CA1050024A - Dyestuffs - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention relates to com-pounds of formula I, I

in which R1 signifies a divalent, mono- or bi-nuclear aromatic radical of the carbo-cyclic or heterocyclic series, R2 signifies a hydrogen atom or an un-substituted or substituted (C1-4)alkyl, phenyl, naphthyl or mono-or fused binuclear heterocyclic radical which is bound through a carbon atom, and each of the R4's in-dependently, sigifies a mono- or binuclear aromatic radical of the carbocyclic or heterocyclic series, or mixtures of such compounds, which compounds and mixtures are useful as colourants.

Description

CA ~IA DA
n~
:~OS0024 The present invention relates to heterocyclic compounds and mixtures thereof, th~ir production and use.
More particularly~ the present invention provides compounds of formula I, N ~ 4 R3 ~ 1 CH ~ 2 in whlch Rl slgnifie~ a 1,4-phenylene radical, a 1,3-, 1,4-, l,S- or 2,6~naphthylene radical, a blvalent radical of furan, ~ thiophene~pyrrole or pyrldine or a ! lo blvalent radlcal of benzofuran, : benzothlophene, benzopyrrole or.
benzopyridlne ln which the bcnds are - ~ ln the 2 9 5- or 2,6- or para- position, : all o~ whlch radicals are either lS unisubstltuted or substltuted ~y a total of up to two substltuents per rlng selected from the group conslsting of chlorlne and bromlne I ~ atoms, hydroxyl, methyl 7 methoxy and - ethoxy groups ~up to two of any of ..

.,...., .._~
:

~ANADA
-- 2 - Case 150-3566 ~OS0~
these~, trifluoromethyl, ~C2 4)~1kanoyl-amlno, benzoylamlno and nltro group~

(only one of any of these), R2 slgnlfies a hydrogen atom; an unsubstituted (Cl 4)alkyl radlcal5 a (Cl 43alkyl radical substltuted by a chlorine or bromine atom, a hydroxy, (Cl_4)alkoxy, (C~
alkylamlno, dl(Cl ~)alkylamino, SC2_4)alkanoyloxy~ (Cl_4)alkoxy-carbonyl, (Cl 4~alkoxycarbonyloxy . . or benzoyloxy; an unsubstituted phenyl radlcal or a phenyl radlcal substituted by a total of up to three substltuents selected rom the ~roup con~lsting of chlorine and bromlne atoms, and methyl . groups (up to three of any of these~, (Cl 4)alkoxY, carbonyl, cyano and nltro groups lup to two of any of these), hydroxy, ~ .

CANADA
- 3 - Case 150-3566 l(~S0024 ;(Cl 4)alkylamino, di(Cl 4)alkylamlno, (C2 4)alkanoylamlno and (Cl_4) alkoxycarbonylamlno groups (only one of any of these); a naphthyl radical; pyridyl-2, -3 or 4;
pyrlmidyl-2 or -4; 2,4-dlmethyl-pyrimidyl-6 ; thlenyl-2; thiazolyl-2 _ . . ~, benzothiazolyl-2; or S-methyl-i~oxazolyl-3, R3 s~gnlfie~ an oxygen atom or a group o ormula _ N-R5 iA whieh R5 has one of the slgnlflcances ! ! glven above for R2, and each of the R4'~ independently, slgnlfles an unsubstltuted phenyl or naphthyl radlcal; a phenyl or naphthyl radical substltuted by a total sf up to three substltuents selected from the group conslstlng of ~hlorlne ~nd ~romlne atoms and methyl group~ (up to three o~ ~ny . ., ' : ~

6 ;ANADA
- 4 - 150~3566 105(~QZ~
of the~e3 ~ (Cl_4)al~coxy and nltrs groups ~up to two of any of these) hydroxy, cyano, ~Cl 4 ) alkylamino, d1 (Cl_4 ~ alkylamino ~ ) alkoxy-carbonYl~ (Cl_4~alkXY(cl_4~alkxY
carbonyl, (C2_4~ alkanoyloxy, ~C2 4) alkanoylarnlno, ~Cl 4) alkoxy-- carbonylamlno and sulpho groups (only one of any of these1; pyridyl-2 , . -3 or -4; a pyrazlnyl radlcal i .. ~hlenyl-2 or pyrryl-2 or -3~

whlch compound,where.R4 contalns ~ sulpho group~ ~8 ~n the free acld or ~alt form.

It wlll be appxeciated that, when ~4 lgnifle~
a phenyl radical substituted by a sulpho group, the com-pounds of formula I may be in the free acid or sal~ form, suitable salts are the alkali metal salts.
The present invention also provldes a process for the production of compounds of ~ormula I, as defined above, or mlxtures thereof, comprisiny condensing a com-pound of formula II, , .' E~.,- .

- 5 ~ Ca~e 150~3566 C~I - Rl - CH ~ ~

ln whlch Rl and R4 are as deflned above, wlth a compou~d of formula III, in which R~ 18 as defined above, or a mixture of compounds of ~ormula III, preferably ln a 1:1 or 1:2 molar ratio.
Where it 18 deslred to o~tain a compound of formula I, whereln R4 ~ignlf~es a sulpho bearing phenyl group, it 18 preferred flrst to prepar~ the non-sulphonated compound and then to sulphonate ~uch compound.
If a slngle compound of formula III i8 reacted wlth a compound of formula II in a l:l molar ratlo, a mlxture of compound~ comprising compounds where R3 i8 0 and compound where R3 18 ~ N R2 are obtained. However, lf 1~ a ~lngle compound of formula III i3 reacted wlth a compound of formula IX ln a 2:1 molar ratio, a sub~tantlally pure product, where R3 i~ ~ N-R2, 13 ob~ained.
: The reaction of the compound~ of formula II
wlth the ccmpounds of ormula III wher2 R2 has a ~gnlfi-c~nc~ other than hydro~en 18 preferably carr~ed out in .

I - 6 - Ca~e 150-3566 ~s~z4 anhydrous alkane acids contalning 2 ~o 4 carbon atoms or alkane acid anhydride~ containing 4 to 8 carbon atom3, glaclal acetlc acid and acetlc anhydrlde being preferred.
The reaction ls also preferably conducted ln the presence of an alkali metal salt of an alkane acid contalning 2 to 4 ca~bon atom~. Suitable reaction temperatures are ln the range of from about 100 to 200Co A preferred method of preparing the compounds of formula I, where R2 slgn~ fie8 hydrogen and R3 signifies ~ N-R5, where R5 has a significance other than hydrogen~
ls to react a compound of formula II, as defined above, with a compound of formula H2N-R5, where R~ ha~ a signiflcance other than hydrogen, ln a 1:1 molar ratio and Yubse~uently to react the product wlth ammonla.
When ammonla ls used as the compound of formula III, ~.e. R2 18 hydrogenO the reaction is prefer-ably effected in an aqueous-al~aline medlum. It 18 ~refer-ably conducted ~n an autoclave at temperatures ranging from about 75 to 160~. In such cases an excess concentrated agueous ammonla ~olu~lon ls generally u~ed.
Sulphonatlon of the c~ndensatlon product may k- c~rrled out by knowD mcthod~.

.

.~

~ ~ 7 ~ Case 150-3566 ~0~

The compound~ of formula II are produced in a manner analogous to that descrlbed by E. Erlenmeyer, Lleblg'~ Annalen, 18g3, 275, 1~
Preferred compounds ~f f~rmula ~, are tho~e o~ ~ormula Ia, I R - ~ 7 - R Ia 1 ~8 ~ CH - ~ CH ~ -R7 O O
, in whlch R6 ~lgnifle~ an unsubstl~uted 1,4-I phenylene radical; a 1,4-phenylene I radical ~ub~t~tuted by up to ¦ two substituentR selected fxom the group consistlng of chlorine and I bro~lne atoms, hydroxyl, methy$, i methoxy and e~hoxy groups; a 1,4-, 1,5- or 2,6-naphthylene radical or a 3,4-dlbromothlenylene-2,5-radl~al, R7 ~ignlfles a hydrogen atom; an unsubsti~uted (Cl 4~alkyl radical; a (~1-4)alkyl rad~cal substituted by a hydroxy, (Cl 4) - 8 - Ca~e 150-3566 alkoxy, (Cl 4) alkylamino or di- (Cl 4) alkylamlno group; an un~ubstituted phenyl radical or a phenyl radlcal substituted by a total of up to two substituent~, preferably one substituent, sele~ted fxom the group consist-lng of chlorlne and bromine atoms, methyl, cyano and nitro groups (up to two of any of these~, (cl_4jalk~xy, ~Cl_4) alkoxycarbonyl, acetylamino, and proplonylamlno groups (only one of any of these); or a 2-pyridyl radical, : R8 signif~e~ an oxygen atom or =N - R7 in which R7 is as defined above, and ~h~ Rg's are the same and ~lgnify an un-qubstituted phenyl radlcal; a phenyl radi~al substltuted by a total~of up to two suhstituents, preferably one substltuent, . '~ ' ', '' . .

~ g - Case 150-3566 selected from the group consist-lng of chlorlne and bromine atoms, nltro, methyl and (Cl_4)alkoxy groups (up to two of any of thase); cyano, hydroxy, acetoxy, propionyl~xy, methoxycarbonyl, ethoxycarbonyl, methoxyethoxy carbonyl, acetylamino, sulpho and propionylamino groups ~only one of any of thes~; a naphthyl-l or

-2 radlcal; or a naphthyl-l or -2 radlcal substltuted by a sulpho group; 2-hydroxynaphthyl-3, 2-hydroxy- ulpho-naph~hyl-3, pyridyl-2, -3 or -4; thienyl-2, : . pyrryl-2 or -3; or pyrazinylr In the dye~ of formula Ia, R6 preferably signifies an unsubstituted 1,4-phenyle~e radlcal or a 1,4-phenylene radical substituted by a total of up to two ~ubstltuents, ~elected from the group con-818~1ng of chlorine a~oms, methyl and methoxy groups, moro preferably, - lO - Ca e 150-3566 l~S~
R6 slgnifies an un~ubstituted 1,4 phenylene rad$cal, preferably signifles a hydrogen atom; an unsubstituted (Cl_4)alkyl radical; a (Cl 4~alkyl radical substituted by a hydroxy, methoxy, ethoxy, methylamino, dimethyl~
S amino, ethylamino or diethyl~mino group; an unsubstl-tuted phenyl radical, a phenyl radical su~tltuted by a total of up to two ~ubstituents, preferably one substi-tuent, selected from chlort ne and bromlne atom~ and methyl groups (up to two of any of these), metho~y, ethoxy, methoxycarbonyl and ethoxycarbonyl group~ (only one of any of the~e); or a 2-pyridyl radical, more preferably, R7 signifies a hydrogen atom; an unsubstituted ~Cl 4)alkyl radical; a (Cl 4)alkyl rad~cal substltuted by a hydroxy, methoxy, ethoxy or dimethylamino group; an un~ubstitu-ted phenyl radlcal; a phenyl radi~al substituted by a total of up to two ~u~tltuents, preferably one substl-tuent, selected from the group cons~stlng of chlorlne ; and bromlne atoms and methyl group~
(up to two of any of these), methoxy, ethoxy, methoxy-carbonyl and ethoxycarbonyl groups (only cne of any of the~e); or a 2-pyrldyl radlcal, or even more preferably, R7 s$gn~fle~ a hydrogen atom, an unsub~tltuted phenyl.

~ Case 150-3566 radical or a phenyl radlcal substituted by a chlorine atom, a methyl, methoxycarbonyl or ethoxycarbonyl group.
Rg preferably slgnifies an un~ubstituted phenyl radical;
a phenyl radical sub~tituted by a total of up to two substituents, preferably one sub~ituent, ~elected from the group consi8ting of ~hlorine and bromine atom~ and methyl groups (up to two of any of these), cyano, nltro, methoxy, ethoxy, methoxycarbonyl and ethoxycarbonyl groups (only one of any of these~; or a 2-, 3- or 4-pyrldyl radlcal, more preferably Rg ~ignifle~ an unsubstltuted phenyl radical.
The compounds of formula I or mixtures thereof, whlch contaln one or two ~ulphonic acid or salt groups contained ln R4, are useful as an~onlc dyes which build up from a neutral bath. Sultable substrates which may be dyed wlth such dyes include ~ynthetlc ox natural polyamides, ~ellulose f$bres or paper. D~eing m~y be carrled out In ¢onventional manner for dyelng with anlonlc dyes.
The compounds of formula I or mixture~
thereof, where~n one or both of R2 and R5, when R3 signlfies - N - R5, have a ~ignlflcance other than hydrogen and whlch contaln no sulpho groups are useflll a~ disper~e dyes. They may be used to exhaust dye, - 12 - Ca~e 150-3566 pad dye or prlnt substrates of seml-synthetlc, synthetlc, hydrophobic~ high molecular weight or~anlc fibres. Sultable substrates conslst of or compxise linear, aromatic poly-esters, cellulose 2-lt2 acetate, cellulose trlacetate or synthetlc ~olyamidesO The dyestuffs may be processed in known manner to form dyelng preparatlons, ~or example, ~y grindlng in the presence o~ dispersion agent~ and/or flllers, optlonally wlth subsequent vacuum or atomizer drying. Conventional dyelng and printlng methods may be employed, fcr example, those described ln French Patent No. 1,445,371. The substrate may be in 1008e yarn, fibre or fab~ic form.
The dyeings obtained ~how notable fa~tnes~y for example fastness to llght, thermoflxatlon, pleating, fastness to water, sea water, washing, perspiration and solvent~, lncluding dry cleaning liqu~rs, to lubricants, rubbing, cross dyeing, ozone, ga~ fumes-and chlorine.
The dy~ings ~how stability to the pre-cure and post-cure permanent press finishing processes, to ~oll releaae finishes, to reducing action in the dyeing of wool, and a~
disperslon dyes they reserve wool and cotton.
The ompounds of formula I or mlxtures thereof, whereln R2 and R5, if R3 signifies = N-R5, slgni~les hydrogen, a~e u~eful as plgments. Theyare sultable CANADA

- 13 - Case 150-3566 ~05(;~)2~
for pigmenting plastics or synthetic resins in the mass.
As examples of such materials may be given polyethylene, polystyrene, polyvinyl chloride, rubber and synthetic leather. They may be inccrporated in such materials in the presence or absence of solvents. They are also suit-abl~ as pigments in surface coating media, whether of an oil or water base, and in lacquers of various composition or spinning solutions of viscose or cellulose acetate.
The compounds are also suitable for use in printing inks, for dyeing paper in the ~tock, for coating textiles and for pigment printings.
The dyeings obtained exhibit notable heat resistance and fastness properties.
The properties of the pigments may be further enhanced by an after-treatment of the crude pigment in or-ganic solvents at elevated temperatures, e.g. 110 -200 C.
Suitable organic solvents include chlorobenzenes (mixtures), nitrobenzene, dimethylformamide, glacial acetic acid, ethylene glycol or quindine.
It will be appreciated that if mixtures of the compounds of formula I are obtained, these m~xtures may, if desired, be separated, although it is preferred to use such obtained mixtures in the admixed forms.

The following Examples further serve to illustrate the invention. In the Examples the parts and percentages are hy weight and temperatures are in degrees Centigrade.

¦ - 14 - Case 150-3566 ~050~Z~
ExamPle _l ~
42 parts of the c~ndensation product of terephth~ldehyde and hlppurlc acid, of formula a NSC6 ~ \ ~ CN ~ ~ ~ C6N5 a are suspended in 1000 parts of glacial acetlc acid, 9, 3 S parts of aniline are added, it 1~ heated to a temperature ln the range of from 30 to 40 and 4 parts of newly molten, anhydrous sodium acetate are added slowly ln small portions. A~ter addlng a further 200 parts of glacial acetlc acld, the suspenslon which is stlrred well O 18 bolled for four hours wlth re1ux coollng, it 18 then cooled, the resldue i8 flltered off, washed so as to be free from acld wlth a little petroleum ether, washed ~inally w~th water, and then dried. The sl1ghtly reddlsh yellow product, which 18 a mlxture of compounds of b and c, O O

H~C6 ~ ~ C~ ~ CH ~ ~ C6~5 b N5C6 ~ ~ CN ~ CN. ~ N~ ~ 6N5 c -- 15 - Ca~e 150-3566 thus obtalned, dyes polyester fibre material in yellow shades with notable fa~tnea~.
The melting point of the dye ls 242, and the electxon spectrum ln dlmethyl formamide ls:

~ = ~36 max.l 466 my ~max.2 XAMPLE
.~ _ 16 . 8 Part3 of the compound of formula ~ of Example 1 and 7.5 parts of aniline are suspended in 150 parts of glaclal acetic acid, 0.5 parts of newly molten sodlum acetat~ are added slvwly and it i~ bolled at reflux for 5 hour3. After coollng, flltering and washing wlth petroleum ether and water, the slightly reddl~h-yellow resldue of formula SC6--N ~ ~ C6~5 . H5C6 ~ ~ N CH ~ CH ~ 6H5 i~ drled. It dyes polye~ter fibre material ln yellow shade~ with notable fastne8s.
The dye ha~ a meltlng polnt of '64, and the electron ~pectrum ln dimethyl formamide is as follows:

J~L = 450 m~ ~log = 4.5) ;~ ~ 475 mp (log ~ 4 4) 5hoikbr - 16 - Case 150-3566 ~ )2~

42 Part~ of the compound o formula a as ~hown ln Example 1 are heated to 130 for 30 hours ln an autoclave ln the presence of 22 parts o sodium carbonate, 428 parts of concentrated ammonla ~olutlo~ and 120 part~
of water, the pressure lncreases to 6 atmospheres. After cooling, the deep red lnsoluble sub~tance 18 filtered of, wa hed to neutral wlth water and dried.
Mass spectrum (m/e = 418), elementary analysis (C2~H18N402) and infra-red spectr~m demon~trate the presence of the compou~d of formula H ~ ~ ~H
5 6 ~ N ~ H ~ CH ~ N~ C5~5 whlch has excelient pigment propertie~; notablyO the fa~tne~ to mlgratlon, and the depth of colour of the ~ brllll~nt yellow dyelng~ ln poly~inyl chloride.
The dye of the above ormula may be conYer-ted by treatme~t for three hours at 50 to 60~ in 20%
ole~, pouring out the cooled reaction rnixture and I flltering, to form a hydro-soluble dye of formula O O
HN~ ~ _NH
~ J=cN~cN~NJ~

which may b~ used e.g. ~8 a paper dye.

.:

- 17 - Ca~e 150 3566 ! In accordance with the procedure of Example 2, if instead of anillne an equimolar amount of para-amlno-benzoic acid ethyle~ter i8 reacted, a valuable disper~ion dyestuff of formula C2-0-C~ ~ 0 ~ ~ 2 5 H5Cç ~ ~ H ~ N ~ C6~5 i~ o~tained, the nuclear resonance spectrum, ele~entary : analysis (C44H34N406) and mass spectrum (m/e = 714) demon~trate the above ~tructur~. The electron spectrum : ~ln dlmethyl form~mide):

~ 465 m~ (log ~ = 4.5), S~oulder max.

In accordance with the procedure of Example 2, lf in tead of anlllne an e~ulmolecular amount of 1-amlno-3-methoxypropane i8 u~ed, the dye of formula CH2-CH;~OCH3 o CH2~ ~ q-- 2C~2CH2~)cH3 H5C6 ~N~CH~CH~LC6H5 : .

18 Ca~e 150-3566 ~ 024 is obtained, whlch i~ demonstrated by the nuclear re~o~-ance spectrum, elementary analysi~ (C34H3~N~04) and mass ~pectrum (mJe ~ 562).
~he electron spectr~m (in dimethyl formamide)~
;~~ max c 445 ~ ~loq ~ = 4.7) The dyestufff glves fast brilliant yellow dyelng~ on hydrophobic ~ynthetlc fibre material.

In accordance wlth the prQcedure of Example 0 2, if in~tead of aniline equimolecular aAount~ of a) ortho-toluldine ~ N-dimethylamlno-3-propylamine are u~ed, the following are o~talnedr a) the dyestuff of formula ~3 ~ 0 0 H5~6 ~ CH ~ CH ~ ~ 6H5 15 mass spectrum ~/e - 598, electron 8pectrum (in dlmethyl formamlde):

7~, max 1 ~ 455 ~u ( log & = 4. 75) ;~ max 2 = 480. ~ ( log & 2 4 . 65) - l9 - Ca~e 150-3566 and b) the dye~tu~f of formula . fH2-CH2-N (CH3 ) 2 CH2-N~5 ~-CH2~CH -CH -M (C}I ) ,¦ H5C~5--b~=CH~CHd~c6Hs 1, ma~s spectxum m/e = 588 electron spectruM (ln dimethyl formamide~:
~ max = 488 m~ ( log ~ = 4,7~
Both are good dispersion dyestuffs and dye substrates dyeable wlth disper~lon dyes in brilllant yellow shades.
Exam~le 7 In accordance wlth Example 2, if instead o~
the 7.5 parts of anlllne, 3.6 parts o~ anlline and 4.3 par~ of a) para-toluidine, or respectlvely b) ortho-toluidine are usea, then mixture~ of dyes are obtained, the p~ysical data of whlch are determlned a~ follows:
~lect~on spectrum (in dlme~hyl formamide):
a3 ~ max l - 450 m~
max 2 ~ 480 m~, Shoulder meltlng polnt ~ 265, - 20 ~ Ca~e 150-3566 ~ 5~2 b ) ,2 max 1 ~ 4 S 5 m,u, max 2 - 480 m~, meltlng polnt - 26C.
,, These dyes give dyeir~g~ c)f a bxllliant 5 yellow shade with good fa~tnes~ and affinlty on polye~ter fibre~ ~

By pxoceedl~g in accordance with Example 1, but using 4.65 parts of anlline and 5.35 parts of a) para-toluidine, or respectively b) ortho toluidine, mixture~ of dye3 are obtalned whic~ have the followlng phy~lcal data-~ 435 ~, a) ~ max 1 ~ - 464 m~, J~ ~ax 2 meltlng point c 240;
~) ~ max 1 = 435 m~, max 2 - 466 m~, `mel~tng po1nt ~ 240.

~
B~ proceeding ln accordance with Example 1, but instead of the anillne using 8.25 parts of anthra-nllic a ld ethylester and 8.25 part~ of para-aminobenzoic . ' ~ ' - 21 - Case 1~0-3566 ~5~

acid ethylester, a mlxture of dlspersion dyes ls obtained, hav1ng a meltlng point of 255 to 260,ani dyein~ fibre ~atexlal conslsting of llnear, aromat~c polyester ln brilliant yellow shadeQ with good fastness.
Mlxtures of dye~ having very simllar proper ties may also be obtained by using instead of the anlline used ln Example 1 a) 6,175 parts of para-chloroanlline and 6.175 part~ o~ ortho-chloroanlline, or respectlvely 6.175 parts of meta-chloroaniline and 6.175 parts of or~ho-rhloroaniline.
The melting point~ of the mixtures are:
a) - 242 t~ 248 b) - 245 t~ 248 Example 10 By proceeding in accordance wlth Example 2, but using 6 . 6 parts of anthranilic acid ethylester an~
6.6 parts o~ para-amlnobenzolc acid ethylester, a mixture of dispersion dy~s i~ obtained, havlng a melting point of 260, and having notable properties as a brllliant yellow disperslon dye.

1 22 - Ca~e 150-3566 2~

The mlxtures whlch are produced in a slmllar manner to that descr1bed in Example 1 consist basica11y of four components, `and the mixtures which are produced ln a manner ~imilar to that described in Examp1e Z consist baslcally of three component~ but ln neither case can the percentage of the indivldual components be given The following table cont~lns further dye~
stuffs of formula I which are produced in a manner analo-gou~ tG that of e1ther Example 1 or 2. R4 a1way~ signifies a phenyl radical. R3 correæpond~ i~ all cases once to an oxy~en atom or to the group ~ N-R2 of the yiven dye~tuff, 80 that each example represents two dyestuffs. The ~yeings of all dye~tuffs on synthetic ~ibre materials result in : yellow shades, ~with the exception of the dyestuff of Example 25 wh1ch gives orange shadeg~ w1th strong f1uore~-cence and notable fastne8s.

- 23 - Case 150-3566 T d b 1 e .. . _____ NO. Rl R2 __ para-phenylene n-propyl 11 2,5-dimethyl-1,4- -C H
phenylene 6 5 12 2,5-dichloro-1,4- -cH2cH2c~2-o-cH
phenylene 3 13 2,5-dibromo-1,4- -cH2cH2cH2-o-c2H5 phenylene 14 2,5-dihydroxy-1,4- -CH2cH2cH2-o-cH2cH2cH2c~3 2,5-dimethoxy-1,4- paxa-chlorophenyl phenylene 16 2,5-diethoxy-1,4- ortho-bromophenyl : phenylene 17 para-phenylene ` -CH2CH2O~
18 para-phenylene ortho-toluyl 19 para-phenylene meta-ethoxyphenyl 1,4-naphthylene n-butyl 21 1,5-naphthylene 2,4-dichlorophenyl 22 2,6-naphthylene . meta-ac~tylamlnophen~l 23 para-phenylene ortho-chlorophenyl 24 para-phenyIene meta-chlorophenyl 2S 3,4-d~romo-thienylene-2,5* C6H5 26 para-phenyIene * Productlon of ~he corresponding dialdehyde according to SteiDXopf et al., Ann. 532, (1937)~ 250 and Ann. 541, (1939), 260.

- 24 - Case 150-3566 1~500;29~
Example 27 4~.2 Parts of the condensatlon product of ~erephthaldehyde and nicotinurlc acld, of formula ~ 1~ , Q ~ CH ~ CH ~ O

O O

are heated to 130 over the course of 30 hours tn an auto-clave ln the presence of 22 parts of sodium carbonate in 120 part~ of water and 428 parts of concentxated am~onia solution. The pressure increases to approx. 6 atmospheres.
A deep red product of ~ormula N
CH ~ CH ~ H
o preclpitate~ i~ pure form; lt ls washed to neutral with distilled water and f~nally drled. The product has a melting poin~ of above 300C, and ~as good pigment proper-ti~.
A very s~milar pigment is o~tained by replacing the conden~atlon product used as a staxting materlal in Exampl~ 27, by that made by condenslng picolinu~ic acid and tereph~haldehyde of formula . - .
. .

- 25 - Case 150-~566 ~ilD5a9~24 N ~
1~L~CH~H--~

Th(3 pigrnent ~?btalned correspt)nds to the formula .' E~LCN ~ CN=~

O O

In the îollowing ~able 2 dyes are shown which are obtained in analogy wlth the operating proc~sses vf Example 1 or 2 . Each example agaln represent~ two dyes 9 5 l.e. R3 ~ 0 or R3 - ~-R2. These dyes give dyelng~ of a brilliant y~llow ~hade on polyester.

- 26 - Case 150 3566 T a b 1 e 2 ~_ ~ __ E~LE Rl R2 ~4 . . ._. ___ _ 28 1,4-PhenyleneC6H5 2-Pyridyl 29 do. do. 3-Pyridyl do. do. 4-Pyridyl 31 do. do. 2-Thienyl 32 do. do. 2-Pyrryl 33 do.-CH2CH2CH2NHC2H5 4-NitrPphenyl 34 do. 2 ~2CH2C2H5 2,4-Dichlorophenyl 2-chloro-5-methyl n-Butyl 4-Bromophenyl phenylene 36 2,5-Dimethoxy-1,4-phenylene-C6H5 4-Cyanophenyl 37 1,4-Phenylene do. 2-Hydroxyphenyl 38 do. -C~2~H2CH20C~3 39 do. do. 2,4-Dinitrophenyl do. do. 2-Ethoxyphenyl 41 do. do. 3,4-Dimethoxyphenyl 42 do. do. 2-Acetoxyphenyl 43 do. do. 2-Methoxycar~onyl-. phenyl 44 do. do~ 2-Methoxycarbonyl-4-chlorophenyl do. do. l-Naphthyl 46 do. do. 2-Naphthyl 47 do. do. 2-Hydroxynaphthyl-3 48 do. n-Butyl 2-Propionyloxyphenyl 49 do. do. ~-E~hoxycarbonyl-phenyl do. do. 2- ~-Methoxyethoxy-carbonyl-phenyl do. do~ 4-Acetylaminophenyl .

- 27 - Case 150~3566 ~)S~ 4 .1 1 ~ .
N~. Rl R2 4 ~_ __ _ , 52 1,4-Pheny?ene n-Butyl 4-Propionylamlno-phenyl 53 do. -C6H5 Pyrazlnyl 54 do. 2-Methylphenyl 2-Acetylaminophenyl do. 3-Methoxyphenyl 3-Chlorophenyl 56 do. 2,4-Dimethylphenyl do.
57 do. 2,4-Dicyanophenyl 3-Methylphenyl 58 do. 2,4-Dinitrophenyl do.
59 do. 4-Nltrophenyl do.
do. 2-Cyanophenyl do.
61 do. 2-Methoxycarbonyl- do.
phenyl _ __ __ __ __ __~

~osoo~
E x a m p 1 e 62 21 Parts of the compound of formula a in Example 1 are dissolved in 200 parts of n-butanol and heated to the boil under reflux~ Under the surface, dry ammonia-gas is introduced and at the same time, over a period of 10 minutes, 2~35 parts of aniline are added. The addition of ammonia-gas is continued for a further 10 minutes, and the colour of the suspension turns from orange to yellowO A further lo9 parts aniline are added, the mixture is refluxed further for 40 minutes, cooled to room temperature, the precipit-ate is filtered, washed with ethanol and dried about at 80. The product which corresponds to the formula H5c6-co-NH-c=cH ~ CH=C-NH-CO-C H

is suspended in 100 parts of phthal~c acid diethylester and heated to 270o Under these conditions the product is solubilized and cryslisized. After cooling to room temperature, the precipitate is filtered, washed with ethanol and vacuum dried at 80.
The melting point of the dyestuff is over 300; the mass spectr~m shows that the compound which is at least 90% pure, corresponds to the formula H C r - N IN ~ C6H5 H5C6- N ~ CH = ~CH ~ NH

O O
(m/e = 4~4) Dyeings made with this disperse-dyestuff have good fastness properties.
APPLICATION EXAMPLE A

~ . _ .
7 Parts of the dyestuff produces in accordance with Example 1 are ground to a fine powder for 48 hours in a ball mill together with 4 parts of the sodium salt of dinaphthylmethane-disulphonic acid; 4 parts of sodium cetylsulphate and 5 parts of anhydrous sodium sulphate.

i~SOOZ~
1 Part of the dyeing preparation thus obtained is made in~o a paste w.ith a little watcr and the suspension obtained is added through a sieve to a dye bath containing 3 parts of sodium lauryl sulphate in 4000 parts of water. The liquor ratio is 1:40. Then, 100 parts of purified poly-ester fibre material are added to the ba~h at 40 to 50, 20 parts of a chlorinated benzene emulsified in water are added, the bath is heated slowly to 100 and dyeing takes place for 1 to 2 hours at 95 to 100o The bright yellow dyed fibres are washed, saponified, washed again and dried~ The even dyeing is fast to light, cross-dyeing, washing, water, sea water, perspiration, sublimation, gas fumes, thermofixation, pleating and permanent-press finishO
APPLICATION EXAMPLE B
To a basic mixture consisting of 63 parts of polyvinyl chloride emulsion 32 parts of dioctyl phthalate,

3 parts of commercial epoxy softener, 1~ 5 parts of stabilizer ~barium-cadmium-stearate-mixture, also commercial) and 0.5 parts of a chelator (commercial~
are added OD5 parts of the pigment of Example 3 and 5 ~arts of titanium dioxide pigment, and these are mixed together intimatelyO
The mixture is rolled for 8 minutes to obtain better pigment distribution in a roller mill heated to 160C and having friction rollers (one turning at 20, the other at 25 revolutions per minute), and the sheet obtained, ~hich is of 0.3 mm thickness and has a yellow shade, is removedO
The dyeing is fast to light and migration, and is heat-resistant.

Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE AS FOLLOWS:

1. A compound of formula I, I

in which R1 signlfies a 1,4-phenylene radical, a 1,3 , 1,4-, 1,5- or 2,6-naphthylene radical, a bivalent radical of furan, thiophene,pyrrole or pyridine or a bivalent radical of benzofuran, benzothiophene, benzopyrrole or benzopyridine in which the bonds are in the 2,5- or 2,6- or para- position, all of which radicals are either unsubstituted or substituted by a total of up to two substituents per ring selected from the group consisting of chlorine and bromine atoms, hydroxyl, methyl, methoxy and ethoxy groups (up to two of any of these), trifluoromethyl, (C2-4)alkanoyl-amino, benzoylamino and nitro groups (only one of any of these), R2 signifies a hydrogen atom; an unsubstituted (C1-4)alkyl radical;
a (C1-4)alkyl radical substituted by a chlorine or bromlne atom, a hydroxy, (C1-4)alkoxy, (C1-4)-alkylamino, di(C1-4)alkylamino, (C2-4)alkanoyloxy, (C1-4)alkoxy-carbonyl, (C1-4)alkoxycarbonyloxy or benzoyloxy; an unsubstituted phenyl radical or a phenyl radical substituted by a total of up to three substituents selected from the group consisting of chlorine and bromine atoms, and methyl groups (up to three of any of these), (C1-4)alkoxy, (C1-4)alkoxy-carbonyl, cyano and nitro groups (up to two of any of these), hydroxy, (C1-4)alkylamino, di(C1-4)alkylamino, (C2-4)alkanoylamino and (C1-4) alkoxycarbonylamino groups (only one of any of these); a naphthyl radical; pyridyl-2, -3 or -4;
pyrimidyl-2 or -4; 2,4-dimethyl-pyrimidyl-5-; thienyl-2; thiazolyl-2;

benzothiazolyl 2; or 5-methyl-isoxazolyl-3, R3 signifies an oxygen atom or a group of formula in which R5 has one of the significances given above for R2, and each of the R4's independently, signifies an unsubstituted phenyl or naphthyl radical; a phenyl or naphthyl radical substituted by a total of up to three substituents selected from the group consisting of chlorine and bromine atoms and methyl groups (up to three of any of these), (C1-4)alkoxy and nitro groups (up to two of any of these), hydroxy, cyano, (C1-4)alkylamino, di(C1-4)alkylamino, (C1-4)alkoxy-carbonyl, (C1-4)alkoxy(C1-4)alkoxy-carbonyl, (C2-4)alkanoyloxy, (C2-4)alkanoylamino, (C1-4)alkoxy-carbonylamino and sulpho groups (only one of any of these); pyridyl-2, -3 or -4; a pyrazinyl radical;
thienyl-2 or pyrryl-2 or -3, which compound,where R4 contains a sulpho group, is in the free acid or salt form.

2. A compound or a mixture of compounds according to Claim 1, of formula Ia, Ia in which R6 signifies an unsubstituted 1,4-phenylene radical; a 1,4-phenylene radical substituted by up to two substituents selected from the group consisting of chlorine and bromine atoms, hydroxyl, methyl, methoxy and ethoxy groups; a 1, 4-, 1,5- or 2,6-naphthylene radical or a 3,4-dibrsmothienylene-2,5-radical, R7 signifies a hydrogen atom; an unsubstituted (C1-4)alkyl radical, a (C1-4)alkyl radical substituted by a hydroxy, (C1-4) alkoxy, (C1-4)alkylamino or di-(C1-4)alkylamino group; an unsubstituted phenyl radical or a phenyl radical substituted by a total of up to two substituents selected from the group consist-ing of chlorine and bromine atoms, methyl, cyano and nitro groups (up to two of any of these), (C104)alkoxy, (C1-4) alkoxycarbonyl, acetylamino and propionylamino groups (only one oi any of these);
or a 2-pyridyl radical, R8 signifies an oxygen atom or in which R7 is as defined above, and the R9's are the same and signify an unsubstituted phenyl radical; a phenyl radical substituted by a total of up to two substituents selected from the group consist-ing of chlorine and bromine atoms, nitxo, methyl and (C1-4) alkoxy groups (up to two of any of these); cyano, hydroxy, acetoxy, propionyloxy, methoxy-carbonyl, ethoxycarbonyl, methoxy-ethoxycarbonyl, acetylamino, proplonyl-amino and sulpho groups (only one of any of these); a naphthyl-1 or -2 radical, a naphthyl-1 or -2 radical substituted by a sulpho group; 2-hydroxy-naphthyl-3, 2-hydroxy-sulpho-naphthyl-3-, pyridyl-2, -3 or -4, thienyl-2, pyrryl-2 or -3; or pyrazinyl.

3. A compound or a mixture of compounds according to Claim 2, in which R6 signifies an unsubstituted 1,4-phenylene radical or a 1,4-phenylene radical substituted by a total of up to two substituents selected from the group consisting of chlorine atoms, methyl and methoxy groups, R7 signifies a hydrogen atom; an unsubstituted (C1-4)alkyl radical; a (C1-4)alkyl radical substituted by a hydroxy, methoxy, ethoxy, methylamino, dimethylamino, ethylamino or diethylamino group; an unsubstituted phenyl radical, a phenyl radical substituted by a total of up to two substit-uents selected from chlorine and bromine atoms and methyl groups (up to two of any of these),methoxy, ethoxy, methoxy-carbonyl and ethoxycarbonyl groups (only one of any of these);

or a 2-pyridyl radical, and R9 signifies an unsubstituted phenyl radical, a phenyl radical substituted by a total of up to two substituents selected from the group consisting of chlorine and bromine atoms and methyl groups (up to two of any of these), cyano, nitro, methoxy, ethoxy, methoxy-carbonyl and ethoxycarbonyl groups (only one of any of these);
or a 2-, 3- or 4-pyridyl radical.

4. A compound or a mixture of compounds according to Claim 3 in which R7 signifies a hydrogen atom; an un-substituted (C1-4)alkyl radical; a (C1-4)alkyl radical substituted by a hydroxy, methoxy, ethoxy or dimethylamino group;
an unsubstituted phenyl radicals a phenyl radical substituted by a total of up to two substituents selected from the group consisting of chlorine and bromine atoms and methyl groups (up to two of any of these), methoxy, ethoxy, methoxycarbonyl and ethoxycarbonyl groups (only one of any of these); or a 2-pyridyl radical.

5. A compound or mixture of compounds according to Claim 3, in which R6 signifies an unsubstituted 1,4-phenylene radical, R7 signifies a hydrogen atom, an unsubstituted phenyl radical or a phenyl radical substituted by a chlorine atom, a methyl, methoxycarbonyl or ethoxycarbonyl group and R9 signifies an unsubstituted phenyl radical.

6. A compound or a mixture of compounds accord-ing to Claim 1, in which R2 and R5, in the case where R3 signifies a group of formula = N-R5, signifies a hydrogen atom.

7. A compound or a mixture of compounds accord-ing to Claim 1, in which R4 signifies a substituted phenyl or naphthyl radical wherein one substituent thereon is a sulphonic acid group, or an alkali metal salt or salts of such compound or mixture of compounds.

8. A compound or a mixture of compounds accord-ing to Claim 1, in which one or both of R2 and R5, in the case where R3 signifies a group of formula , has a significance other than a hydrogen atom and which compound or mixture of compounds is free from sulphonic acid groups or salts thereof.

9. A compound according to Claim 5, of formula

10. A compound according to Claim 5, of formula

11. A compound according to Claim 5, of formula

12. A compound according to Claim 5, of formula

13. A process for the production of a compound of formula I, or a mixture of compounds of formula I, as defined in Claim 1, comprising condensing a compound of formula II, II

in which R1 and R4 are as defined in Claim 1, with a compound of formula III, in which R2 is as defined in Claim 1, or a mixture of compounds of formula III, in a 1:1 or 1:2 molar ratio.

14. A process for dyeing substrates consisting of or comprising synthetic or natural polyamides, cellu-lose fibres or paper, comprising using a compound or a mixture of compounds according to Claim 7, as dyeing agent.

15. A process for dyeing or printing substrates of semi-synthetic, synthetic hydrophobic, high molecular weight organic materials, comprising using a compound or a mixture of compounds according to Claim 8, as dyeing or printing agent.

16. A process for pigmenting plastics in the mass or paper in the stock, comprising using a compound or a mixture of compounds according to Claim 6, as pigmenting agent.