US3560491A - Anthraquinone dyestuffs - Google Patents

Anthraquinone dyestuffs Download PDF

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US3560491A
US3560491A US651980A US3560491DA US3560491A US 3560491 A US3560491 A US 3560491A US 651980 A US651980 A US 651980A US 3560491D A US3560491D A US 3560491DA US 3560491 A US3560491 A US 3560491A
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acid
amide
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amino
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Rutger Neeff
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/205—Dyes with an unsaturated C on the N atom attached to the nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/56—Mercapto-anthraquinones
    • C09B1/58—Mercapto-anthraquinones with mercapto groups substituted by aliphatic, cycloaliphatic, araliphatic or aryl radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
    • C09B5/04—Pyrazolanthrones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
    • C09B5/14—Benz-azabenzanthrones (anthrapyridones)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
    • C09B5/16—Benz-diazabenzanthrones, e.g. anthrapyrimidones

Definitions

  • This invention concerns anthraquinone dyestuffs of the formula wherein A is an anthraquinone radical, n is an integer from 1 to 4 and R and R complete the residue of aliphatic or heterocyclic amines. These dyestuffs are prepared by reaction of the appropriate cyanoacetic acid amide with N-anthraquinonyl-N'-formamidium salts. These dyestuffs are useful for dyeing or printing of textiles.
  • This invention comprises new and valuable anthraquinone dyestuffs, and the production and use thereof.
  • A stands for an anthraquinone radical
  • R and R stand for hydrogen, alkyl, aryl, or alkylene when employed with N and with -2 additional heteroatoms from the group O, N, and S to form a cyclic structure
  • x is an anion and n is an integer from 1 to 4.
  • N-anthraquinonyl-N'-amidinium salts used in the process of the invention may contain in the anthraquinone radical, besides the grouping one or more substituents, for example, halogen atoms, such as fluorine, chlorine or bromine; hydroxy groups;
  • tetracyclic anthraquinone radicals are 1,9-isothiazole-anthrone, 1,9-anthrapyrimidine, 1,9-pyrazoleanthrone or N-methyl- 1,9-anthrapyridone.
  • the type of anion of the N-anthraquinonyl-N-amidinium salts used according to the invention is of no importance for the condensation with cyanoacetic acid amides.
  • the anion may be a halogen ion, such as a chlorine or bromine ion, a nitrate, sulphate, phosphate, boron tetrafiuoride, benzene-sulphonate, toluene-sulphonate, oxalate or succinate anion.
  • the nature of of the group of the amidinum salts is likewise of no importance for the condensation with cyanoacetic acid amides.
  • N-anthraquinonyl-N-formamidinium salts used according to the invention are the following compounds:
  • the cyanoacetic acid amides employed to prepare the novel anthraquinone dyestuffs of this invention have the formula:
  • R in addition to the above, stands for aryl or a heterocyclic radical.
  • amides are the unsubstituted cyanoacetic acid amide, the methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, tert.-butyl-, amyl-, isoamyl, or hexylamide; the dimethyl-, methyl-ethyl-, dipropyl-, diethyl-, diisopropyl-, dibutyl-amide; the 2-chloro-, 2-bromo-, 2- fluoro-, 2-hydroxy-, 2-ethoxy-, 2-propoxy or Z-cyanoethyl-amide; the bis-(2-chloro-ethyl)-, -(2 hydroxyethyl)-, -(2-methoxyethyl)-, (2-etl
  • the process can be carried out by condensing the N- anthraquinonyl-N'-formamidinium salts with cyanoacetic acid amides at 0-250 C. in the presence of an acid-binding agent; it is possible to use equivalent amounts of the reaction components or an excess of the cyanoacetic acid amides and acid-binding agents.
  • organic solvents for example alcohols, such as ethanol, propanol or ethylene glycol; ether alcohols, such as glycol monomethyl ether or diethylene glycol monomethyl ether; ethers such as dibutyl ether; esters, such as glycol monomethyl ether acetate; carboxylic acid amides, such as dimethy formamide, dialkyl sulphoxides or sulphones, such as dimethyl sulphoxide or tetramethylene sulphone; ketones such as butanone- (2); or hydrocarbons, such as benzene, toluene, chlorobenzene, o-dichlorobenzene or nitrobenzene.
  • alcohols such as ethanol, propanol or ethylene glycol
  • ether alcohols such as glycol monomethyl ether or diethylene glycol monomethyl ether
  • ethers such as dibutyl ether
  • esters such as glycol monomethyl ether acetate
  • Suitable acid-binding agents are, for example, oxides, hydroxides or salts of alkali metals or alkaline earth metals with weak inorganic or organic acids, such as calcium oxide, sodium or potassium hydroxide, sodium or potassium carbonate, sodium or ammonium hydrogen carbonate, sodium or potassium acetate, and also tertiary organic bases, such as triethylamine, N,N-dimethyl-aniline, pyridine, picoline or quinoline, or organic metal compounds such as sodium methylate or sodium ethylate.
  • weak inorganic or organic acids such as calcium oxide, sodium or potassium hydroxide, sodium or potassium carbonate, sodium or ammonium hydrogen carbonate, sodium or potassium acetate
  • tertiary organic bases such as triethylamine, N,N-dimethyl-aniline, pyridine, picoline or quinoline, or organic metal compounds such as sodium methylate or sodium ethylate.
  • Another method of carrying out the process consists in converting amino-anthraquinones in known manner in a suitable solvent into the N-anthraquinonyl-N-formamidinium salts mentioned above and condensing the latter, without isolation, with cyanoacetic acid amides in the presence of acid-binding agents.
  • the dyestuffs are thus obtained in a very simple manner and in high yields.
  • the process according to the invention preferably yields dyestuffs which correspond to the formula in which A stands for a anthraquinone radical; R and R stand for hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, and alkylene when employed together with N and with -2 additional heteroatoms from the group O, N and S to form a cyclic structure; R in addition to the above, stands for aryl or a heterocyclic radical, and n is an integer from 1 to 4.
  • R and R stand, for alkyl groups, those are preferred which contain 1 to 6 carbon atoms and may be substituted by one or more substituents of the following type: halogen atoms; hydroxy group which may be acylated by aliphatic carboxylic acids or carbonic acid semiesters; alkoxy, hydroxy-alkyleneoxy, alkoxyalkyleneoxy, alkoxycarbonyl or cyano groups.
  • Example of these optionally substituted alkyl groups are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl and hexyl groups; the 2-c-hloro-, 2-bromo-, 2-fluoro-, 2-hydroxy-, 2- methoxy-, Z-ethoxyand 2-cyano-ethyl radicals; the acetoxy-ethyl radical; the methoxy-carbonyloxy ethyl group; the ethoxy-carbonylmethyl and methoxy-carbonylethyl radicals; the 3-chloro-, 3-hydroxy-, 3-methoxyand 3- ethoxy-propyl groups; the 4-methoxy-butyl radical; the hydroxy-, methoxyor ethoxy-ethyleneoxy ethyl groups.
  • Examples of cycloalkyl groups are cyclopentyl, cyclohexyl or
  • R and R are alkylene groups which are linked with one another, optionally with 0-2 heteroatoms, i.e. O, N, or S, to form a heterocyclic structure with the amido ni trogen, R and R will preferably be alkylenes of 1-6 methylene groups.
  • the resulting heterocyclic structure may, for example, be pyrrolyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, oxazolinyl, thiazolinyl, oxadiazolyl, triazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperidinyl, triazinyl, oxazinyl, morpholinyl, thiazinyl, benzopyrrolyl, benzimidazolyl, benzthiazolyl, quinolinyl, quinoxalinyl.
  • R and R are alkenyl groups, these preferably comprise the vinyl, propenyl-(l) or propenyl-(2) groups or a phenyl-ethenyl radical. If R and R stand for aralkyl groups, these are preferably benzyl, ,B-phenylethyl or 'yphenylpropyl radicals which may be substituted by halogen atoms, lOWer alkyl, alkoxy, carboxyalkyl or cyano groups.
  • R stands for an aryl radical, this is preferably an unsubstituted or a monoor polysubstituted phenyl radical which may be substituted by substiuents of the following type: halogen atoms, such as chlorine, bromine, fluorine; alkyl groups with 1 to 6 carbon atoms which may in turn be substituted by halogen, alkoxy, cyano or carboxyalkyl radicals; alkoxy radicals with 1 to 6 carbon atoms which may again be substituted by halogen, alkoxy, cyano or carboxyalkyl groups; esterified carboxy groups; sulphonic acid ester or sulphofiuoride groups; trifluoromethyl, acetyl, urethane, sulphonic acid amide, alkylsulphone, alkylthio or arylthio radicals.
  • halogen atoms such as chlorine, bromine, fluorine
  • alkyl groups with 1 to 6 carbon atoms which may
  • substituents of this kind are the methyl, ethyl, propyl, butyl, isobutyl, t-butyl or amyl groups; a methoxyor ethoxy-methyl group; a ,8-
  • methoxyor ethoxy-ethyl radical a 'y-methoxyor ethoxy-propyl group; the methoxy, ethoxy, propoxy or butoxy radicals; a methoxy-, ethoxyor propoxy-methoxy or ethoxy group; the ethoxyor propoxy-carbonyl groups; the methoxyor ethoxy-carbonyl-methyl or -ethyl groups; the methoxyor ethoxy-carbonyl-methoxy or -ethoxy 10 radicals; a methoxyor et-hoxy-carbonylamino group; a N-phenylor N-phenyl-N-methyl-sulphonaniide radical; a methyl-sulphonyl or -sulphinyl group; a methyl-, ethylor phenyl-thio radical.
  • the dyestuffs which can be obtained by the present process are suitable, for example, as pigments for dyeing plastic masses and lacquers fast to migration.
  • the dyestuffs or mixtures thereof serve primarily for dyeing natural fibres and synthetic materials, preferably polyamides, polyurethanes, polyacrylonitriles, polypropylene and polyesters;
  • the polyesters in particular, embrace linear aromatic polyesters, such as polyethylene terephthalate or polyesters from terephthalic acid and 1,4- bis-hydroxymethyl-cyclohexane, as well as cellulose esters, such as cellulose triacetate or cellulose ZVz-acetate.
  • cellulose 2 /2-acetate for example, is dyed in the presence of Marseilles soap at 60-80 C.
  • cellulose triacetate and polyamide fibres can be dyed at C.
  • the usual dyeing accelerators can be added or dyeing can be carried out at -145 C. under pressure.
  • Dyeing or printing is preferably carried out according ot the thermosol process in which the printed or dyed fibre materials are heated, optionally after an intermediate drying, for a short time to temperatures in the range of about l80220 C. This heating is generally performed for periods of time of 30 seconds to 2 minutes.
  • the dyeings and prints obtained with the dyestufi's which can be produced according to the invention are characterised by a very good texture, a high dyestuffs yield and clear shades having excellent fastness to light, Washing, thermofixing and ironing.
  • a fabric of polyethylene terephthalate fibres is impregnated on a foulard with a liquor containing, per litre, 20 g. B(l-anthraquinonylamino) a cyanoacrylic acid morpholide and 10 g. of a thermosol auxiliary, particularly a polyester as is described, for example, in Belgian patent specification No. 615,102.
  • the fabric is then squeezed to a weight increase of 70% and dried in a suspended nozzle drier or drying carbinet at 80- 120 C.
  • the fabric is subsequently treated in a stenter or nozzle hot flue with hot air at -220 C.
  • the reductive after-treatment in order to remove any dyestuffs particles superficially adhering to the fibres can be carried out by introducing the fabric at 25 C. into a liquor which contains 3-5 cc./ litre of a sodium hydroxide solution at 38 B and 1-2 g./litre of concentrated hydrosulphite, heating to 70 C. within about 15 minutes and keeping at 70 C. for a further minutes.
  • the fabric is subsequently rinsed hot, acidified with 23 cc./litre of 85% formic acid at 50 C., rinsed and dried.
  • a golden yellow dyeing which is characterised by a high dyestufr yield and very good texture and by excellent fastness to light, thermofixing, washing, rubbing and sublimation.
  • a golden yellow dyeing is obtained when the polyethylene terephthalate fibres are replaced with polyester fibres from 1,4-bis-hydroxymethyl-cyclohexane and terephthalic acid or with cellulose triacetate or polyamide fibres.
  • EXAMPLE 2 water, 465 g. of crystal gum 1:2, and 20 g. of sulphonated- Calculated C23H19N303 castor oil.
  • An alginate thickener may be used instead of Fellndi N, crystal gum.
  • the printed and dried material is passed at When prlnt h y eceofdlhg to Example 190-220 C. over a high capacity stenter or through a the dyestlltf y e 0h fibres of p y y P condensation apparatus in order to fix the dyestuif.
  • the thalate, Cellulose tflileetate 0f p ly Clear golden duration of the treatment is about 30-60 seconds.
  • the yellow Shades h a haracterised by excellent fastfixed print so obtained is subsequently rinsed cold, soaped heSS t0 g Washlng, thefmefixlhg, h g and ewith 1-2 g./ litre of an anionactive detergent at 7080 C.
  • e y OF y the print is obtained when the polyethyleneterephthalate fibres y or dlethylamlde, 9 Y Y" are replaced with polyester fibres from 1,4-bis-hydroxy- Y- z-eyaneethylamlde, the 'hy Y h3 )1 methyl-cyclohexane and terephthalic acid or with cellulose Y YU- y y the t t t or l id fib acetoxyethyl)-amide, the his (2 methoxy-carbonyloxy- (d) 10 parts by weight polyethylene terephthalate fibres yD- the v y y mi are dyed at 125-130 c.
  • polyurethanc fibres can be used with equally good results.
  • Analogous [3-(4-hydroxy 1 anthraquinonylamino)-acyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the methylor isopropylamide, the methyl-ethylor diethyl-amide, the cyclohexylor 4-hydroxycyclohexyl-amide, the 2-chloro-, 2-hydroxy-, 2-methoxyor 2-cyano-ethylamide, the bias-(Z-hydroxyethyl)-, bis (2 ethoxy-ethyl)- or bis (2-cyanoethyl)- amide, the acetoxyethylamide or bis-(acetoxyethyl)- amide, the bis-(methoxycarbonyloxethyl)-amide, the ethyl-(2-cyanoethyl)-amide,
  • EXAMPLE 14 40.4 parts 1-amino-4-methoxy-anthraquinone in 250 parts nitrobenzene are converted into the amidinium chloride with 12.6 parts dimethyl formamide and 21 parts thionyl chloride according to Example 1(a). The melt is mixed with 27 parts cyanoacetic acid pyrrolidide and 40 parts of anhydrous sodium acetate and the mixture is stirred at 5070 C.
  • Analogous ,8-(4-methoxy-1- anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid pyrrolidide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the dimethylamide, n-amylamide, fl-propoxyethylamide or ,B-cyanoethylamide, the bis-(2-hydroxyethyl)- or -(2- cyanoethyl)-amide, the bis-(fl-acetoxyethyD-amide, the ([l-cyanoethyl)-(/3-acetoxyethyl) amide, the ethoxycarbonylmethylor S-methoxycarbonylmethyl-amide, the 4- methylcyclohexylamide, the morpholide, thiomorpholide or piperidide, the allylamide or li
  • Analogous 13-(4- alkoxy 1 anthraquinonylamino) a-cyanoacrylic acid amides are also obtained by using for the condensation with cyanoacetic acid amides the 4-ethoxy-, 4-propoxyor 4-benzyloxy-l-amino-anthraquinones, instead of the 4-methoxy-l-aminoanthraquinone mentioned in the present example.
  • EXAMPLE 16 28.8 parts N (4,8-dihydroxy-5-amino-l-anthraquinonyl)-N-dimethyl formamidinium chloride and 13.6 parts cyanoacetic acid diethylamide in parts nitrobenzene are mixed at 50-60 C. with 14 parts of anhydrous sodium acetate, and the mixture is stirred until the formation of the dyestuff is completed.
  • Analogous B- (4, S-dihydroxy-S-amino- 1 -anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using for the conversion of N-(4,8-dihydroxy-5-amino-1- anthraquinonyl)-N-dimethyl formamidinium chloride, instead of cyanoacetic diethylamide, cyanoacetic acid amide or the following amides of cyanoacetic acid: the n-hexylamide, di-n-butylamide, bis-(B-n-propoxy-ethyD- or -('y-hydroxypropyl)-amide, the bis(4-meth0xy-butyl)- or -(w-methoxy-B-ethoxyethyl)-amide, the 4-ethoxybenxylamide, y-phenylpropylamide, the morpholide or piperidide, the N-ethylanil
  • Brominated or chlorinated B-(4,8-dihydroxy-5-amino- 1 anthraquinonylamino) a cyanoacrylic acid amides which dye in reddish blue shades are also obtained, when brominated or chlorinated N-(4,8-dihydroxy-5-amino-1- anthraquinonyl)-N-dimethyl formamidinium chlorides which are obtainable from 1,5 diamino-4,8-dihydroxyanthraquinones containing 5 to 25% bromine or chlorine and prepared by bromination or chlorination of 1,5- diamino-4,8-dihydroxy-anthraquinones in solvents such as o-dichlorobenzene or sulphuric acid, are reacted according to Example 16 with the stated cyanoacetic acid amides.
  • acetic acid amide or the following amides of cyanoacetic EXAMPLE 24 acid the t-butylamide, the ,B-methoxycarbonyl ethyl- 32.6 parts N-(4,S-dihydroxy-8-amino-7-methylthio-1- amide, the ethyl-(2-cyanoethyl)-amide, the cyclohexyanthraquinonyl)N-dimethyl formamidinium chloride in amide, the pyrrolidide, piperidide, morpholide or thiomor- 180 parts nitrobenzene are condensed according to Expholide, the bis-(fi-allyD-amide, the anilide, 4-,3-ethoxyample 18 with 14.7 parts cyanoacetic acid piperidide in ethyl-anilide, the 3 5 ethoxyethoxy-anilide, 3-sulphonthe presence of 14 parts of anhydrous sodium acetate.
  • the dyestuff yields on fibres of polyethylene terephchlorides which can be obtained from 4,5-dihydroxy-1,8- thalate, cellulose triacetate or polyamide navy-blue shades diamino-anthraquinones containing 525% bromine or of very good fastness to light, washing and thermofixing.
  • Analogous 8-(4-phenylamino-l-anthraquinonylamino tat-cyanoacrylic acid esters are obtained by using for the conversion of N-(4-phenylamino-l-anthraquinonyl)-N' dimethyl formamidinium chloride, instead of cyanoacetic acid-bis-(B-methoxyethyD-amide, cyanoacetic acid amide or the following amides of cyanoacetic acid: the methylamide, diethylamide, 4-hydroxy-cyclohexylamide, 2-acetoxyethylamide; the bis-(2-cyanoethyl)- or -(2-hydroxyethyl)-amide; the bis-(2'-acetoxyethyl)- or -(2-methoxycarbonyloxy-ethyl)-amide; the ethyl (2 cyanoethyl)- amide; the bis-(w-methoxy-fl-e
  • EXAMPLE 31 27.4 parts 1-amino-4-(p-methoxyphenylamino)-anthraquinone and 6.3 parts dimethyl formamide in 150 parts nitrobenzene are mixed at 5060 C. with 10.5 parts thionyl chloride, and when the formation of the amidinium chloride is completed, the mixture is stirred in a vacuum for about 1 hour. parts cyanoacetic acid-bis-(Z-acetoxyethyl)-amide are then added, 20 parts anhydrous sodium acetate are introduced and the mixture is stirred at 5060 C. until the formation of the dyestuff in the shape of darkblue small needles is completed.
  • cellulose EXAMPLE 40 21.6 parts 4,5,8-trihydr0xy-l-amino-anthraquinone and 6.3 parts dimethyl formamide in parts o-dichlorobenzene are mixed at 5060C. with 10.5 parts thionyl chloride, and when the formation of the amidinium chloride is completed, the mixture is stirred in a vacuum for about 1 hour. 15 parts cyanoacetic acid morpholide and 20 parts of anhydrous sodium acetate are then added and the mixture is stirred at 5060 C. until the formation of the dyestuff is completed.
  • the dyestuff When dyed or printed according to Example 1(b) or 1(0), the dyestuff yields on fibres of polyethyleneterephthalate, cellulose triacetate or polyamide yellowish red shades of very good fastness to thermofixing, light and washing.
  • Analogous B-(4,5,8 trihydroxy 1 anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned above in the present Example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the diethylamide, Z-methoxyethylamide, bis-(B-cyanoethyD-amide, benzylamide, piperidide or thiomorpholide, the anilide, N-methylanilide, 4-methoxyanilide, N-methyl-4-methoxyanilide or the 4-fihydroxyethoxycarbonyl-phenylamide.
  • EXAMPLE 41 23.9 parts 5-nitro-4,8-dihydroxy-l-amino-anthraquinone in parts o-dichlorobenzene are converted with 6.3 parts dimethyl formamide and 10.5 parts thionyl chloride into the amidinium chloride according to Example 40. 15 parts cyanoacetic acid morpholide and 12 parts of anhydrous sodium acetate are added, and the mixture is stirred at 5070 C. until the formation of the dyestulf in the shape of red prisms is completed.
  • the dyestutf yields on fibres of polyethylene terephthalate, cellulose triacetate or polyamide bluish red shades of excellent fastness to light, washing and thermofixing.
  • Analogous ,8-(-nitro-4,8-dihydroxy-l-anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the dimethylamide, 2-cyanoethylamide, ethoxycarbonylmethylamide; the bis-,(2-methoxyethyl)- or -(2-acetoxyethyl)- amide; the fl-allylamide; the piperidide or pyrrolidide; the anilide, 3-ethoxyanilide, 3-fluoro-anilide or 4-ethoxycarbonylmethoxy-phenylamide.
  • EXAMPLE 42 22.2 parts 1-amino-5-acetylamino-anthraquinone are converted with 6.3 parts dimethyl formamide and 10.5 parts thionyl chloride in 150 parts nitrobenzene at 50 60 C. into the amidinium chloride, and parts cyanoacetic acid morpholide and parts of anhydrous sodium acetate are then added. The mixture is stirred at 50-60 C.
  • the dyestuff yields on fibers of polyethylene terephthalate, cellulose triacetate or polyamide clear goldenyellow shades of excellent fastness to light, washing, thermo-fixing and rubbing.
  • Analogous ,B-(S-acetylaminol-anthraquinonylamino)-o-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the n propylamide, 2-hydroxyethylamide, di-(n-propyl)- amide; the bis-(2-fluoroethyl)- or-,(2-hydroxyethyl)- amide; the bis (2 -methoxyethyl)- or -(2-methoxycarbonyloxyethyl)-amide; the 3-methoxy-propylamide; the piperidide, pyrrolidide or thiomorpholide; the benzylamide; the anilide, N-methyl-anilide, 4-methyl-analide, 3-butoxy-anilide or the 4-fl-methoxyethoxy
  • EXAMPLE 43 15 parts 1,S-diamino-anthraquinone are converted with 10.5 parts dimethyl formamide and 16.8 parts thionyl chloride in 150 parts nitrobenzene at 50-60 C. into the bis-amidinium chloride; 24.2 parts cyanoacetic acid anilide and parts of anhydrous sodium acetate are added and the mixture is stirred at 50-60 C. until the formation of the dyestuff is completed.
  • the dyestuif is suitable as a golden-yellow pigment which is fast to light and solvents.
  • EXAMPLE 44 20 parts 1,4-diamino-anthraquinone are converted with 14 parts dimethyl formamide and 23.6 parts thionyl chloride in 210 parts nitrobenzene at 5060 C. into the bis-amidinium chloride; 30 parts cyanoacetic acid-B- methoxyethylamide and parts of anhydrous sodium acetate are added, and the mixture is stirred at 50-60 C. until the formation of the dyestuff is completed.
  • the dyestulf yields on fibres of polyethylene terephthalate or cellulose triacetate brownish red shades of very good fastness to light, Washing and thermofixing.
  • the dyestuif is incorporated as a pigment with lacquers of synthetic resin, a brownish red coloration is obtained, which is fast to light and solvents.
  • EXAMPLE 45 22.7 parts 4,8-diamino-1,S-dihydroxy-anthraquinone are converted with 14 parts dimethyl formamide and 23.6 parts thionyl chloride in 210 parts nitrobenzene at 50- 60 C. into the bis-amidinium chloride Which crystallises in the form of pale violet prisms; 28.4 parts cyanoacetic acid-B-methoxyethylaanide and 40 parts sodium acetate are added and the mixture is stirred at -110 C. until the formation of the dycstufi' in the shape of blue-violet small needles is completed.
  • the dyestutf yields on fibres of polyethylene terephthalate or cellulose triacetate red-blue shades of excellent fastness to light, washing and sublimation. If, instead of 4,8-diamino-1,5-dihydroxy-anthraquinone, the isomeric 4,5-diamino-1,8-dihydroxy-anthraquinone is used, then there is obtained 4,5-bis-(2' 6-methoxy-ethylamino-carbony1-2'-cyanoethyleneamino) 1,8 dihydroxy anthraquinone which dyes polyester fibres in red-blue shades.
  • EXAMPLE 46 22.6 parts 1,4,5,8-tetraamino-anthraquinone are converted with 27 parts dimethyl formamide and 44 parts thionyl chloride in 320 .parts nitrobenzene at 70-80 C. into the tetrakis-amidinium chloride; 45 parts cyanoacetic acid dimethylamide and 75 parts of anhydrous sodium acetate are added, and the mixture is stirred at 120 C. until the formation of the dyestutf is completed.
  • the dyestuff can be used as a red-blue pigment which is fast to light and solvents for the coloration of synthetic materials.
  • the same dyestutf is obtained in an analogous manner by using, instead of N-(2-anthraquinonyl)-N'-dimethyl formamidinium chloride, the N-(2-anthraquinonyl)-N- gen, alkoxy of l-6 carbon atoms, cyano, and carboxyalkyl of l-6 carbon atoms in the alkyl group, esterified carboxy, sulfonic acid ester, sulfofluoride, trifluoromethyl, acetyl, urethane, sulfonic acid amide, alkylsulfone of 16 carbon atoms in the alkyl group, and phenylthio; and R and R may be an alkylene of l-6 methylene groups combined with the N in the above formula and -2 additional hetero atoms selected from the group consisting of O, N and S to form a heterocycle selected from the group consisting of pyrrolyl, imidazolyl, imi
  • a dyestufi of claim 1 /3-(l-anthraquinonylamino)-otcyanoacrylic acid morpholide.
  • a dyestulf of claim 1 ,8-(1-anthraquinonylatmino)-ucyanoacrylic acid piperidide.
  • a dyestutf of claim 1 B-(4-hydroxy-l-anthraquinonylamino)-acyanoacrylic acid morpholide.
  • a dyestulf of claim 1 [3-(4-methoxy-l-anthaquinonylamino)-u-cy anoacrylic acid morpholide.
  • a dyestuff of claim 1 fi-(4-phenylamino-l-anthraquinonylamino)-ot-cyanoacrylic acid morpholide.
  • a dyestuff of claim 1 fi-(4-p-methoxyphenylaminol-anthraquinonylamino)-ct-cyanoacrylic acid morpholide.
  • a dyestuff of claim 1 fl-(4p-methylpheny1amino-1- anthraquinonylaminoya-cyanoacrylic acid morpholide.
  • a dyestufi of claim 1 ⁇ 3-(l-anthraquinony1amino)- a-cyanoacrylic acid amide.
  • a process for the production of an anthraquinone dyestuff of claim 1 which comprises reacting at 0-250 C. a cyanoacetic acid amide of the formula:
  • R and R have the meaning given in claim 1, in the presence of an acid-binding agent selected from the group consisting of alkali metal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxide, salt of an alkali metal or alkaline earth metal with a weak inorganic or organic acid, tertiary organic base, and alcoholate of an alkali metal or an alkaline earth metal, with an N-anthraquinonyl-N'-formamidinium salt of the formula:

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3759958A (en) * 1968-07-26 1973-09-18 Ciba Geigy Ag Anthraquinoid dyestuffs
US4284411A (en) * 1978-08-10 1981-08-18 Bayer Aktiengesellschaft Anthraquinone derivatives for pigmenting organic macromolecular substances
US4389215A (en) * 1979-08-04 1983-06-21 Bayer Aktiengesellschaft Anthraquinone-azomethine compounds, processes for their preparation and processes for dyeing synthetic fibre materials and for pigmenting organic macromolecular substances
CN104053651A (zh) * 2012-03-07 2014-09-17 株式会社艾迪科 新型化合物及担载有该新型化合物的担载体
CN113156766A (zh) * 2021-03-29 2021-07-23 江南大学 一种感光树脂组合物及其应用

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3759958A (en) * 1968-07-26 1973-09-18 Ciba Geigy Ag Anthraquinoid dyestuffs
US3759959A (en) * 1968-07-26 1973-09-18 Ciba Geigy Ag Anthraquinoid dyestuffs
US3759957A (en) * 1968-07-26 1973-09-18 Ciba Geigy Ag Anthraquinoid dyestuffs
US4284411A (en) * 1978-08-10 1981-08-18 Bayer Aktiengesellschaft Anthraquinone derivatives for pigmenting organic macromolecular substances
US4389215A (en) * 1979-08-04 1983-06-21 Bayer Aktiengesellschaft Anthraquinone-azomethine compounds, processes for their preparation and processes for dyeing synthetic fibre materials and for pigmenting organic macromolecular substances
CN104053651A (zh) * 2012-03-07 2014-09-17 株式会社艾迪科 新型化合物及担载有该新型化合物的担载体
US9496095B2 (en) 2012-03-07 2016-11-15 Adeka Corporation Compound and carrier system having the compound
CN104053651B (zh) * 2012-03-07 2016-12-21 株式会社艾迪科 化合物及担载有该化合物的担载体
CN113156766A (zh) * 2021-03-29 2021-07-23 江南大学 一种感光树脂组合物及其应用
CN113156766B (zh) * 2021-03-29 2023-06-23 江南大学 一种感光树脂组合物及其应用

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BE701421A (de) 1968-01-15
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GB1119429A (en) 1968-07-10
CH474608A (de) 1969-08-15
NL6709830A (de) 1968-01-17

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