CA1047487A

CA1047487A - Monoazo pigments and a process for their manufacture

Info

Publication number: CA1047487A
Application number: CA235,289A
Authority: CA
Inventors: Stefan Hari; Rudolf Mory
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1974-09-16
Filing date: 1975-09-12
Publication date: 1979-01-30
Also published as: CH599294A5; GB1467589A; FR2284644A1; JPS5155322A; FR2284644B1; DE2540803A1

Abstract

Abstract of the Disclosure Mono azo pigments of the formula

Description

10474~7 , . .
It has been fourLd that valuable, new monoazo pigments of the forJnula ~ =N ~ ~ =y (I) R CO~ l . 1 X R2 : : .
. . .
,.
wherein Rl and R2 denote H atoms, alkyl groups containing 1-4 C atoms, or aryl radicals, R3 denotes an alkyl radical which contains 1-4 C atoms and which can opti.onally contain halogen atoms, alkoxy groups containing 1-4 C atoms, or an aryl, aryloxy or arylmercapto group as substituents, or ~ denotes an aryl or heterocyclic radical, X denotes an O atom , or an lmino group, Y denotes an O or S atom or an imino group, and Xl and Yl deno-te H or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or a nitro, cyano or trifluoro-methyl group, but Xl and Yl must not be H atoms if R3 repres-ents an unsubstituted alk~Jl group, and wherein the acylamlno group is ln the m- or p-position to the azo group, are obtained ',- if the diazo compound of an amine of the formula X
i ~ NH2 (II) CONH r . Yl .
: is coupled wi-th a coupling component of the formula .. .

:'. . ' ' ~ . ':

: ~o474~7 O R
- ~ (III) .,, ~rN
;';' n I
X R

' Pigments of particular in-terest are those of the ~ormula I wherein R3 denotes a phenyl radical which optionally ~contains halogen atoms, alkyl or alkoxy groups con-taining 1--4 C
': atoms, or nitro or alkoxycarbonyl groups containing 2-6 C ato~s, ` and those wherein R3 denotes a radical of' the ~ormula ;
,~ PhOCH2-,:
wherein Ph denotes a phenyl radical which optionally contains ;halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or alkoxycarbonyl groups containing 2-6 C atoms.
jParticularly preferred pigments are those of the formula , ~ OCH~COHN ~ ~ N=N ~ ~ o (I~

y 3 ORC O R' t wherein R' denotes a H atom or a methyl group, RL~ denotes an alkyl group containing 1-4 C atoms, and X2, X3 and Y2 denote H or halogen atoms or alkyl or alkoxy groups containing 1-4 C atorns.
.
_ 3 _ ~ - . . . ~ , .
, - . . . : . : . :
:
.. . . . . ..
.

10474~7 : The diazo components used are preferably amines of . . .
, the iorrnula II ~Jherein R3 denotes a phenyl radical which ,~ optionally contains halogen atoms, alkyl or alkoxy groups ., containing 1-4 C atoms, or nitro or alkoxycarbonyl groups con-'' taining 2-6 C atoms, or ~herein R3 denotes a radical of -the formula ' ~ PhOCH2--.
.... .
wherein Ph deno-tes a phenyl radical which optlonally contains halogen atoms, alkyl or alkoxy groups containing 1-4 C atom~ 5 or'alkoxycarbonyl groups containing 2-6 C atoms, and particu-larly those of the formula '.
., .

OC~2CO~ ~ NH2

2 ~4 " ' ' " ~,' ' ' .
wherein R4 denotes an alkyl group containing 1-4 C atoms, and X2, X~ and Y2 denote H or halogen atoms or alkyl or alkoxy groups containing 1-4 C atoms.
The following should be mentioned as examples of diazo components: l-amino-2-chloro-5-acetylamino-benzene, l-amino-2-methyl-5-acetylamino-benzene, l-amino 2-methoxy-5-acetylamino-benzene, l-amino-4-methyl-5-acetylamino-benzene, l-amino-4-methoxy-5-acetylamino-benzene, 1-amino-2-ethoxy-5-acetylamino-benzene, l-amino-2-methoxy-5-propionylamino-benzene, l-amino-2-chloro-5-propionylamino-benzene, 1-amino~2-metllyl-5-.. i . .
.. . . ..
' . ,, ~ : :
.. .. , .

, ~047487 bu-tyrylaMlno-benzellf~ amino-2-chloro-4-acetylamino-benzene, .,. l-amino-2-Methyl-4-ace-tylamino-benzene, 1-amino-2-methoxy-4-ace-cylamino-benzene, l-amino-2~nitro-4-acetylamino-benzene, 1~
: amino-3-chloro-4-acetylamino-benzene, 1-amino-3-metho~-4-,...
acetylarnino-benzene, l-amino-3-cyano-4-acetylamino-benzene, 1-: amino 3-methyl-4-acetylamino-benzene, 1-amino-2-chloro-4-, .. propionyla~ino-benzene, l-amino-2-methyl-4-butyrylamino-~. benzene, l-amino-2-methoxy-3-acetylamino-benzene, 1-amino-2-'- chloro-3-acetylamino-benzene, 1-amino-2,5-dichloro-4-acetyl-amino-benz~ne, l-amino-2,5-dime-thyl-4-acety-lamino-benzene, l-amino-2,5-dimethoxy-4-acetylamino-benzene, 1-amino-2,5-. . dlethoxy-4-acetylamino-benzene, l-amino-3,5-dichloro-4-acetyl-,. amino-benzene, l-amino-2-methyl-5-chloro-4-acetylamino-benze.fle,~J` l-a~ino-2-chloro-5-methyl-4-acetylamino-benzene, 1-amino-2-., methox~-5-chloro-4-acetylamino-benzene, 1-amino-2-methoxy-5--methyl-4-acetylamino-benzene, 1-amino-2-me-thoxy-5-nitro-4-... .
acetylamino-benzene, l-amino-2-methoxy-5-chloro-4-propionyl-amino-benzene, l-amino-2-chloro-4-methyl-5-acetylamino-benzene, l-amino-2-methoxy-5-benzoylaminobenzene, 1-amino-2-methoxy-5-(2'-chlorobenzoylamino)-benzene, 1-amino-2-methoxy-5-(4'-chlorobenzoylamino)-benzene, l-amino-2-methoxy-5-~2~,4~-dichlorobenzoylamino)-benzene, l-amino-2-methoxy-5-(2'-, thienoylamino)-benzene, l-amino-2-methoxy-5-(2'-furoylamino)-benzene, l-arnino-2-methoxy-4-benzoylaminobenzene, 1-amino-2-methoxy-4-(2'-chlorobenzoylamino)-benzene, 1-amino-2-methoxy-4-(4~-chlorobenzoylamino)-benzene, 1-amino-2-methoxy-4-(2',4'-dichlorobenzoy].amino)-benzene, l-amino-2-methoxy-4-(2'-methy]-.- . ~ , - ~ ~ .
.' .
. .
.
, : , . ,:
. . : : .
.. . . .; ~ , ,. . . - : .
.
. . , . ~ . ' :
- . , : ~
. .

', t 10~7~7 benzoyi~3.mino ) -benze-rle, 1-amino-2-me-thoxy-4- ( 4 ' -methylbenzoyl--amino ) -benzene, l-amino-2 methoxy 4- ( 2 ' -methoxybenzoylamino ) -benzene, l-amino-2-methoxy-5- ( 2 ' -methylbenzoylarnino )-benzene 9 .,~
-1-amino-2-methoxy-5 - ( 4 ' -methylbenz oylamino ) -benzene, l-amino-2-metho~y-5 - ( 2 ' -methoxybenz oylarnino ) -benzene, 1-amino-2-methoxy-5- ( 4 ' -methoxybenzoylamino ) -benzene, l-amino-2-methox~J-

3-benzoylaminobenzene, 1-amino-2-methoxy-6-benzoylaminobenzene, l-~mino-2, 5-dimethoxy-4-benzoylaminobenzene, 1-amino-2, 5-dimethoxy-4- ( 2 ' -chl orobenzoylamino ) - benz ene, 1 amino-2, 5-dime-thoxy-4~ (4 ' -chlorobenzoylamino )--benzene, 1-amino-2, 5-dimethoxy-4- ( 2 ', 4 ' -dichlorobenzoylamino ) -benzene, l~amino-2, 5-dimethoxy-~- ( 2 ' -methylbenzoylamino )-benzene, 1-amino-2, 5-dimethoxy-4- ( 4 ' -methylbenzoylamino ) benzene, 1-amino-2, 5-dimethoxy-3-benzoylaminobenzene, 1-amino~2-methoxy-5-methyl-4-,, benzoylaminobenzene, l-amino 2-methoxy-5-methyl-4- ( 2 ' -chloro-benzoylamino)-benzene, l-amino-2-methoxy-5-methyl-4 (4'-chlorG- ~
: benzoylamino )-benzene, l-amino-2-rnethoxy-5-methyl-4- ( 2 ', 4 7 - :
dichlorobenzoylamino )-benzene, l-arnino-2-methoxy-5-methyl-4-.
( 2 ' -methylbenzGylamino ) -benzene, l-amino-2-methoxy-5-methyl--4-. (4'-methylbenzoylamino)-benzene, 1-amino~2-methoxy-5-methyl-4-: (2 '-me-thoxybenzoylamino)-benzene, 1-amino-2-methoxy-5-meth.yl-

4- ( 2 t -thi enylamino ) -benzene, 1-amino-2-methoxy-5-methyl-4- ( 2 ' -~uroylamino ) -benzene, l-amino-2-methoxy-5-chl oro-4_benzoyl-aminobenzene, l-amino-2-methoxy-5 -chl oro-4- ( 2 ' -chl orobenz oyl-amino ) -benzene, l-amino-2-methoxy-5-chl oro-4- ( 4 ' -chl orobenz oyl-amino )-benzene, l~amino-2-methoxy-5-chloro-4- ( 2 ', 4 ' -dichloro-benzoyla~nino~-benzene, l-amino-2-methox~y-5-chloro-4-(2 '-, . '' . ;

~ 047487 methylbenzoylami-no)-benzene, l-amino-2-methoxy~5-chloro-4-(4'-methylbenzoylam-no)-benzene, l-ami.no-2-methoxy-5-chloro-4-~2--methoxybenzoylamino)-benzene, l-am:ino-2-methoxy-5-chloro-4-(2'-thienylamino)-benzene, 1-amino-2-methoxy-5-chloro-4-(2'-~uroylam.ino)-benzene, l-amino-2-methoxy-5-ni-tro-/-~-benzoyl-aminobenzene, l-amino-2-methoxy-5-nitro-4-(2'-chlorobenzoyl-amino)-benzene, l-amino-2-methoxy-4-phenacetylaminobenzene, l-amino-2-methoxy-5-phenacetylaminobenzene, 1-amino-2--metho~y-3-phenacetylaminobenzene, 1-amino-2,5-dimethoxy-4-phenacetyJ-, aminobenze~e, l-amino-2-methoxy-5-mcthyl-4-phenacetylamino-benzene, l-amino-2-methoxy-5-chloro-4-phenacetylaminobenzene~l-amino-2-methoxy-5-naphthylacetylarninobenzene, 1-amino-2-; methoxy-5-phenoxyacetylaminobenzene, l-amino-2-methox~r-5-(4'-chlorophenoxyacetylamino)-benzene, l-amino-2-methoxy-5-phenyl~
: thioacet;ylaminobenzene, l-amino-2-me-tho~y-4-phenylthioacetyl-aminobenzene, l-amino-2,5-dimethoxy-4-phenylthioacetylamino-benzene, l-amino-2-methoxy-5-methyl-4-phenylthioacetylamino-benzene, l-amino-2-methoxy-5-chloro-4-phenylthioacetylamino-benzene, l-amino-2,5-diethoxy 4-(2',4'-dichlorophenylthio-acetylamino)-benzene, l-amino-2-ethoxy-5-benzoylaminobenzene, l-amino-2-ethoxy-5-(2'-chlorobenzoylamino)-benzene, l-amino-2-ethoxy-5-(4'-chlorobenzoylamino)-benzene, 1-amino-2-etho~J-

5-(2',4'-dichlorobenzoylamino)-benzene, 1-amino-2-ethoxy-4-~2'-chlorobenzoylamino)-benzene, 1-amino-2-ethoxy-4-(4'-.
chlorobenzoylamino)-benzene, l-amino-2-ethoxy-4-(2',4'-dichlorober,zoylamino)-benzene, l-amino-2-ethoxy-5-(2'-methyl-benzoylamino)-benzene 5 1-amino-2--ethoxy-~--(4'-methylbenzoyl-'-, ' ~ ' , . ~ "' ' " .

' .
. :

~0474~7 arni no ) -benzcne, 1 --arnino-2-ethoxy-4- ~ 4 ' -methylbenz oylamino ) -benzene, l~amino~2-ethoxy-4- ( 2 ' -methylbenzoylamino ) -benzene, , . , . ~ l-arnino-2~ ethoxy-5 - ( 4 ' -me, hoxybenz oylamino ) -benzene, l-amino-~. 1 2-ethoxy-4- ( 2 ' -methoY~ybenzoyl.amino ) --benzene, l-amino-2, 5-~ diethoxy-4-benzoylaminobenzene, 1-amino-2,5-diethoxy-4-(2'~
`- chl or obenzoylamino ) -benzene, l-arnino-2, 5 -di ethoxy-4- ( 4 ' -chl orobenz oylamino ) -benz ene, l-amino-2, 5-di ethoxy-4- ( 2 ', 4 ' -di chl orobenzoylamino ) -benzene, l-amino-2, 5 -di ethoxy-4- ( 2 ' -; ` methylbenzoylamino ) -benzene, l-amino-2, 5-die-thoxy-4- ( 4 ' -, methylbenzoylamino ) -benzene, l-amino-2, 5 ~di ethoxy--4- ( 2 ' -- methoxybenzoylamino )-benzene, 1-amino-2-ethoxy-5-me-thyl-4-,:, benzoylaminobenzene, l-arnino-2-e-thoxy-5-chloro-4-benzoylaminG-.. .
:~ benzene, l-amino-2-ethoxy-4-phenacetylaminobenzene, 1-arnino-2-ethoxy-5-phenacetylaminobenzene, 1-amino-2,5-diethoxy-4-! ~
phenac etylaminobenzene, 1-amino_2, 5 -di ethoxy-4-phenoxyac e-tyl--aminobenzene, l-amino-2,5-diethoxy-4-(4'-ch].orophenoxyacetyl amino )-benzene, l-amino-2, 5-diethoxy-4-phenylthioace . ylarnino~ .
benzene, l-amino-2-methyl-5-benzoylaminobenzene, 1-amino-2-methyl-4-benzoylarninobenzene, 1-amino-2, 5-dimethyl-4-benzoyl-aminobenzene, l-amino-2-methyl-5-chloro-4-benzoylaminobenzene, l-amtino-2 methyl-5-phenacetylaminobenzene, 1-amino-2-methyl-4-phenacetylaminobenzene, l-amino-2--methyl 5-phenoxyacetylamino-benzene, l-amino-2-methyl-4-phenoxyacetylaminobenzene, l-amino-2,5-dimethyl-4-phenacetylaminobenzene, 1--amino-2,5-dimethyl-4-phenoxyac etylaminobenzene, l-amino-2, 5 -dimethyl-4- ( 4 ~ - chl oro-phenoxyac e tylamino ) -benzene, 1-amino-2, 5 -dimethyl-4-phenyl-thioacetylami.nobenzelle, l-amino-2-chloro-5-benzoylaminobenzene, ., ;:

~0474~7 l-arfiino-2-clllorc-4--benzoylaminobenzene, 1--amino~2,5-dichlsro 4-benzoylarninGbenzene, ].-amiro-2-chloro-5-methyl-4--benzoylamino-benzene, l-amino-2~chloro--5-phenacetyl~minobenzene, 1-amino~2-chloro-4-phenacetylaminobenzene, ',. amino-2-chloro-5-pher acetylam-noben~ene, l-amiro-2-chloro-4-pheno~yacetylamino-benzene, 1-amino-2,5-dichloro-4-phenace-tylaminobenzene, 1- ~ -amino-2,5-dichloro-4-phenoxyacety]aminobenzene, 1-amino-2,5~
dichloro-4-(4'-chlorophenoxyacetylamino)-benzene, 1-amino-2,5 dichloro-4~phenylthioacetylaminobenzene, 1 amino-2-nitro-5-benzoylaminobenzene, 1-amino~2-nitro-4-benzoylaminobenzene, l-amino~2-nitro-5-methyl-4-berlzoy]aminobenzene, 1-amino-2-nitro-5-chloro-4-benzoylaminobenzene, 1-amino--2-nitro-4-phen-acetylaminobenzene, l-arnino-2-nitro-4~phenoxyacetylamirlobenzene, 1 amino-2-nitro-4-(4'~chloropllerloxyacetylamino)-benzene and l-amino-2-nitro-4-phenyltkioacetylaminobenzene.
The diazo components mentiored are, ~ithout exception, known compounds.
Barbi-turic acid, in particular, should be men-tioned as a coupling compGnent; in addition, its functional derivatives can be used, for example N-methyl-, N,N-dimethyl-, N-ethyl-, N,N-dialkyl-, N-phenyl- or N,N-diphenyl-barbituric acid and thio- or imino-derivatives thereof of the formula ~g--N~ (C \`C=~H or ~ ~C-NH

' ' "''', _ g _ ,' ' : : ''' '''' ' '~ ' "

-.
, ~ ' ~ ' ` ~ lV474~7 Pre~erred barbituric acids are those of the forrnula ~,., O ~i O
.. I t .

wherein Rt denotes an alkyl group containing 1-4 ~ atoms, or a phenyl group which is optionally substituted by halogen atoms or alkyl or alkoxy groups con-taining 1-4 C atoms, but par-ticularly denotes a H atom.

The barbituric acid derivatives mentioned are kno~
, . .
compounds.
rne coupling is appropriately carried out by addlng the diazoniu~. solution gradually to the aqueous solu-tion of -the coupling component at a pH value of 4-6.
It is advan-tageous to adjust the p~I value by adding a buffer. Examples of buffers ~hich can be used are the salts, particularly alkali metal salts, of formic acid, phos-phoric acid or acetic acid. Furthermore, it is possible to add to the coupling solution wetting agen-ts, dispersing agents or emulsifiers, ~or example an aralkylsulph-onate, such as dodecylbenzenesulphonate, polycondensa-tion products of ethylene oxides, such as the product from the reaction of ethylene oxide with p-tert.-octylphenol, and also alkyl esters of sulphoricinoleates, for example n-butyl sulphoricinoleate. The coupling dispersion can also advantageously contain protective colloids, for example methylcellulose, or minor or major amounts of inert, water~

' . ` ' , .

i 10~7~
miscib:l~ organic solvents, such as ace-to-ne, rnethyl ethyl ketone, methanol, ethanol or isopropanol, as well as dime~hyl~
formamide or N-methylpyrrolidone or pyridine By vir-tue of their insolubility, -the resulting pig-ments can be isolated from the reaction mixtures by filtration.
In most cases these pigments have an excellen-t texture after drying. It proves advantageous in some cases to give the resulting pigments an af-ter--treatment with an organic solvent, preferably a solvent boiling above 100C.
Solvents which prove particularly suitable are benzene derivatives which are substituted ~y halogen atoms or alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, and pyridine bases, svch as pyridine, picolix-e or quinoline, and also ketones, such as cyclohexanone, ethers~
such as ethylene glycol monomethyl or monoethyl ether, amides, such as dimethylformamide or N-methylpyrrolidone, and sulpholane or dimethylsulphoxide.
The after-treatment is preferably carried out by heating the pigment in the solvent to 100 to 150C, whereby, in many cases, a coarsening of grain takes place, which has a favourable effect on the fastness to light and migration of the resulting pigments.
The coupling can also be carried out with advantage by continuously combining an acid solution of the diazoxium salt with an alkaline solution of the coupling co~ponent in a mixing jet, an immediate coupling of the components taking place. The resulting colorant dispersioxi is con-tinuously . . . -- . , .

' - :
, ' ' :

~o47~87 withdrawn from the mixing jet and the colorant is isolated by filtration.
Finally, it is also possible to accomplish the coupling by suspending the amine to be diazotised in an organic solvent, together with the coupling component, and -treating the mixture with a diazotising agent, particularly an ester of nitrous acid, such as methyl, ethyl, butyl, amyl or octyl nitrite.
The new colorants are valuable pigments which have good fastness to light and migration and which can be used in a ~inely divided form for pigmenting high~molecular, organic material, for example cellulose e-thers and esters, such as :
ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymeri-sation resins or condensation resins, for example aminoplasts, particularly urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyole-fines, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile or polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, on their own or as mixtures.
It is immaterial here whether the high-molecular compounds mentioned are present as plastic compositions or melts or in the form of spinning solutions, lacquers or paints.
Depending on the application, it proves advantageous to use the new pigments as toners or in the form of preparations.
The new pigments have a good tinting strength, fastness to light migration, solvents and weather.
Compared with the colorants described in British . .

lU474~
,, Patent S7~eci:Eicatio;fl 513,414, the colorants according to -the invention are distinguished by be-tter resistance -to heat.
By virtue of their high tinctorlal strength, purity and transparency, the new colorants are suitable, in particular, for vse in printing inks, such as in let-terpress, gravure and offset printing.
In the examples which follow, unless otherwise specified, the parts denote parts by weight and the percentages denote percentages by weight.

., 13.5 parts of 1-arnino-2,5-diethoxy-4-(4'-chlorophenox-y-acetylamino)-benzene are dissolved in 150 parts by volume of glacial acetic acid at 55C. The brown solution is stirred with 10 par-ts by vol~ne of concentrated hydrochloric acid and -the resulting suspension (hydrochloride) is cooled to 6C and 9.5 parts by volume of 4 N sodiurn nitrite solution .... . . . .
are added dropwise over the course of 25 minutes and at 6C.
The diazo compound obtained in this way is a beige~coloured suspension.
4.5 parts of barbituric acid are then dissolved in 100 parts of water by means of 17.5 parts by vol~rne of 30Q~o strength sodium hydroxide solution. The colourless solution is added dropwise to the diazo suspension at 5C, over the course of 30 minutes. In the course thereof, a red precipitate is formed. The resulting suspension is adjusted to a p~ value of 5 by adding 100 parts by volume of 30/0 strength aoueous sodiurn hyclroxide solu~ion, stirred .. . . ,- , ~ , ,,, .. . .. . ~ ..
. ~

': ' -~ ' ~ ~ - .

.. , ~

`~ 10474E~7 ,; . .
for 4 hGurs a-t ~ temperature which rises up to 20C, heated -to 75C over -he course of an hour and filtered whilst hot.
The residue is washed free from salt and dried in vacuo at 60C. This gives 17 6 parts, corresponding to 100%
. of theory, of a poppy-red powder of the formula ~`, . . OC2H5 ~1 ~ O ~ 0C~2CHN ~ -N=N-IIC~ ~C=~
`' OC2H5 ,..
~, .
Following af-ter-trea-tment in nitrobenzene (2 hours at 152C), fast, red colorations are obtained with this pigment, milled into polyvinyl chloride. Polyes-ter resins are also coloured with this pig.ment in pure, and very fast, red shades.
~` An~lysis:
Calculated: C 52.4 H 4.4 N 13.9%
Found: C 51.6 H 4.4 M 13.7%
The table which follows describes further colorants which are obtained by coupling the diazotised bases of -' col~nn I wi-th the coupling components of column II.
Column III indicates the colour shade of a PVC sheet coloured with 0.2% of these pigments.

.

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: 104748~
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1~47~87 Ex~.eT ,~
12. 9 P--lrtC; GL l~ar~ino-2 methoxy-5-chloro-4--acetylamino--benzene are dissolved in 200 par-ts by volume of glacial acet-~c acid at 22C, The bro~m scIuticn is stirred with 16.8 parts by volu~.e of concen-trated hydrochloric acid and t.he resulting suspension (hydrochloride) is diluted with 40 parts of water and coc,led to 5C and 16,2 parts by volume of 4 N
sodium nitri-te solution are added -dropwise over the course cf 20 minutes, at 5C~ and the resulting violet diazo solution is clarified by filtration. 7.7 parts of barbituric acid are then dissolved in 180 parts of water by means of 30 part,s by volume of 3~,'o strength sodivm hydroxide solu-tion. The diazo so].ution is added dropwise a-t 5C and over the course of 35 minutes to the colourless solu-tion~ In the course thereof~ an orange tinged red precipitate is formed. The resulting suspension is adjusted to a pH value of 5 by adding 185 par-ts by volume of 30~0 s-trength sodi~n hydroxide solution~
It is stirred for 4 hours at a temperature whicll rises to 23C, heated to 75C over the course of an hour and filtered ~hilst hot, The residue is washed free from salt and dried at 60C in vacuo. . This gives 20 parts, corresponding to 94% of theory, of a brownish-tinged red pigment of the formula ~3~ /CO-NH~
CH3CO~ N--N - CH ~C~O
CO_NH
C~

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1()47~8~
FollJ.~,~g a.~-ter--t-^eatment in dimethylformamide (1 hour at 134C), fas-t oran~;e colorations are obtained with ~his pigment, milled lnto polyvinyl chloride l-Amino-2 l~ethoxy-5-chloro-4~acetylaminobenzene can be ~` prepared in the following manner:
a) ~ ~o-4-ni.-troaniline . A suspension of 500 parts of 2,5-dichloro-4-nitroaceta-ni-~ lide ln 3,60G parts by volume of 2 N sodiurn hydroxide so].uti.on is heated to 90C, stirred for 3 hours at 90 to 95C and then ;. cooled to 22C. The product is filtered off, washed wi-ih ., water until neutral and dried at 60C i:n vacuo. The 2,5-dichloro-4-nitroaniline obtained in this way is a yello~l po~de..
: which melts a-t 150 to 151C. ~me yield is 412 par-ts ~ (93.5yO of theory).
-~ Analysis:
_ Calculated.: C 34.8 H 1~9 Cl 34.25 N 13.5%
Found: C 34.9 H 2.1 Cl 34 5 N 13.6%
b) 2-Chloro-5-m ~ a-niline 72 parts of powdered sodium hydroxide are added, over the : course of 5 minutes and at 23C, to a suspension of 125 parts ~- of 2,5-dichloro-4-nitroaniline in 1,200 parts by volwne of methanol. In the course thereof the temperature of the suspension rises to 50C. The mixture is heated to 70C.
A solu-tion is formed, ~lich is stirred for a further 13 hours at 70C and is then cooled to 20C. The 2-chloro-5~
methoxy-l-~-nitroaniline which has precipi~ated is filtered off, washed with 100 parts by vclume of methanol, washed with water ~ 21 -.
- .. , , ' ,., :, :,: :
- . - " ' :. ' , :~
: , , ~ -.' ' ~ ' ' ' , ` 1047~L87 uniil rl'71-l ra.!. a-nd dried at 60C in vacuo. This gives 98 5 parts (~J% of theory) of an ochre yellow po~rder. The rnelting point of the product is 1~7 to 159C.
Analysis:
Calculated: C 41.4 H 3.5 N 13.8%
Found: C 41.5 H 3.7 N 14.0%
, ~
c) 2-Methoxy-4-acetvlamino-5-chloro-nitrobenzene A suspension of 96 parts of 2-chloro-5-me-~hoxy-4 ni-tro-an:~line in 500 parts by volu~e of glacial acetic acid and ~0 parts by volurne of acetic anhydride is heated to 98C. In the course thereof a solu-tion is formed, which is stirred for further 6 hours a-t 98C and is allo~ied to cool. The product is precipitated. The new suspension i:s allowed to s-tand for 16 hours and is filtered. The material on the filter is washed with water until it is neu-tral and is dried at 60C in vacuo. The 2-methoxy-4-acetylamino-5-chloro-nitrobenzene obtained in this way melts at 145 to 146C.
The yield is 104 parts (90~ of theory).
Analysis:
Calculated: C 44.19 H 3.7 N 11.45%
Found: C 44.5 H 3.8 N 11.6%
d) l-Amino-2-methoxy-5-chloro-4-acetylamino-benzene 104 parts of 2-methoxy-4-acetylamino-5-chloro-nitrobenzene are suspended in 1,000 parts by volume of alcohol and are hydrogenated with hydrogen, using Raney nickel, for 17 hours at 30 to 40C. Absorption: 29.6 1, theory: 28.61 1.
The Raney nickel is ,iltered oIf from the resulting solution at "

- . , - . ,. , . . : ~ : ,. . . . .

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-: '' ', '. ,' , ' ,'- ~ , ', . , - ~Q47~7 40C anc! the fi~trate is completely evaporated in a rotary evapora-tor. The product is suspended in a li-ttle wa-ter, filtered off and dried at 60C in ~acuo, The amine is a light grey powder which mclfs at ]23 to 124C, The yield is 82,5 par-ts or 89% of theory.
Analysis:
,;
, Calculated: C 50.36 H 5.16 N 13,05 ; Found: C 50,7 H 5.2 N 13,4%
.
Example 60 11.5 parts of 1-amino--2,5-diethoxy-4-(4~-chlorophenoxy- -... ,~ .
acetylamillo~-benzene are dissolved in 130 parts by volume of '~ glacial acetic acid at 60C, The brown solution is stirred with 8.6 parts b-y volume of concen-trated hydrochloric , acid and the resulting suspension (hydrochloride) is dilu-ted ,;, with 25 parts of water and cooled to 4C, and 8,15 parts by volume of 4 N sodium nitrite solution are added dropwise over , the course of 25 minutes and at 4C, and the resulting bro~m , diazo solution is clarified by filtration.
~' 6.1 parts of l-phenylbarbituric acid are then dissolved ~' in 90 parts of water by means of 15 parts by volume of 30~
.~
,; strength sodium hydroxide solution. The diazo solution ~, is added dropwise, at 5C and over the course of 20 minutes, to the colourless solution. In the course thereof, a red precipitate is formed. The resulting suspension is adjusted to a pH value of 5 by adding 76 parts by volume of 309 strength sodium hydroxide solution. It is stirred for 4 hours at a temperature ~Jhich rises -to 22C, heated to 75C

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.; over the cou.~se of arl hour and ~ ~7tered whil~t hot, The ;' residue is ~,Ta~.hed free from salt and dried at 60C in vacuo.
,.............. This gives 17.1 parts, correspond:ing to 9~' of theory, of a,~ red, sof-t powder of the formula , ~OC2H5 / C0-NH
Cl ~ --OCH2COIIN ~ ~_ N-N-C~I / C50 ; ' OC2K5 .''. ' ~
,,' Even ~ithout after-trea-tmen-t in an organic solvent, this ,.~
.' pigment colours both polyvinyl chloride and polyester resins '~ in fast red shades.
The table which follows describes .further coloran-ts ~ hich are obtained by coupling the diazotised bases of colu~ I
'~ with the coupli.ng components of colu~mn II, Column III
. gives the yi.eld of '' pigments in ~O The products are used'for colouring withou.t recrys~,allisation. Colu~n IV
. indicates the colour shade of a PVC shee-t coloured with 0.2~
of these pi.gments.
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~047~4~7 65 parts of stabilised polyvinyl chloride, 35 parts ofdioctyl pllthalate and 0,2 part of the colorant obtained in accordance with Exarnp]e 1 are s-tirred together and the mixture ,, ;~ is then mi]led for 7 minutes at 140C on a twin-roll calender.
A red sheet with very good fastness to ligh-t and rnigration i5 obtained.
v~i Exarnple 78 1.00 g of -the pigment prepared in accordance with Exarnple ~; 1 is finely ground on an Engelsmann grinding rrlachine together with 4.00 g of lithographic varnish of the following composition:
,- 29.4% of linseed oil s-tand oil (300 poises), 67.2% of linseed oil stand oil (20 poises), 2,1% of cobalt octoa-te (S% of Co) and 1.~% of lead octoate (24% of P~) ,i and is then printed, at 1 g/m2, on art printing paper with the ' aid of a block using the letterpress process, Th:is gives ,` a deep, pure red shade of good transparency and good gloss~
The pigment is also suitable for other printing processes, such as gravure printing, offset printing and flexographic printing and gives very good results here too.
, .

Claims

WHAT IS CLAIMED IS:

1. A monoazo pigment of the formula wherein R1 and R2 denote H atoms, alkyl groups containing 1-4 C atoms, or aryl radicals, R3 denotes an alkyl radical which contains 1-4 C atoms and which can optionally contain halogen atoms, alkoxy groups containing 1-4 C atoms, or an aryl, aryloxy or arylmercapto group, as substituents, or denotes an aryl or heterocyclic radical, X denotes an O atom or an imino group, Y denotes an O or S atom or an imino group, and X1 and Y1 denote H or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or a nitro, cyano or trifluoromethyl group, but X1 and Y1 must not be H atoms if R3 represents an unsubstituted alkyl group, and wherein the acylamino group is in the m- or p-position to the azo group.

2. A monoazo pigment according to Claim 1, wherein R3 denotes a phenyl radical which optionally contains halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or nitro or alkoxycarbonyl groups containing 2-6 C atoms

3. A monoazo pigment: according to Claim 1, wherein R3 denotes a radical of the formula PhOCH2-wherein Ph denotes a phenyl radical which optionally contains halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or alkoxycarbonyl groups containing 2-6 C atoms.

4. A monoazo pigment. according to Claim 1 of the formula wherein R' denotes a H atom or a methyl group, R4 denotes an alkyl group containing 1-4 C atoms, and X2, X3 and Y2 denote H or halogen atoms or alkyl or alkoxy groups containing 1-4 C
atoms.

5. The compound according to Claim 1 of the formula

6. The compound according to Claim 1 of the formula

7. The compound according to Claim 1 of the formula

8. The compound according to Claim 1 of the formula

9. The compound according to Claim 1 of the formula

10. High molecular weight organic material having incorpo-rated a pigment as claimed in Claim 1.