DE1644562A1 - Process for the production of polycyclic dyes - Google Patents

Description

PATENT LAWYERS

D R.-I NG. H. FlNOKE DIPL.-ING. H. BOHR DIPL.-ING. S. STAEGER

Telephone: 2249 41

8 MUNICH 5. Müllerstrasse 31

2U. M.

ΙΊ & ρρβ: 20556/657 Gases; D.19119

description

To patent the

XMPSRIAL OKElIICA] J IEDUSiCRIKS LIMIO) EB, London S.W. '

concerning:

"The process of producing polycyclic dyes"

The invention relates to new polycyclic dyes, in particular new polycyclic dyes, which are valuable aur Coloring of synthetic linear polyesters in bulk are.

According to the invention, herds of polycyclic dyes of the formula:

COOR

suggested, wherein D is a polycyclic dye residue represents the free / on sulfonic acid groups and at least

109815/1569

contains four condensed hinge, X the group -HH- odor -S- means, R is a hydroxyalkyl- or hydroxyalkoxyalkyl-

means root and η represents the number 1 or 2

The hydroxyalkyl radicals represented by R are preferably hydroxy-lower alkyl radicals, v / ie β-hydroxyethyl, γ-hydroxypropyl, 8, f «dihydroxypropyl and β-, γ- or 6-hydroxy-n-butyl radicals. The hydroxyalkoxyalkyl radicals represented by R are precautionary hydroxy-lower-alkoxy-lower-alkyl radicals, such as β- (β * -hydroxyethoxy) -ethyl and β- or r- (β ^p -hydroxyethoxy) -propyl radicals. However, R preferably represents the β-hydroxyethyl radical.

The terms "I-lower alkyl" and "lower alkoxy * mean here always alkyl «and alkoxy radicals, which have 1 to 4 · carbon atoms ·

Preference DWQioe represents η the number 1 and is the -COOR group bound to the Bensolrirtg in ortho division to X.

The polycycliachen Farbatoffreste represented by D may be the residue of any polycyolischon Ringayetens eein _t normally present in polyoyolischen dyes, and where nigatens four fused rings vorsugsweiee four to eight fused rings, having which carbocyclic or heterocyclic rings or a combination may be of both types. If desired, this polycyclic dye-

109815/1569

contain other substituents besides sulphonic acid groups, which are usually present in such chemical residues, such as chlorine or bromine atoms, carboxylic acid groups, lower Alley Iresto, such as the l-iothyl radical, lower alkoxy groups. such as the ilethoxy radical, hydroxyl groups, araino groups, iMJiedri & allcy! amino groups, Vfio Hetliylemino-j Xthylaraino ■ - <· 33iHothylamiiio and Mäthylasiino groups, and acylanino groups, such as''AcylDiaino-aliphatic acids, which from : ien _T wio Acetylsainc- and 3? ropionylaiüinogruppen, or of laonocycliachen aryl carboxylic acids, like the Benaoylrjninoprappon. Voraugov / oiso represents D a 1 ', 9'-Anthrapyridon-, 1' j9 ^! --Aiithi ^: apyrotiraidin- ', - 'Pj'ra Eolanthron- or one?' , 4'-phthaloylacridone dye residue dp.r..)

The Farbatoffrest is ΰ at & atom represented by X v.ß oiler the group represented by X group by a carbon atom present in X) Arylrin ^ cs, the voraugsv / Eiso a Bonaol · - 'ring is bound.

i) ae inventive method for dividing the polycyclic Dyes is a dye compound the formula:

D—

COOH

with a glycol ö.or formula Ρν-ΟΙϊ umäueetzon, where D, X _r η and R have the meanings given above,

10 9 815/1569 _BAD original

The procedure can be conveniently carried out by any the Hur esterification of carboxylic acids with glycols known Grounding methods independently. For example, the Pnrbötoffverbindimg · converted into the corresponding acid chloride v / erdoiij bcißpiolev / eioo durcli UnaetEimg with thionyl chloride, one then hit an excess of the glycols converted v / i Ed.

As a special Itairspiole of the glycols ο ei en ethylene glycol, " γ -Düiydroxypropan" and M- {ß - hydroxyethyl) -ether called "

Mo polycyelic paraffin verbiiidunijeu dor I ^? Ormoľ I can i3olbot by condensation of the appropriate Verbindimg of the formula D- (Z) wherein Z in chlorine or ο a Broir.atora darste3.lt, with a Ani3.inepJ bonsäure or lißrcaptobensolcarbonsäuro obtained on v;? he "on"

With another 1! G3? kraal dor the invention there is an alternative method to the production of the polycyclic carbatofiO in the conversion of a metal salt, preferably an alkali metal, a dye compound of the formula I with a compound of the formula RK ₅ in which R and 7 , have the meanings given above.

This, erfindungsgeiaäase Alternativverfaliren can been easily performed dj.c Iloaktionskompononten iuclcn initoinaiader, voraugsweise at t> ne of l'enperatur swisehen 100 and 140 ⁰ O, in

4 ORIGINAL BATHROOM

10 9 8 15/1569 __

S I6U562

aincm Hiö ^ ngEiüittel, öcn the pre-augsweise an excess of the 'compound ö.qv 3? OMe \ L RZ iet, and preferably in the presence of c-inc-s .basiychsn Ka talycsators, v / ie Mäthylsmin or piperidine voraührt we ^ "The eater obtained can then be isolated by the usual methods."

As special examples of preliminary compounds of the formula H-Z are

eiiiy Äthylenbromliydrin, ß ~> or f-Ohlor- {or xmA ß-Cß'-OhloräthoxyJ-ethanol called.

There is another Hercraal of the invention Alternative methods for the preparation of the polycyclic dyes obtainable according to the invention include a compound the formula:

D «(Y ¹ ) _n II

and a compound of the formula:

v / orin D, η and H have the meanings given above,

1 2

and an a dor symbols 7 and Y a chlorine or a bromine atom

"» 12

and * the other of the symbols Y and Y is a Morcapto- or an Arai.no group means to react with one another.

This alternative method of the invention can be convenient be carried out by the reaction components with

10 9 815/1569

each other in a T-b'aimgsiaittel and in the presence of an acid-binding HiIiUoID ₅ v / io sodium carbonate or potassium acetate, and given in the presence of oineo Kupferlcatalyaatora, like copper f. λόπζο, copper acetate or copper (I) ~ chlo3? id, heated The solvent is then removed, for example by distilling off, optionally in the presence of steam, and the remaining dye is then isolated and, if desired, purified by treatment with a hot aqueous solution of hydrochloric acid.

As examples of compounds of Formula II which can be used in these methods. Let be 6-broin ~ 5'i4 ^f -phthalo ~ ylacridone, S-alaino-3 '»4' -phthaloylacridone, 6 ~ brom ~ 3 ~ methyl" 1 ', 9'-anthrapyridone and 5- or 7 ~ amino ~ 1 • (S), 9 ^f -isothiazolanthron called, and as examples of compounds of the formula III ooien ß-hydroxyethyl-o-chlorobenzoate, ß-hydroxyethyl-iaaminobenzoate and ß-hydroxyethyl-o «, m- or p-browbenzoate ge ~ naniit.

The polycyclic dyes obtainable according to the invention, when incorporated into synthetic linear polyesters by mass dyeing procedures, give orange to green shades "which have excellent fastness to light, washing, steaming, sweat, dry cleaning", rubbing after steaming and dry heat treatments. It was also found that the colorations can be produced in deep tones, without the properties of the synthetic linear poly *

9 "e1- S" /

tO 9 "e1- S" / 1 5 6 9

_iÄD

J? tier da: caun produced fibers

eater oclGJ turn around

! The following. }? oiopielo explain the invention without adding to it i-v.'nkcUc All iüGilo are weight steep.

A mixture of 6-jlmino-3 ', 4'-pththaloylacridone, 70 ropes ß-IIydro; 1000 ropes of nitro. Bensol is stirred for 4 hours at 20.5 ° liuig Ms 21O ⁰ G. That

The oil is then removed by distillation in the presence of Banpf, and the raw carbon dioxide is filtered off, with YfeßSGj. ¹ G'evmnohen imd gotroclmet.

If the dye obtained is surpassed by the dye of polyethylene-te3: ophthalate The polymer becomes green in color straightened; e: iehneton] 3chtlieitseissenensaften colored.

j) or the same dye is obtained if the 70 ropes are ß-hydroxyethyl-'O-clilorbensoate by the equivalent amount of ß-IIydroxyäthyl-o-bromobenzoate replaces v / earth.

V / eim one instead of the 70 part of the one used in this example ß-Hydroxyethyl-o-chlorobenzoate 86 ropes ß- (ß '~ hydroxyethoxy) "- Uthyl-o-chlorobenzoate is used, a similar dye is obtained.

10Θ8Ίl7i669

⁸ ^ D QHiGHNAL

Din mixture of 200 UJcilcn of ITatriuinscilsoB of 6- (o-0arl) oxy ~ Giiilino) -3-BGthyl '1' j9 ^f "anthrapyridone _t 500 parts of ethylene chlorohydrin 5 and ropes diethylamine for 20 hours at 1? 0 ⁰ C stirred biö 1AO “Then GOO ΐοϋο water is poured out, and the precipitated dye is filtered off, washed with a dilute aqueous solution of sodium hydroxide and then with water and finally dried

If the Parbatoff obtained is only used for a mas ο cf firing of polyethylene terephthalate, the polymer turns carmine red ! Shades of true authenticity dyed "

Am Geniseh of 010 '.Uoilen 6'-Brcm-3', 4 ¹ -phthaloylac3.- ^| idon, 400 files ß «" IIydro :: yä1; hyl-4 "nercaptobenaoat, 420 'files anhydrous - cw. Potassium carbonate and 4000 '.Peilen ethyl glycol is stirred for 20 hours at 145 ° C. The mixture is then poured into 10,000 parts of water, the resulting mixture is acidified by adding an aqueous solution of hydrochloric acid and the precipitated dye is filtered off, with V / Otherwise washed and dried.

When the dye obtained is used for dyeing polyethylene terephthalate, the polymer turns bright blue. dyed in shades of excellent fastness.

In the following table are further examples of the invention " geiiüsa available polycyclisohon dyes indicated which

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by implementation of the polyaycliachGii I dye compounds indicated in the previous column of the table and the esters listed in the third column by methods similar to those described in Eaispiol 1, prhalten νιοτάοη. In the fourth column of the table, the color tints are given which are produced when polyethylene terephthalate is treated with the dyes obtained.

⁰ ^ ORIQiNAL

I ¹ PXyGyClJsee tannin compound eater

4 6- ^ ino-3 ~ ethyl ~ 1% 9'-anthrapyridone B.

bencoat

6ö _rt 8 6 * bromine ~ 3 ~ roethyl-1% 9 ^f -'enthrapyridone ß-kydroxyethyl-m-araino-

ti β »" benzo at

<l '■

benzor.t ~

6 "ß-Hyäroxyä-ethyl-p-bromo-"

bansor.t

7th "ß-Cß'-hydroxyethoxy)"

Wl CT.

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Instead of the 200 'file of the sodium salt of 6 ~ (o-Garboxy ~ anilino) -3-roethy1-1.9'-rnthrapyridone, which is used in Example 2, 190 parts of the ifr.trium salt of 6 --- (o-Cs.rboxyphonvlthio) -3 ^l, 4- ^l -pli "fchaloyl criöon £ 180 or TEI Ig doc liatriumaalisoo 4- or T-io-carboxyanilino) -. ¹ is used, 4'-phthaloylacridone? , whereby dyes are obtained ί which after application in polyethylene terephthalate by liasoofarbenarbeitsv / eissen l> laus _s purple colors © or kprmin-red shades with apparent fastness properties result.

Example 10

A mixture of 10 Teileii 6- (o-Garboxyanilino) -3-raothyl-1 ', S'-anthrapyridon, 5 parts ihionylchloriö, 75 parts of toluene and 0.2 parts of pyridine is 2 hours under a layer of fluoskiUi3.er ειιια boiling erhitct. the Genisch then yri.rd 0 to 20 ° and filtered the abgekülilt auögef allene acid chloride and washed with toluene. the solid is then stirred with 50 parts Diiithylenglylcol for 20 hours at 150 ⁰ C · Bas mixture v / ith abgclcühlt and poured into water, and the precipitated ester is filtered off, washed with a dilute aqueous solution of sodium carbonate and then with water and finally dried.

^v. if the dye is used for mass coloring of polyethylene terephthalate, the polymer is colored in carmine-red shades of excellent fastness properties,

109815/1569 bath - 11 ~

1644öb2

Kin X 'dye of similar properties is obtained if clic! 50 ropes of the one used in the example above Diethylene glycol B has been replaced by 50 parts of ethylene glycol "

A mixture of 197 Ttilen dos Hatriunsalaes of 5- (c-carboxy-anilino) -1 _^(l O ^t "(li) -iaoiih ± azolcü \ throne ', 300' file ethylene chlorohydrin and 2 parts Diäthylanin is carried out at 130 to 140 ⁰ C. Stirring for 20 hours.Dr.ö Hoateticnsgemißch then becomes ßegoosen in 2000 Eeilo Y / anco.v and the Festaubottuiz which also fell

tricrtf nit V'nase :? and then a dilute aqueous ni 'from Hatrivj.ihydroJ-ycl and finally with Y / nsoej? ^ gwaschen un ^r l finally dried. Wonn the received _Dye siu? IlaüGcfrebsun.'i of Polyäthylontorophthalat is used, v / erden orcn ^ e-gelco Parbtöno τα ± · 'ΰ auagö draw tön authenticity = property obtained.

Ijin Goraicch of 144 parts doo lOinptriurioalzeo 'of 6,8-His - (o-carboxyaniliuo) - 3 ~ nethyl-1', 9 ^f -anthrapj ^ ridon, 300 parts of Äthylonchlorliydriu and 1.5 ropes of Diüthylomin will be 130 to 140 ⁰ C for 20 hours. The mixture is poured into 2000 parts of acid and the mixture is acidified with an aqueous solution of hydrochloric acid and the precipitated Feetsubstans tibfiltriort and washed with Yfeosor. The Festeub-RtoniES is then with a dilute aqueous solution of

iircl then washed with V / asnor * and removed

15/1569 BADORIG ₁ NA ₁ .

i!: dissolve the dye for a melt staining of alialBt has been used with fibers iis niul from ^ ez-eicnneton KciibliGitseigenoclipften

■ j; iiF5 in tliosoiii} 3eispio3. Vervjondete e, Ö-BiO '- (o ~ oarboxya2iilino) -3-; i: 3thyl-'i' - ^ '"Eirkhrapyriclone was obtained by dissolving 6-bromine ~' 8-chloro-3-n-ethyl-1 ^f , ^ '-aivtlirapyridon (obtained by Broiaieren of 8-Chloi * "- 3 ~ ⁱ ne fcliyl-1 _f ^l 9 ^l -fisithi * apyridon) TiIb KaliuQ & ntbraiiilat: ln Äthyleiig'lykol in Gc.genvrart a Kupferlcatalyoators at J60 bio 1SO ⁰ O obtained .

Claims (1)

where D represents a polycyclic dye residue free '/ on sulfonoacid groups and at least four condensing cc Rin & e contains, X denotes the group -M- or -S- * "R denotes a Hydroxyalkyl or Hydroxyalkoxyallcylrest and η denotes the Represents the number 1 or 2, characterized in that a dye compound of the formula: D— with a glycol of the formal K-OH maoetat, rrobei S ₁ X, a and B have the meanings given above. 109815/1569 BATH 1S 2. Ancestors according to .Anspruch 1, thereby gokennaeiohnet that the 3-arbrvtoff compound in that acid chloride is converted, clan then unset with the Glylrol. y » Modification of the procedure ncili claim 1, thereby gekemiaeiclmot that nan a lietoll salt of a dye compound of the formula: COOH sii-i; a compound of the formula R-Z, in which B, X, R and η the; in claim 1 have narrow meanings and Z represents a chlorine or broia tone. 4. Modification of the procedure after.Anspruch 1, thereby ge ~ denotes, dos;?, one is a compound of the formula: D- (Y ¹ ) and a compound of the formula: GOOR v / orin D, η and R have the meanings given in claim 1 - 15 10 9 815/1569 1 6 U 4 5 b 2 1 2 own and one dor nyj.ib.olo Y and Y a chlorine or 12th Gin .Broiaaton and aas other of the symbols Y and Y a Hercr ^ pto- odoi "· represents an ArainagruppG, together .tunSQtKt, e / Polycyelißcho I dyes tier Pormeü: ^v 00011 wherein D oinon polycycliaclion dye travels aaratellt. the sulfonic acid free:.! and at least four icon-denaed Rl en1; mä.t, X denotes the group -ίίΙΙ ~ or "S-, R denotes a hydroxyalkyl or hydroxyalkoxyalkyl radical and η which represents Ί or 2» 6. PolycyelisGhe i'arerstoffo according to / aiapruch 5 »dr.cluj-i.ii rioliicrAiiioi not that the group -COOK at dom. Banaolrins in Orthoijtollvni-j ' Is bound to X « 7 «Polycycliache dyes according to claim 5 or 6, duflurrh ^ koiinaeiclinGt, danr D an aiithrftpyrioonfarbstoffrorrt int., Poly cyclische rarstoffo nnoh /aiop.fuoh 5 or ( ^: , d « ^r -by goiioiehp.et» änne P a r] ii; lialoyliicx * idoni ^r r.rb: 3 "to: iM rest, j ^ t. svj. H (' 1 (19 ίί 1 '■■' 1