- naphtholactam-118 - N-phenyl'-fl3i? Ht0lactùae -1f8 and N -. (4 | -ûethylphenyl) -na5htol3etame * 1> 8 * These lactams can be obtained for example by heating , preferably at a temperature between 130 "and 18000, the corresponding carbamic acid chlorides in the presence of friedel and C: catts catalysts, in solvents ilip2toâi p'ab execiple in di- or tri-chlôrobengènèi Likewise, it is possible to use the substitute products of the lacteals obtained in this manner, such as N-mthyL-.4.b, omonrhtdLactam.ï, F; K-ethyl-4-broîaO'-aa'phtolactaas-1 S j} I'y, -4. chloro-naphtholautan-1,8 {X-ethyl-e4-diChloedm naphtholctam ', 8; .-. ethyl * 4- (N' '* - bisacetylamino)' -naphthola <; tan.e'1.8;

   1-ethyl-4-dimethyl-

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 EMI6.1
 amino-naphtholactew1,8. ethyl * "4 * aelC> tyl * naph <'tOlactam-1,8; (4'mthoXyphéhyl) * na? htolao tame-1,8; NthylëthMyhhtola6ta: ne' '- 1 <8 and -Ethyl * 2ethoxyfhaphtslaet! & Me-1.8.



  Compounds of the formula VI which can be used are, inter alia, N, J-dQthYanilin and II, N-è1: i & .ethylanilifies t lt: l. "'n ... uti t; yl..lf ... b $ t.1-ohloroethylaniline, the 2"' Gtho :: Y1li., ... garlic.! l1âth:, 'llràn11ine. j-methyl-dimâ-chylanilirM <1: q "'; I1thyll, Ocl.: I.phrtylam; iM, N.ethyl-d1phéYlam1ne, .mth14 ... ethoxy-diphenylaiainef W-ethyl-'éthÔjty- âiphêîaylaniitte, the 1..dim6tnylEl ..: Lno ... ntlpht: i \: I.nè and 'the 1 ... tliethylwn: Lno-
 EMI6.2
 naphthalene.
 EMI6.3
 



  As a:.; EJits of oMefis.-tion one should, for example, consider lys hlo # nUeQ of phosphorus acids, such as phosphorus oxihloride, phosphorus etoxybromide), phosphorus pentachloride and phosphorus trichloride {additionally sulfuryl and thionyl chloride, as well as phosgene, otannic chloride, herbal ttrachote, 1nc oh16rur, aluminum chloride, boron triilubrUrë and silicon trachloride Or dom tiilânjoz from ded compbzdst
 EMI6.4
 To implement the method as
 EMI6.5
 modified, by using the eoiapoëantâ (V) and (VI), one can proceed from there following mnîêeë 1 the lactam is heated with the amna - âü needed in a diluent - * at a temperature between enti4o '70 "and 1500at then

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 EMI7.1
 add the agent;

   of condensation.
 EMI7.2
 We can e..ie, ent Y.uf '.r first the
 EMI7.3
 milk with the condensing agent and add
 EMI7.4
 Then, for this procedure, lower temperatures are often sufficient, for example temperatures between 30 ° and 100 ° C * It is generally sufficient to add the amount. tita of Heine equizolar to that of I. cty3 v put o little * however use an excess, this axoè9 being! However, if the amine seevo of solvent Oocyae diluents are quite important, they are suitable in addition ah.saxc.re, 1,2-dichloroethane, "t 1 ,, fitr chlorq4ne, nltrobenzene, aùnbsnzra and leg di and the isomepated trichlorobensenes, as well as phosphorus oxychlopide and chloride
 EMI7.5
 thionyl,
 EMI7.6
 In the new cutting edges ba9.1,!.:

  1! 1 4 * the present invention, the rste X repress senna Z'al eme1 + t an anionic residue, for example 1 reet of hydrochloric acid, su acid, u '$, t of 7.'ac , c phosphoric or aQtq40 acid.



  It is quite obvious that it can GeQIU1.t y with! L4. to stay. other acids, because they are used only slowly for the solo formation of basic dyes without the prcpr "t3 tinptaiPale 0.
 EMI7.7
 be modified,
 EMI7.8
 your new coar, xnt present it
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 invention are suitable, particularly for dyeing, printing or hanging and spinning

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 mature products which consist entirely or mainly, in general of more than 65%, of polymerized acrylonitrile or vinylidene cyanide.



     It is in this connection remarkable that, when one dyes mixtures of these Wholes and wool, they hardly dye the animal fiber. A particular advantage of the novel basic dyes of the invention is their high yield, which gives the possibility of realizing very dark dyes and prints. The dyes and prints obtained have remarkable fastnesses,

   and in particular the fastness to light. to decatising and washing; they are distinguished by regular penetration and a beautiful shine. The new dyes of the invention are further suitable for lowering and printing tanned cotton, cellulosic esters, cellulose acetate and as well as for making anchors and ball pencil pastes.



   The present invention also relates to nitrogen-substituted peri-naphrolactams, corresponding to formulas (V) or (VII) of the appended table, [in which one of the Y represents the group R7-N- and the other Y represents the group # C = O, the radicals R7 signify identical or different alkyl, cycloalkyl, aryl or aralkyl radicals and the aromatic rings as well as the alkyl or cycloalkyl radicals may bear a substituent

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 EMI9.1
 hydroxy and / or ac104 groups and in addition the aromatic rings can g, 1iatn (and bear alkyl and / or aryl substituents.>,

   and that we can, among other things, use teotano intermediates to make a dye corresponding to formula (1)., We obtain the peri-naphtaiûctaads responding to formulas (V) and (vil) according to a new proeedj, characterized by the fact that one heats halo al1uroc of acids t: rbedaiquo6 corresponding to. \ :. x 1'ort.1ul3 general (VIII) or (1k) of the attached table, in Pl'03Si :: tlCe of a Friedel catalyst and cêaftse
 EMI9.2
 in an inert solvent, and at a temperature above
 EMI9.3
 sant 10CoC, preferably a tperatvbfe comprised between '130 and 180 "Ct' #>, 'In formulas (V), (VII), (VII) and (! JG) du cable au anneixe, Hal rijpré, G , fluorine) chlorine or bromine, one of the two symbols X | represented: rdtc and the other 119;

   croup ';' # ,, '
 EMI9.4
 
 EMI9.5
 the R7 annuities of remaining alkyl, cycloalkyl, aryl or aralkyl iuèntiques or diiTire-ntaî aranicttiquea as well as the r $ S alkyl or cyôlûalkyle can, in the king-auloc (VIII) and (IX) carry as substituents alkoxy groups and / or acyl, and in the foraules (V) and (VII) these 'nuclei and / or ra.3tes carrying tioiiae Gubst1tuafits des
 EMI9.6
 hydroxyl groups (formed by breaking down groups

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 EMI10.1
 alCOXY during the removal of the condensation) or acyl groups, Dafia all of the formulas (V), (VII), (VIII) and (IX) aromatic numbers can;

   in addition to carrying further substituents of the alkyl and / or aralkyl groups. It is possible to obtain by known methods the organic halos which serve as the starting materials for the arbamic acid rolitibous decisions. Eonviaiiftiant puetlculïëtemontd A common process of debutiôâtiôtï of the diilot4ileâ of carbamic acids consists in luira :: aj.t 'i: .VC10 of the phos- gene of the alpha-naphthylaftinea zippropriéoâ or their salts, by uxemp3.o the hydrochlorides. agents, for example in di or trichlurobenzene. Naphthyla1rlês which may be suitable are, for example 1 ... mt1c: 1J; '1111ho "' nphthalne; 1-ethyl-amino-napht alene} lëM-îi- prâpylaiBihû-naphthafie li6opropylamino '* na.pht & l6opropylamino' * na.pht butylamino naphthalene;

   1 * steiffylaaiino nâphthalen6; 1 "- cyclohexylaaitto-naphthalene; 1-bnyl & mino" naphthalene; 1-btta-phnyldthylataino-naphthadeo 1 ... phenylaminownsphthalrte, 1 ... p-tolylâminonahthalene; 1,1.4thxyphetlwmino ... naphthalen; 1-methylamino-2 * -et; hôxy * ftâtilit; awl | 1-ethyla ... ttino-2-n-butoxynâphthalèho; I-thylatdino-7-Zethoxy-naphthalene; Io 1 * ethylalkyl-.4-phenylsulfonyl * naphthalene; 1ethylaMno4thylnaphthalene; 1-ethylaminQ.6h1tftâphthalne; 1 ... ethylamino.

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 EMI11.1
 



  4.4dOAoro.naphthalene; the 1, .. bi; ptr ,, rg.



  ; htr, xxo 1,5-bis-ethylamino..nphthlèn, 1,1Wbis *> p4; enylamino-naphtcaene and 1,4-bis-t tkox; 7.ax.na) -naphtha7. anG.
 EMI11.2
 



  For the realization of the new process of
 EMI11.3
 manufacture of the new intermediate products ex) pu (VU), the Friedel and rafrss catalysts which are suitable in the first place are halo $ en9a 'a..ue such as 1 \ 1n \\ m chloride; Zinc cMorno, boron fluoride ein1 as 1'8 çfe3, form III ojrare, titanium tetraçhlcride, Stannic chloride and tricxk: .7.oride antijaûiwa,
 EMI11.4
 as well as mixtures of these catalysts and other *
 EMI11.5
 very catalysts of Friedel and Krafts, OO! W: 1t) solvent $ inertia s that are preferably the di- and the trl.rfOÎiXO'1 3.obenene, the biphenyl, the bipl \ él1Y + Qf.i c4lnough alone or in mixture, which enter;

   in c9na1dJ: tIatQn, I ast particularly advantagewtxx., taccadt7.r oem.! 1IQlvants already during the manufacture 4 $$ Qh0- rides of cirbamic acids, because it is then 1nqt1 of ipep the acid chlorides ogrbam4eqt; çg . 9 carries out the reaction in general at temperatures higher than 1000G The preferred temperature is between 1300 and 18000 approximately.



  The process for making intermediates (V) or (VII) is surprisingly p + how the reaction takes place, since iX; faXX, a4-t? expect that, in the presence of Friedel and Crafts catalysts, an unq oonddnsntipn will occur

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 intermolecular, and it could not be predicted that instead there would be intramolecular condensation, which results in a very tight ring system.



   Under the influence of Friccie and Craits catalysts, besides the proposed ring closure reaction, other reactions can also occur, such as the scission of ethor bonds. Under the reaction conditions indicated, the alkoxy substituents optionally present can therefore be transformed into hydroxyl groups.



   The parts indicated in the following non-limiting Examples are parts by weight.



   Example 1.



   To a solution of 37.8 parts of compound (F) of the appended table in 300 parts of anhydrous toluene, 13 parts of neutral methyl sulfate are added dropwise between 100 and 105 ° C., the mixture is further stirred for 2 hours at 100-105 C, then allowed to cool. The separated dye is filtered off under vacuum and recrystallized from 1000 parts of 5% acetic acid with the addition of 1 to 3 parts of activated carbon. The dye thus obtained corresponds to formula (S) of the annexed table, it gives on polyacrylontrile dyes and dark blue-violet impressions, exhibiting remarkable solidities.

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     The compound used as starting material was made from the following strip: dilute 169
 EMI13.1
 parts of naphtholactaae (1) and 22 parts of with 1,000 parts of ohlorobenzene. Between 90 "and 10060, 10 parts of phosphorus oxychloride are added dropwise, the mixture is then stirred for one hour at 100" - 110 C, allowed to cool and the chlorobenzene is removed by entraining it. z: steam * After having decanted the supernatant water, we c3issrut. The residue is in 1000 parts of boiling alcohol, the solution is filtered and after cooling is made alkaline by adding the necessary quantity of 20% alkaline solution of potassium or sodium hydroxide.

   We perfect the precipitation of the base of
 EMI13.2
 reddish-orange color by adding drop by drop 1 * 000 parts of water. in cyclohex, nc the 'melting point'. Ïa. 'ba.3e.', '' free is 1-10 C .. # 'm, -'. ''. ' Example 2.



  In a solution in 500 parts of to-
 EMI13.3
 lene of 33t5 parts of compound (C) of the annexed table, is introduced between 1 'r "It7'd,' dt methyl chloride until the mixture. has a pure blue appearance and a drop of the toluene solution, deposited on paper, no longer lets any reddish liquid flow.
 EMI13.4
 mix and wring out the dye thus forced under viùo,

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 which answers the formula (T) of the table. 'This dye
 EMI14.1
 gives on polyac: t ')' îÓt: t'11è are dyes and solid prints of a blue tending to red.



   The composa serving as sabric starting material in the following manner @ one dilutes 20.4
 EMI14.2
 parts of 4-chlorQ.nâphtQlQtroaG - ('t8) and 15 parts of; r, ... d.1ôthYl \ .1nilil'lo with 10 parts of chlorobenzene; to this mixture were then added between 1000 and 110 * 0 34 parts of phosphorus QuhlOfU.

   The mixture is boiled for a further 2 hours, then cooled to 0 ° C., the reaction product which has separated off is filtered off under vacuum.
 EMI14.3
 dissolved in 350 portions of hot tebs alcohol. A 20% alcoholic solution of potassium or sodium hydroxide is added dropwise to the solution until) the original solution-
 EMI14.4
 .ment blue, becomes roUËSi * On. then dilute the. #,;

  ) 'solution with 500 to) 0''t'p' <!! s of water and we, '- \ VV # wring out the precipitate SI.11SxiJ. After drying and recrystallizing from cyoldhexane, the compound thus obtained has a melting point of 4a 13400.



  . 1 1 1. i "1 ..



  Fifty-five parts of the tor- mule compound (G) used in Example 2 were dissolved in 100 parts of chlorobenzene and this solution was added dropwise, at 1008 to 110ClC, 13 parts of neutral sodium sulfate. methyl- After having stirred the mixture reactivates! for another hour at 100 -

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 EMI15.1
 11Q C, çrç éliaJno the ohlorobensehe by entrained with water vapor, one completes it. '1 litru with
 EMI15.2
 do the tsciu the dye solution obtained and after cooled sow sal3 :: 1V.,; C of ael wa? in Qn * holds the dye of Example 2.



     Example 4-.



   Has a solution of 41.3 parts of the compound. (1) of the annexed toblau, in 120 part of dim-
 EMI15.3
 thyWop & ieraide, we add between 110 * $ '? 12qçt 18 parts of ester atetyllue do l'ldt! ; .toluë'ns "'# E5ulòn.iqu <?, on agita lo ctulange endan''2 iîures') i" tè35> v.15Q G, on IQ laisaa rue: roi4ce on la dll aV {fQ Ob parts dljiu and do we add 10 '? parts 4 $ salt m4en, 1 "j product Ôrqr6 is filtered off under vacuum and pn recrystallizes it in 2.Q00 parts of 94; $ by adding 1 to 2 parts of activated charcoal. The colorant corresponding to the formula is thus obtained
 EMI15.4
 (Tj) of the table; it gives on pOh3ç² * Qnt%. "J, .e a blue, bright solid.



   The compound serving as the starting material
 EMI15.5
 e been; made from 4chloronn3ntc!). aC! te (1fµ) & t do 4ethoxy "A-methYldiph61nne. C9n; Qi \ péroenl al4 procedure indicated in the cond paragraph of Example 2; point dQ! e1 40 this compound is neighbor of 138 C.



   Example 5.
 EMI15.6
 



  Qn dissolve 36.9 parts of the clm: po $ q (tf) of the appended table, in 500 parts of xylene tQ1 +, .. nique, dried over calcium chloride, and one inqopf

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 pore drop by drop to the solution, between 110 and
 EMI16.1
 115 C, 13 parts of dinethyl sulfate. After having had the mixture reacted for an hour at 110-115 ° C., it is allowed to cool and the precipitate formed is filtered off with suction. Dye
 EMI16.2
 thus obtained responds to. the formula (Z) of the table; 4ine; ç4; it dyes the polyacyylonitrile a solid blue.



   The compound serving as the starting material
 EMI16.3
 was made from 4ç 2, -d1chloJ; "o.aphtolao- '#ta" "(1 µ) and do diétb.yia.1 +; i.JJ.9, conformed to the procedure indicated in the second paragraph of
 EMI16.4
 1 as'urp7u; the melting point of this compound is 1 'G.



  EXAMPLE 6 197 parts of li-ethyl-p4-naphtholactemo and 27 parts of ft * 6oxy'-N -nethyldiphjnylamine A 50% are melted together, and 19 parts of 50% are added to the melt while stirring. 'phosphorus oxychloride, the mixture is stirred for 24 hours ± 50-55 ° C. and the paste is introduced. The colorant thus obtained in 2000 parts of water. After breaking down the oxy-r
 EMI16.5
 Phosphorus chlpiuce in eoes, 0.5 to 1 part of activated charcoal is added to the solution, heated to 95 ° C. and filtered.

   By adding sodium acetate, sodium carbonate or sodium hydroxide solution, we adjust the pH value of the filtrate between 3 and 4, then add drop

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 EMI17.1
 from 50 to 100 parts of saturated marine soil solution, which has.:.:

  zze 3a separation under crystalline foras of the dye drilled, which corresponds to the formula (AL) of the annexed table The r-rdeme4t ost very good This dye gave on fabrics in P01Y- acrylonitrilo of tointuroa 90 impressions of a blue drawn strongly on the light *> 6fct PeMarquableNent solids to lightw The Mt.thyl'-perimpht & the <! Tatae 0'ut be made in the animating way at a> wfi- board of 26.5 part do dh.trtlr. of anhydrous altwpafalum in 100 partial of 1 '<di <ihlor.o & this was added dropwise between 11 and 160 "C and stirring, a solution of 2; t parts of acid chloride in 50 parts of ut then the mixture is stirred for an additional 30 minutes at 160 ° C. Once the mixture has been rinsed, one is poured into 100 parts of place, one is left with 1 acuue bud and the organic layer is diluted. -VL.0 60 parts of 20% solution of std3 carbonate;

  uausece! that the layer of dîc.1ôlobeiizêhe is free of acid After having separated the solution of sodium oarbow nate * lo distilled under reduced pressure One can purify the crude iii-e thyl-peri-naphtolactasa testing, by diatillation under vacuum or by rucristallis.tion in normal ilhoxane or cyclohex-MSt after having stirred
 EMI17.2
 activated charcoal. It is thus obtained in yellow crystals

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 EMI18.1
 fluorescent greenness lonat at 68000 The 416bllition point under 15 US att is 02 - jo6OC # your yield is almost qualitative *. 2.



  At 10 5 will leave N ut dà 51 parts of N, N ... aiiaûthylaniliriô, one added puU to can enttu 700 ot 80 0 and at the same time, GO pet1es of dhloruzo
 EMI18.2
 of anhydrous zinc. we then add drop by drop
 EMI18.3
 30 parts of trin1oe due ph0ëph, then we drink the Solange for 10 to the mibutès at 8000 and
 EMI18.4
 it is then diluted with 200 parts of benzene
 EMI18.5
 Anhy1ro, After liming the mixture at the boiling point for 12 hours, it was left to cool to 5060 ehvïe0he it was vctfse daiié to 10oo parts of water, the eleiüloibn formed until the phosphophyte trichlotide was decomposed. and we separate the cou6h - '' b @ N & qu We éliatofra # "# the aqueous solution of C] ht ,! O "'9, dO with de / 0.5 il 2 parts te 6hdïlbjb1n'c, tl4ifl; o! 4 bH the filter.



  The stream b <5 dttl'tyùt was separated by adding this marine * Ca, CO1011ant. ropôlid to the formula Afi. of the attached table; There is one lo1etbleU tibbua of polyacrylonitrile or 8 <ai'd'aoét6ta * We heat at J06b a7. parts of x-itonoi-
 EMI18.6
 
 EMI18.7
 bromo..l; .. thyl "!, éi'1" nphÓlactulJJll; 11G. 8 parts oxyf phosphorus chloride and 6.5 parts J, N-d1ethyl.
 EMI18.8
 aniline. To the melt obtained oh add drop

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 EMI19.1
 $ drip, stirring and for 5 minutes, parts it stannic chloride.

   It is necessary alo :: '; 3 will take Qon that the temperature does not rise above 10'Ot After & vo4- stirred the melted susse for # 5 thin at 110' = 'C, it is poured into 2,000 parts 41a1., \, On 4co 4p ose the excess of agent dGi conr 4Qnat, we then incorporate into the solution of ,, ca3 # btQ'1. \ 1e do 0.2 to 2 paptias of orbo-Pr <1- 0 ... it, We caf'3 until the 6bUlltion en and we ': #xa, En ajoi4ticnt eutto, eouttot 8g .1.
 EMI19.2
 cooled ratio obtained from 50 to 100 parts of solution
 EMI19.3
 sa. \ 1t''J .te marine pol, we get with a. tpèu good: rn ..: '1nt ot under forau crist Iline the dye d. corresponding to formula (Av) of the attached table. Go ro- Q; t, ', U1.t polycrylonitrile tissue donor dyes and ir p:; assio: brilliant ot very soliwoo.



  We can make 0 1-. m4nber 81.V6; the nt.mQb: t'mq..i ... cithYl..n:;,. phtoL9tsne used! To a solution of 197 parts of W- et5 [1 P tS: I; \, n:; 1! HtQ; l.l) ct'3; e d ::. Nf, 3,580 parts of Q '1; .4qo. banana, we add èntr9125 and 1, OQQ an out1Qn is 160 p9rti $ e of bromine in 3QO parts 4 1f2 * 4i, * a, axsb.rèxza, we stir the nullanrai for another 15 minutes; 4 13000t we let cool? 4 Ov7QC ost the solvent is removed by distilling it off aoya 1? pp of mercury approx. It is also possible to kl.t3x 10 1, ', da.pro'boxènc by 0nt1nmnt to the yapeuy of water. One can easily obtain in the pure state 19

 <Desc / Clms Page number 20>

 
 EMI20.1
 b: t'Ol! 1çh.lac: tarne remaining by recrystallizing it-c in do 1? acetone; it melts at 116OC L <3 is
 EMI20.2
 almost quantitative.
 EMI20.3
 



  Example C) Heated for 15 minutes at 600C 18 ,,, parts of Npiethyl-perinaphtolctamveo 1893 parts of phosphorus oxychloride. Then 21.1 parts of butyl-Nwbêtu chlorethylaniline are added to 1 ° C., with stirring, the mixture is added for 5 hours at 8000 and diluted to 8000 ° C. 50 parts of chlorobensene, in the courtyard 11 heated to 80 C, After having kept the mixture & SO90QC for 12 hours onee-rô, Iloxyçh'4, ojruro of the phosphorus in excess by adding
 EMI20.4
 drop 4 drop 20 parts of water Then remove
 EMI20.5
 IQ cftlorolwnzene by stripping with quarts steam after adding 0.5 part of charcoal
 EMI20.6
 activa to the remaining aqueous dye solution,
 EMI20.7
 we filter it * By salacious we get with a good
 EMI20.8
 yield of the dye corresponding to the formula (AD)

   
 EMI20.9
 té4-pleiix mnex4-; he dyes the polyacrY1Qnitr11e t1 br4e blue violet
 EMI20.10
 We can manufacture according to the procedure
 EMI20.11
 according to the! l ... metl1.; Yl! "'peril" aphtolact; e ut11isél 24 parts of 1-roethylino n1'ht = \:' enl.J in $ 400 parts of 1t.4 ... trichlorobnrz are heated : èe The solution thus obtained is treated, laying for 2 hours at 1 $ C '"160''C 3v -., c phosg, èneo The excess pt.oeon is then eliminated: one blowing in the dry air . AT

 <Desc / Clms Page number 21>

 
 EMI21.1
 to the solution of oax? bûtoiq \ 4th jinoi acid chloride obtained, one adds little by little, entered 1656 and 170 0 6 parts of aluminum chloride afihidre and the solution is stirred for a further 20 minutes.
 EMI21.2
 you are at this temperature.

   The mixture is then cooled to about 50 ° C. and the mixture is poured onto 10O0 ice cream scents * Chduitd is treated in a similar manner to that of 1 "J.tl !! l clunâ the operating stage of Example 6, for iJ * -ethyl * peri-naphtholact8as i.



  With a very good 2 '<9MjiaÉat, the I & éhyi- which boils at 1S ... 04C under 12 mm of mercury is obtained. The product rises in normal hexa or in cyloReXane melts 77 ** 78 C.



   Example 10.
 EMI21.3
 



  We melt 2ig parts of phenyl. pe: .. i-nphtoll1ataJnl3 tiV 2 'your parts' of n "ethyl ... d1phenylm1nG. Between 900 and 10000 we run into this molten iLt2.Ssô, while stirring, 20 parts of phosphorus oxychloride and the mixture is stirred. mixing for 8 hours at this temperature $ If the mass becomes too viscous, it can be diluted by adding another 10 to 20 parts of phosphorus oxychloride Once the time indicated has elapsed,

   the phosphorus oxychloride is decomposed by pouring the sheared into a mixture of 500 to 1,000 parts of ice and 100 parts of saturated aqueous solution of sodium acetate.
 EMI21.4
 sodium.

   The blue dye is deporeated at ta & ëâi atom nt

 <Desc / Clms Page number 22>

 
 EMI22.1
 It is suitable for coloring in the madde of polyacrylonitrilë LG H-phéiiyl * p <âMttaphtholûctÉiaô can be made from the following mânïàto i We introduce little by little JJô pattïoâ of acid chloride N * piUayl * ïM-ttd $ htyl * ti & tf ! It is in a m6larW ,,, e4 chïdttè at 1; o.coët COMPOUÉ of 70 parts of ohidrurû d 'ul wn1niWt1 tlnh: r;' 4G ot of 200 parts of This mixture then lays 10 $ 1 mifiutes at 1600 - 170 * C and then it is cooled to 30-30 * 0 Oh then add Cputto z dripped, oh for about) 0 minutes, 506 parts of 15% hydrochloric acid and the shower is separated from dJ !. dhlo1 "o'bn2lèbe and we add from 1 to part & da Activated carbon After having asit Pèfid:

  U1t. 2 hours ohvirch the solution is filtered and the Id 1,2wdlohlorôbenâênà is removed by vacuum distillation. The crude phenyl-'pôri 'naphtholactaae posted by re-crystallizing it in evolohemanee is put in the form of vrdâtr yellow crystals, which produce at 160 ° C. The yield is good. bL1J1 ..- 1.1.



  > Parts of N-ethyl-CKS '"1 bis-act11) .amln-pe1 * n3phtólatme are introduced into a mixture of j parts of 4 .jtaethoi y *' NJ> 6thyi diphéttylatiino and 6 parts of Óxyehlb1 \ tt ' o ds phosphorus The aasae is heated for 40 minutes at 95-100 0 and After ta-

 <Desc / Clms Page number 23>

 
 EMI23.1
 rmi4poient it is vrse in -100 uju prtj.3.



  32n adding? do sodium acetate to the. solution of dye fRxt ;; en.t acido thus obtained, one r..t .: lw its pii to L 4 approximately. It u-j already separates some of the dye. We p, richZîv ,, In separation by adding; dropwise a saturated solution do - ,, R1, '. rrt. This pont purify the crude colorate or Xq 'pQcrstaH'is, mt in 100 pr; i. 4 $ 5 of ac't-is & 5 acid It coppospond to the fqx;' ua (AB) of tbJ.eu! '1x ',, si? f, and! it overlooks the. po.!. yc? y3'onit'pl9 dia <.iNtu, p / et des: mpx4s., iaxs of a blou'tiyMH on 1q 4: ', can fjtvpiqusr 19 # et? nyl- <H *, îï 'lî4a i.



  R5l.rm.rRpx.n.gha3.a: u (points 9 pipR I'7Q 'uti; i * 3 - from N, 4CY7.,.: X, n.a: f..a.



  'M9 pap ttlon with 2,' nitric acid in 30. 'Uon 414ru; rqu "*, reducing: lv derivative mp'ngr4tr4 (point C1C ,,' 1, ', Oxx' i7" '7pr! Aveo d' M fep derivative 3xa% no (pvlnt do .fusion 19ccc) e4 un cnsùf Jî (ï te 'd3pivc!' 3in6 syyc an excess of aetsic anhydride.



  Shall we heat up? hour 80 * 0 6 parts of Iastayl-d mty7.tm.rjér, néttt. and, 6 xtta of 4-6thoNwN6thyldtpnyw aVQ <! P4opphprpp oychloywe 4Q xR 3 A a. .4a na,; e cooled, the majg%; ro perttg of the phosphorus oxychlorurj is removed by 4ist1 | Hation under vlclep Dissolve the crude dye remaining in 30P

 <Desc / Clms Page number 24>

 
 EMI24.1
 parts of water. The pH of the solution is adjusted to 5
 EMI24.2
 oar with sodium acetate, and we repair
 EMI24.3
 the dye formed, corresponding to the formula (AF) of the table, Qn adding salt mà * rnt It dyes the tables 3sus 9 in. yaar1.4n, 'r, Q in blue pulling on the
 EMI24.4
 green.
 EMI24.5
 



  , the placp of the c'ùox3rN * 'GhY.- diphenylapine, one uses the acme quantity of Ntzi "bstats-c, l.ro..éthy.i.us, or obtains, eA operated z> fj> a? 4ill urs' in the * zatiag way, a dye 'having' it 'lacquer; (Ad) 4u- annajeé table;, it dyes' Ife #' po.lya'eyylpnitrile get (1 'pn can * get the If-4tl ylW (dl..thylminp) w naphtholsctam used starting from thy.az, no ..



  (n3phtQlo.otiOTQ '(see 3xepple 11), by s4vee methylftion of the neutral sulphate of 4n6thylQ between, 100 and 110 "C It can be peorijstallisar in oyclohexçme and it .fooae.dHa crystals or? .age3 melting 112-l13 "Ct 'We heat 59 parts as Nothyl-peri-f, apîit! 0j.96t! 3X? E and 61.2 parts of cxYs3..oz, t' of .h9ophor, r 45.:,. Nutss to 70 * 0 * We add '' ensutta 'drop by drop, to the trap Qrt, .usl, sct' <'' 67 parts of N,., D, tra;, r ,, 3, .0 'act the mixing during 7 Louros 4959 .-, 1000C, then 3, q is poured into 1000 parts of water. The color solution obtained at 95 ° C. is obtained at 95 ° C. with 2 parts of activated charcoal and then the filter The dye obtained is separated by

 <Desc / Clms Page number 25>

 
 EMI25.1
 added i0a part of ael ftiariiu Co coloring kills it in shades purple-
 EMI25.2
 blue.
 EMI25.3
 



  Ai in this example oh r, replaces the ii, U-diethylanillne pax, An * equivalent amount of 2-zethoxy4.iï, ilwdimethylhiline, ehlë.fûH,, dx3y.a, tx3.13, ria de wéthl '; üßt; bctaah, o roethyl aniline, d <9 iî * phèxliaoī ± h6Jiiw iV% ifaphenyl * jpipériaihc, ac ITc'b, dlso ,, l.t3nthyi: 3 ;; ,, i, '. r re M <Ise & ayl'-N -'ethyl & ïiiiiHa, Me .thydiMnylilie, de 1 * di! & ét'hylM.iMnipht! .3lene of td127.ami * naphthalene, oh obtained in oprttit pai1, .7.t, r. âs li rnSme ïOaMiêï'o also 'ded ct.eß, 3hru3 ants whose color goes from Violat-blue to Meu * Si, in the tteis of û & loï'aRts'que l'bn can obtain suîv, .int J, invrn3bn 3 ,; "r! â pdea nions other than 01" and usual colozzhts bu3ct :, it does this product aubvuiô adii3, a:, 'itn dee properties' .iilr3 ', lc'i.C3, dyes'! '' in a buae:

   n 3, c, of 6 'pefftiû of alualhium chloride anIydi'a.dMd -100 parts of 1,2- C't..Ct: .E71 "tlC -'. t1" 'G /' i, ' f oh .ijoutj or dropwise between 140 and 160ri4j while stirring, a solution of 2315 loss of Ch.b.'i, trt do a.fi0 $$ o it-ethyl'-Kl-naphthyl Gârbamique1 in 50 parts of 2 " diehlûrobunz & ne and then aâlatige it for another $ 0 aihutùs Once the mixture has cooled, we read 4ta out of 100 parts of Claèct oh grabs the watery mouth and dilutes the organic layer with

 <Desc / Clms Page number 26>

 
 EMI26.1
 60 parts of solution àd voo de eafrbôriàte de sôuutt until iâ CÔUêhu de dl <shlo0b <! Nh & no more meid <3 * Uha times the èolutioh, do caf * bonito de soditül sêiiafée, ôR êiiiiilfto 1 dichlo *. banteno by dist111? 10n, sqIPoêG! n induced One can easilyeaeM.put'ifj.J4th '* piph tolactamu brut i-ostkttt p4Ë "iJi.ab: L;

  Ut1Qn under 1/11141 or in the rcrists.11j, dated sMt: the normal 14hoxtÀne or in the cyclehexàho arirëo have added char * good activated. We get it though. ti 1111, <ln c'tfistiaua.aUtté fluorescent verdaet-ro, of which theI Pd1t of fusion word of 68601 The boiling point ist .dé '2C * 2 * 2ÛÔ * Ô under 15 aun e Mcûurët Le- reüêment would have almost
 EMI26.2
 quantitative.
 EMI26.3
 i1ttJOb, j.



  We do; (\ rH1 (ÛI:) JÓ t; he à la tütAP6Z. I Turkish ambient c.nc lrr 66lÙti & M dé 4 drt, o -rfido 1 "'úthylc1lJ1inO"' fiIiPhtÙên âifts fU8OO ', tl ,,' d! 3 1,2wd, chl, oxcïca # ri '' d, 4 tir1 i'ûi i ri, ": V '., Y 1 #' ':; 1 .iil' -U '' l, 1: '' ' # j '\, 1 t "mpJrat \ 1rIJ de.'. t, i ','! 60 * 0 sïi''e8p.'el, 1 y from 19 to 0 f.l1nutIJo ob, ôh,; y wsrimo p ; ssal 'du phc; ru for ± hours at c: & tt, tet: 11'H51.'3tt # (jt AU eommenouaeht do l' t1b! 3Mdtld1l phQsgêne he sc fottae uh rushed .r., ifr, cbrtét1tuê pl 'du dhlb; 'ethylad1nOnapht1ht hydrate' which is produced during the: act, cn We can write the course of the reaction by determining the quantity of chlorhyric acid fotftté

 <Desc / Clms Page number 27>

 
 EMI27.1
 Once the phosntion tda3, z4a, we drop from qbod le, phosgèns in:

   excess by injecting that llairi c. then distilled off under reduced pressure to reduce 1,4% to 1,2-dichlorobenzene. All in
 EMI27.2
 stirring, the remaining solution is poured into
 EMI27.3
 i a suspension, Embossed at 14Q'm? G, of. 5} 'by? tics do cY.pxuxa d'7.u, n, .u anhydro s # t 1.000 parts of 1 d, l.xaben, àno. a reaction is, exQthej3i4que 1 it is necessary to take care qU'1: L.: vtcmpé ...



  1 '# ,,. 3? twft, ne, pal3.,; e not 160eC ApP <9 av; .. r 'acted, the 1 f4ang for 40 to 50 minutes 101', it is
 EMI27.4
 
 EMI27.5
 lal3s PO xuna.d.r 50 C and o + vse we have so much sw 1ooo part of ice. Qn PQI-1, rS), reads the line or have qiuziq in the z: 1cde op- $ ratJoA, 7th of 1'Sxer '1 pl '14, We obtain the product according to the .procede, a. the, wtr. 14, with ejalùHsnt an effective ppep- qn-j qnntitive. "#Nv qui Exempio 16. \ 0 + 1 made passi? Of phosgene, 4/8 \ a pension of 501 parts of hydrochloride d, 1tïijfla t, zoaaha.nd.daz 3, QSA parts of 1 | (2 diotyl, 0ïr $ laanaèn ent! te 1Oo and 160 Cf juoqu tà <a: q, 11p l9 all the time; either; dissolved. We then continue to do pwp phosgeae for another hour at a> i: hf3WP $ and dq ... ,.



  Mix and then remove from it, 5QQ psrtiiea dp d.h.utar bcnaene by distillation under reduced pressure The remaining solution would be poured, while stirring in a suspension heated to

 <Desc / Clms Page number 28>

 
 EMI28.1
 14016000 of 600 parts of chlorinated aluminum in h'Oc7p parts of 1,2'rdichlorobcnzene. After setting the trap for another 30 minutes
 EMI28.2
 1600ot it is allowed to cool and it is poured over 2,000 pites of ice. The organic layer is separated
 EMI28.3
 It was first made with 00 parts of 10% sodium hydroxide solution, then with 500 parts of water and then fractionated by vacuum distillation.

   The product is obtained according to the process of the invention, of Example 14, also with rounding; almost-quantitative.



    Example 17 *
 EMI28.4
 24 parts of 1-methylamino-naphth alene are heated with 70 parts of 1,2,4-trichlorobenzene. The solution obtained is treated for 2 hours at 1500 ° C. to 160 ° C. with phosgene. Excess phosgenu is then removed by injecting air
 EMI28.5
 Dry '4 the carbamic acid chloride solution thus obtained, 40.6 parts of anhydrous almainium chloride are gradually added to 165 and 170 and the solution is stirred for a further 20 minutes at this temperature. The solution is then cooled to .50 0 e.v3.ron and the mixture is poured over 1,000 parts of ice.



  The treatment of a ma, .4èrçyanalogue to that indicated for the procedure of Example 14 is continued. The N- is obtained with a very good yield.
 EMI28.6
 m6thypÓi-np4t1Gtame boiling under 12 r4na of mercury at 19 & -204 "C. The product rcarist.vlis in normal do 1 * li * xane ov in cydohex:; mQ melts at 77-78 C.

 <Desc / Clms Page number 29>

 



    Example 18.
 EMI29.1
 



  56 pa.1'tloB of chloruru of the acid were added little by little in a laélanse * heated to 150..170 0, 70 parts of anhydrous aluminum chloride and 00 parts of 1,2-dichlorobcnzèna. Then arita the mixture for 10 to 15 minutes between 1600 and 170 C and in *
 EMI29.2
 then it is cooled between 30 "and 5o * c, We add then drop to drip we space it 0 minut4l'lat
 EMI29.3
 500 parts of hydrofluoric acid is separated off the layer of dichloro'benzene and mixed with 1 to 2 parts of activated charcoal. After about 2 hours of stirring, the solution is filtered and heated.
 EMI29.4
 remove 1,2-dichlorobensen <3 by vacuum distillation. The remaining crude N-phenyl-eri-naphtholcytaxas is purified by rOcrist8ln in @. @ @ cyclohexane.

   This lactam forms greenish yellow crystals, which melt at 110 C. The yield is
 EMI29.5
 Well. ,, tt "',' 1.:, '," ExGap919' r '. 1' A solution of 46.6 parts of N. (4..xthylptny1) - 'Lntptyfaine in 340 parts of 1, is heated to 11500. 2-dichlorobenzene. While passing phosgene, the temperature is raised to 160boa over 15 to 20 minutes and phosgene at this temperature is passed through the solution for 2 hours.

   After eliminating the phosgene we have excess by injecting: dry air, we let flow, stirring,

 <Desc / Clms Page number 30>

 
 EMI30.1
 the chloride solution of carbonic acid obtained
 EMI30.2
 held in a melanso, heated to 160 * 01 by 70 by *. ticks of anhydrous aluminum chloride and 200 parts of 1f.dichlorobGnzèn; the mixture is maintained for 10 min;: '"10'Ó, O; puiâ on'I'e l'oià-f1';. to cool. The completion of the treatment is done in a similar way to the procedure described in Skofuple 186 kills? T- (4t-methylphenyl) -peri-naphth? o- latitating bbtonu melts at? 7?



  If, instead of the U- (4'-methylphéhyl) - 1naphthylinu, one word in reaction 51.5 partial of N- (4'-etihÓphenyl) - !. nphtyline, one obtains then, by operating in the same way, and . by OPENING the alcomy group to convert it to a hydroxy group, K- (4'-hydr9xyphenyl) -perl- naphtholàctamu, which has a melting point of 252 "C.


    

Claims (1)

R E S U M E A. As new industrial products: 1) Colorants having the formula EMI31.1 in which R1 represents an alkyl, cycloalkyl, aryl or aralkyl residue, and in which the aromatic rings as well as the alkyl or cycloalkyl residue can bear as substituents nonionogenic substituents, such as halogen or alkoxy, acyl, acylamino, dialkylamino groups and / or alkylarylamino, the aromatic rings may furthermore also bear as substituents alkyl and / or aryl groups, Ar represents an arcmatic residue and R2 and R3 each signify an alkyl or cycloalkyl residue, aryl or aralkyl, the alkyl radicals can also be, taken in common, constituent elements of a saturated heterocyclic ring system, and the aromatic rings, as well as the alkyl and cycoalkyl radicals, can bear as substituents halogens or alkoxy, acyl groups , dialkylamino, and / or alkylarylamine, the aromatic rings can furthermore also bear as substituents alkyl and: or aryl groups, and in which X is an anionic residue. 2) Colorants corresponding to the formula: EMI31.2 <Desc / Clms Page number 32> in which R 1 is a lower alkyl residue, R 5 represents EMI32.1 is hydrogen, or an alkyl or cycloalkyl residue, su is hydrogen, or an alkyla or aryl residue, and X- EMI32.2 represents a monovalent acid residue, the alkyl09t / OR the aromatic nuclei can reinforce the substituents EMI32.3 no.1onogne8. B. Process for the manufacture of basic dyes as described under A2, characterized by the following points, either individually or in combination. EMI32.4 3a Compounds of general formula are treated with 3lky.ntioa agents: EMI32.5 in which R5 represents hydrogen or an alkyl or cycloalkyl residue and R6 hydrogen or an alkyl or aryl residue, the alkyl residues and / or the aromatic rings EMI32.6 that * being able to benefit from non-lonogeneous substituents. 4) The alkylation is carried out with neutral methyl sulfate or with methyl chloride, in an inert solvent and at elevated temperature, preferably between 80 and 130 C. C. Process for the manufacture of basic tolu dyes as described under A1, characterized by the following points $ pria alone or in combination: 50 Heat in the presence of de-condensing agents. EMI32.7 '8hydrating naphtholactaaes of the general formula EMI32.8 <Desc / Clms Page number 33> EMI33.1 (in which represents resta IL and cycloalkyl, (in which 7 represents a resta alkyl, cycloalyl, EMI33.2 aryl or aralkyl and in which the aromatic rings are EMI33.3 like the alkyl or 4, ydloalkyle moiety / carry coaaa vane * tituants halogens or-groups, alkoxy, acyl, a4, yit. mino, dialkylaaino and / or alkylarylaaino, aroasa- kernels EMI33.4 ticks which may also carry major substituents EMI33.5 pes alkyl and / or aryl), with arstx groins, for general formula 4 EMI33.6 EMI33.7 (in which Q represents an aromatic test and and 80 each signify an alkyl, cyoloalkyl, aryl or, - aeaikyleg the alkyl residues: 0 can also, taken in com. iaun, to be co t3.tuti's elements of a cyclic system EMI33.8 saturated heterocyclic, and arctic nuclei as well EMI33.9 that the alkyl and cyelbalkle residues can carry coame EMI33.10 substituting for halogens) or alkoxy, acyl groups, EMI33.11 dialkylamino and / or a.kr, g ylam3, aa, the Q-, 1 rings '.aromatic * can also carry ci = 0 substituting a #' of alkyl groups and / or aryl). '' #, '# 6) The starting components of the lower alkyl nrphtolactamea1,8 ubstitwaouts are formed and reacted and the reaction is carried out between 70 and 150009' and preferably between 90 "st'1117 C. D. Manufacturing process of peri "naphtholactaaes EMI33.12 substituted on nitrogen, corresponding to the formula EMI33.13 <Desc / Clms Page number 34> in which one of the Y represents the group R7-N- and the other Y the group # C = O, the radicals R7 represent the same or different alkyl, oycloalkyl, aryl or aralkyl radicals and the aromatic rings as well as the res- EMI34.1 the alkyl or cycloalkyl may bear hydroxy or acyl groups as a substituent and the aromatic rings may additionally bear further alkyl and / or aryl groups as substituents, this process being characterized by EMI34.2 the following points, taken individually or in combination! s- * 7) Treated in the presence of a Friedel and Crafto catalyst, in an inert solvent, at a temperature above 100009 and preferably between 130 and 180 ° C, halo-tdnurec acids op ' bote, quee having for formula EMI34.3 where one of the X represents hydrogen and the other X represents EMI34.4 1 It \ .. group! : EMI34.5 EMI34.6 the roatos 7 represent alkyl, eycloolkyle aryl or aralkyl and Hul represents' fluorine, chlorine or bromine, las nuclei: oCtitiâa as well as the allcy- or oycloalkyl radicals may bear as substituents alkoxy and / or acylo groups, the aromatic rings may EMI34.7 in addition, as well as Substitutes for alkyl and / or tryl groups .. ', <Desc / Clms Page number 35> EMI35.1 6) We have \ tt1, :: e QO;: 411'3 Friedel catalysts and EMI35.2 EMI35.3 Cafts: .4e "h! F.éu.e '.a, + Ll';!" ,. 7.C:.: Chloride of ziF '::, fJ, ucNu9 of 1; ::> rc \ chloride '-q f',; r In, EMI35.4 EMI35.5 du t'a.'7. .'l, x'a of herbal tea, tN 'ni?, Qru.'4' d 'é; 1 or 1r; l.ohlruN;'. ^ .: "C l.lt.:19. el process w11,?;,. ûctr.fJdl 3oc coloras such as C \ ,: 't: 3 p u3, J1.1 and 2 vcw1 tú1r.dN, ipri :: ez or teindr-a e .fJ. \ ve subotalices pst.GuJ en tçtnl 0.4 in t. a, y;: t. <'u. d9 çY "G d9 vi \ {lid x.3u1.3x, wés. fi A 414re of products industry 4ar EMI35.6 EMI35.7 veal? <t of pubstancpe - and in psrfciculief '4eS p! lO-' duits gui t; JQn cQn $ itu4- n whole or in H1djeq ", the part #. # df4çpyifl4, t 4; i, e or do cyww d4 vinyidôv 'ne PQl;>' 1Uttvh .. te: \. l1tc, .apritG as or colqpéss clzno la r4oq4e v: dep dyes such as d6ov $ soua A1 og o A2,