US3872137A - Anthraquinone compounds - Google Patents

Anthraquinone compounds Download PDF

Info

Publication number
US3872137A
US3872137A US199811A US19981171A US3872137A US 3872137 A US3872137 A US 3872137A US 199811 A US199811 A US 199811A US 19981171 A US19981171 A US 19981171A US 3872137 A US3872137 A US 3872137A
Authority
US
United States
Prior art keywords
parts
acid
water
formula
amino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US199811A
Inventor
Wolfgang Frey
Wolfgang Schoenauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fidelity Union Bank
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US199811A priority Critical patent/US3872137A/en
Application granted granted Critical
Publication of US3872137A publication Critical patent/US3872137A/en
Priority to US05/931,753 priority patent/US4267115A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/54—Amino-hydroxy-anthraquinones; Ethers and esters thereof etherified
    • C09B1/542—Anthraquinones with aliphatic, cycloaliphatic, araliphatic or aromatic ether groups
    • 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • C09B62/80—Anthracene dyes

Definitions

  • ABSTRACT [52 U.S. (:1 260/374, 260/371, 260/372, Water-soluble anthmquinone y which bear one Or 260/373 two 3,5,5-trimethy1cyclohexylamino groups in the l- 511 161. ct. ..C09b1/30,C09b 1/34, C09b 1/52 and/9r 4-p9siti9ns and one or two .-1 g p [58] Field of Search 260/371, 374 bound either directly Carbon atom of an aromatic ring or indirectly over an oxygen atom to a carbon 5 R f e Ci d atom of an aliphatic chain.
  • R for hydrogen, alkyl or alkoxy having 1 to 9 carbon atoms or halogen
  • R for -CH Ch -CH Ch -CH ---on2 on--, -cn-o1n, -o1n-o1r-orr2 nn 6113 on or --CH CH,(OCH CH R for hydrogen or lower alkyl
  • the SO H group in formula (V) may be in the 6' or 7-position; the nucleus B may bear a chlorine atom or an SOgH group in the 6- or 7-position or two hydroxyl or amino groups or one hydroxyl and one amino group in the 5- and 8-positions, respectively; the nucleus C may bear 1 to 3 lower alkyl or alkoxy groups; ifn stands for 2 or 3, every substituent R may have a separate significance.
  • the preferred compounds are those of formulae (III;
  • the new compounds are produced by reacting 1 mole of 3,5,S-trimethylcyclohexylamine with 1 mole of an anthraquinone compound of formula (I? NH: NHR13 Hal Hal I Q o NIIR4 l l ll0aS- ll 0 Hill where Hal stands for chlorine, bromine or fluorine,
  • a variation of the process consists in reacting 1 mole of an anthraquinone compound of formula (1? Hal NII I CI I;
  • a second variation of the process consists in reacting 1 mole of an anthraquinone compound of formula NIIz ( NII II with a compound of formula (XIII) Hal-Ih-OH and treating the product with sulphur trioxide or an agent yielding sulphur trioxide; or reacting 1 mole of the aforesaid compound with 1 mole of an alkylenecarboxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position or with a halogenoacetic acid or with a functional derivative of these acids, and then reacting with an amine of formula s) n r-G R1 (XIV) in the presence of an inorganic acid halogenide and treating the product with sulphur trioxide or an agent yielding sulphur trioxide.
  • a process for the'production of anthraquinone compounds of formula IIII'I-RI 5 consists in reacting 1 mole of 1,4-dihydroxyanthraqui' none-6- r -7-sulphonic acid with 1 mole of 3,5,5-trimethylcyclohexylamine and 1 mole of an ,amine of formula R NH or reacting 1 mole of a (XVI) consists in reacting 1 mole of an anthraquinone compound of formula (IX) with 1 mole of 3,5,5-trimethylcyclohexylamine and reacting the product with 1 mole of a compound of formula and treating with sulphur trioxide or an agent yielding sulphur trioxide.
  • Examples of suitable compounds of formula (IX) are l-amino-2,4-dibromoanthraquinone, bromo, l-amino-4,6- and 4,7-dibromo, 1-amino-4- bromo-o-chloroand -7-chloro-, 1-amino'-4-bromo-6- and 7-fluoro, 1-amino-4'bromo-6,7-dichloroanthranquinone-Z-sulphonic acid, l-amino-4- brom0anthraquinone'2,6- and -2,7-disulphonic acid.
  • aminoanthraquinone and -4-bromoanthraquinone-6 and '7-sulphonic acid and their derivatives which bear in this phenyl nucleus alkyl or alkoxy radicals having 1 to carbon atoms (methyl, ethyl, isopropyl, n-propyl, n-butyl, namyl, tert.
  • butyl isobutyl, methoxy, ethoxy, n-butoxy, dimethyl, trimethyl, methylethyl, methylmethoxy, dimethoxy, diethoxy, diethyl) halogen atoms, (chlorine, bromine, fluorine or lower acylamino radicals, (acetylamino, propionylamino, n-butyrylamino, methoxycarbonylamino, ethoxycarbonylamino), as well as the corresponding compounds which are sulphonated in the substituted or unsubstituted phenyl radical; l-(2-hydroxyethylamino)-, l-(3-hydroxypropyl-2-amino)-, 1-(2',3-dihydroxypropylamino), 1- (4-hydroxybutyl-3'-amino)-, l-(4-hydroxybutyl-2- amino)-4-chloroand -4-bromoanthr
  • halogen atoms chlorine, bromine, fluorine
  • lower acylamino radicals acetylamino, propionylamino, n-butyrylamino, methoxycar bonylamino, ethoxycarbonylamino
  • the compounds of formula (X) can be produced by reacting 1 mole of a compound of formula n Hal (X VII) with 1 mole of an amine R -NH- or by halogenation of a compound of formula
  • the compounds of formula (X), in which R represents a radical of formula (Rah can be obtained by reacting 1 mole of a compound of formula (XVII) with 1 mole ofan aminocarboxylic acid H N-alkylene-COOH and reacting with an amine of formula (XIV) in the presence of an inorganic acid halogenide or alternatively reacting with an amine of formula (XIV) with subsequent sulphonation.
  • Another mode of operation consists in reacting 1 mole ofa compound of formula with 1 mole of an alkylenecarboxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position, or with 1 mole of a halogenoacetic acid or a functional derivative of one of these acids, after which the product is reacted with an amine of formula (XIV) in the presenceof an inorganic acid halogenidc or reacted with an amine of formula (XIV) and sulphonated.
  • suitable compounds of formula (XI) are l-isopropyl-, l-sec. butyl-, l-sec. amyl-, l-sec.
  • hexyl-, lcyclohexylamino-and l-(3 ,5 ,5 -trimethylcyclohexylamino)-4-chloroor -4-bromanthraquinone-6- or -7- sulphonic acid can be prepared by reacting 1 mole of l,4-dihalogenoanthraquinone-6- or -7- sulphonic acid with 1 mole of an amine R NH or by halogenation, preferably bromination, of a l-R NH-anthraquinone-6- or -7-sulphonic acid.
  • the reaction of the 3,5,5-trimethylcyclohexylamine with the compounds of formulae (IX), (X) or (XI) can be effected at temperatures ranging from 40 to 220C.
  • the water soluble anthraquinone compounds are best reacted in an aqueous or aqueous-organic medium, e.g. at temperatures of 45 to 100C or preferably 45 to 85C for the compounds of formula (IX) in which Y stands for SO H while the water insoluble anthraquinone compounds are best reacted in organic medium,
  • aqueous-organic media e.g. at 80 to 200C or preferably 100 to 150C, more particularly 1 10 130C, for the compounds of formula (IX) where Y stands for a bromine atom.
  • Mixtures of water and one or more solvents which are at least partially water soluble and are indifferent to the reactants are employed as aqueous-organic media, e.g.
  • the 3,5,5- trimethylcyclohexylamine itself is employed as solvent or a solvent is used which is indifferent to the 3,5,5- trimethylcyclohexylamine and of high boiling point, e.g. 130 to 220C, for example monoor dichlorobenzene, dimethylformamide, dimethylacetamide, dimethylsulphoxide, glycol others and in particular nitrobenzene.
  • suitable acid binding agents are an excess of the amine, a tertiary amine of low volatility and of higher.
  • the final products are isolated in the normal way, e.g., by evaporation, preferably at reduced pressure, water vapour distillation, or dilution with a suitable agent, e.g. with water when water soluble solvents are used, or with a lower alcohol such as methanol, ethanol or isopropanol or a hydrocarbon such as petroleum ether or ligroin.
  • a suitable agent e.g. with water when water soluble solvents are used, or with a lower alcohol such as methanol, ethanol or isopropanol or a hydrocarbon such as petroleum ether or ligroin.
  • a suitable agent e.g. with water when water soluble solvents are used, or with a lower alcohol such as methanol, ethanol or isopropanol or a hydrocarbon such as petroleum ether or ligroin.
  • reaction product After condensation of the 3,5,5-trimethylcyclohexylamino with a compound of formula (IX) in which Y stands for a bromine atom the reaction product is reacted with a neutral, water soluble sulphite in aqueousorganic, e.g. aqueous-alcoholic or aqueous-phenolic (phenol itself, a cresol or cresol mixture) medium, in which the concentrated sulphite solution forms the aqueous phase, at 100 to 150C, preferably l20 130C, under pressure.
  • aqueousorganic e.g. aqueous-alcoholic or aqueous-phenolic (phenol itself, a cresol or cresol mixture) medium, in which the concentrated sulphite solution forms the aqueous phase, at 100 to 150C, preferably l20 130C, under pressure.
  • the rate of reaction is greatly accelerated so that the temperature can be reduced to, e.g. 60 l30C or preferably C, when the amine itself is used as solvent, and/or the reaction time is shortened or the formation or by-products can be greatly reduced.
  • acylating agents are lower alkanesulphonic acid chlorides (methane-and ethanesulphonic acid chlorides), arenesulphonic acid chlorides (benzene or 4-methylbenzenesulphonic acid chlorides), chlorocarbonic acid alkyl esters (chlorocarbonic acid methyl or ethyl esters) and in particular lower carboxylic acid chlorides and anhydrides (propionic acid chloride and anhydride or preferably acetic acid chloride or anhydride).
  • the acetyl compound can be formed by adding the anthraquinone compound to five to ten times its amount of acetic anhydride containing 2-5 zinc chloride on the weight of the anthraquinone compound, raising the mixture from 60 to about l35l40C or preferably 80-l00C and holding it at this temperature until the starting compound has disappeared, on which the mixture is cooled, run into water, the excess acetic anhydride carefully saponified and the precipitated product suctioned off, washed with water, dried and if necessary recrystallized in 100 acetic acid or in an alcohol.
  • the acyl group is split off, e.g. by treatment in 55-80 or preferably 6065 sulphuric acid at.
  • reaction ofthe anthraquinone compounds of formula (Xll) with an amine R -Nil can be accomplished under the aforestated reaction conditions.
  • prior acylation of the trimethylcyclohexylamino group accelerates the rate of reaction, given a substantial excess of the unsulphonated amine.
  • an alkali metal acetate, carbonate or hydroxide can be employed for an aromatic amine, depending on the strength of the amine or an alkali metal carbonate or. hydroxide for an amine of different type.
  • anthraquinone compound (XIl) bears an -SO H group in the 6- or 7-position it is advisable to react in aqueous or aqueous-organic medium in the presence of an acid-binding agent, e.g. an alkaline metal acetate, bicarbonate, carbonate or hydroxide when an aromatic amine is employed, or an alkali metal hydroxide in the case of an aromatic-aliphatic amine.
  • an acid-binding agent e.g. an alkaline metal acetate, bicarbonate, carbonate or hydroxide when an aromatic amine is employed, or an alkali metal hydroxide in the case of an aromatic-aliphatic amine.
  • Suitable amines R NH include aminobenzene, l-amino-2-, -3- or -4-methyl-, -ethylor -isopropylbenzene, l-amino-2,4-, -2,5- or -2,6-dimethylor -diethylbenzene, l-amino-2,4,6- or -2,4,,5-trimethylbenzene, l-amino-2-methyl-4,6-diethylbenzene, l-amino-4-nbutyl-, -4-isobutyl-, -4-tert-butyl-, -4-tert-amyl-, -4-namyl-, -4-isooctyl-, -4-tert-octylbenzene, l-amino-2-, 3- or -4-chloroor -bromobenzene, l-amine-2,4- dichlorobenzene
  • halogen compounds suitable for reac-' tion with aminoanthraquinone compounds of formula (XIII) may be mentioned bromobenzene, 1,2-, 1,3- and 1,4-dibromobenzene, l-bromo-2-, -3- and -4-methyland -ethylbenzene, l-bromo-2-, -3- and -4- chlorobenzene, 1-bromo-2-, -3- and -4-methoxyor -ethoxy-benzene, l-bromo-2,4,6-trimethylbenzene, 1- bromo-2-methoxy-5-methy1benzene, l-bromo-4- isopropyl-, 4-nbutyl-, -4-tert-butylbenzene, l-
  • aminoanthraquinone compounds of formula (XIII) with alkylencarboxylic acids having 3 or 4 carbon atoms and a double bond in a-position, or with functional derivatives of these acids, e.g. acrylic acid, acrylic acid ester, amide, or nitrile, methacrylic acid, methacrylic acid ester or crotonic acid, can be conveniently effected in sulphuric acid solution using sulphuric acid preferably of 50 to 96 7t strength.
  • the reaction takes place at temperatures between 40 and 100C or preferably at 60 80C.
  • the amount of alkylenecarboxylic acid employed must be at least 1 mole. It is often of advantage to employ an excess of the alkylenecarboxylic acid in order to achieve good yields.
  • the addition of a further acid, e.g. concentrated phosphoric acid, can accelerate the reaction.
  • the functional derivatives are often hydrolysed to the free acids. Should this not be so, hydrolysis is carried out subsequent to the reaction.
  • reaction products can beisolated as described in British Pat. No. 841,927.
  • an alkali metal acetate and I a copper compound if desired in the presence of an alkali metal acetate and I a copper compound, at temperatures of 60 to C or optimally at 8090C, or in an inert organic solvent such as phenol, a cresol or cresol mixture or naphtha in the presence of an alkali metal acetate and a copper compound at temperatures of 100 to C or preferably l00120C.
  • an inert organic solvent such as phenol, a cresol or cresol mixture or naphtha
  • the product is best to distill off the solvent, c.g. with water vapour or under reduced pressure; the product is then precipitated by the addition of salt or acid, filtered offwith suction and purified in the normal manner.
  • a halogenated or unhalogenated hydrocarbon such as chloroform, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, or in an ether such as dioxane,l,2-dimethoxyor 1,2-diethoxyethane, diisopropyl-, di-n-propylether, or in a tertiary amine (pyridine, a mixture of pyridine bases, quinoline, dimethylaminobenzene or diethylaminobenzene).
  • pyridine a mixture of pyridine bases, quinoline, dimethylaminobenzene or diethylaminobenzene
  • the amine of formula (XIV) itself can be employed as solvent.
  • the reaction is effected at temperatures between 0 and 50C in the presence of one of the aforenamed acid halides and is brought to a close at temperatures of 0 to 100C or preferably 40 to 80C.
  • the resulting carboxylic acid phenylamides can be isolated in the normal way as described in the examples of British Pat. No. 1,061,424.
  • an alcohol such as ethanol, n-propanol, nor isobutanol, nor iso-amyl alcohol
  • a glycol such as ethylene glycol, LIZ-propylene glycol, diethylene glycol, dipropylene glycol, or triprop
  • reaction product of formula CH CH at temperatures of e.g. 50 to 200C, preferably at 50 to 150C or optimally at 60 to 120C in the case of the thick compounds, and 100 to 200C or more particularly 110 to 180C in the case of the hydroxyl compounds, and in the presence of acid-binding agents such as alkali metal carbonates or hydroxides. It is advantageous to react in an inert solvent, e.g. an alcohol such as ethanol, butanol, cyclohexanol, an ether alcohol such as 2-methoxy-, 2-ethoxyor 2-butoxyethanol.
  • an inert solvent e.g. an alcohol such as ethanol, butanol, cyclohexanol, an ether alcohol such as 2-methoxy-, 2-ethoxyor 2-butoxyethanol.
  • An excess of the thiol compound may be employed as solvent.
  • Suitable solvents for the reaction with hydroxy compounds include pyridine, a mixture of pyridine bases, quinoline, nitrobenzene, 2,6-di-tert. butyl-4- methylphenol, or a excess of the hydroxy compound itself.
  • any water present or formed prior to or during the reaction is eliminated.
  • a copper catalyst e.g. copper-l-chloride, especially in the case of thiol compounds.
  • the reaction products are precipitated in the known way, e.g. by dilution with a lower alcohol or, if water-soluble or alkali-soluble hydroxy] or thiol compounds have been employed, with water or with alkali hydroxide solutions, and then fil tcred off with suction, washed and dried.
  • the treatment with sulphur trioxide in gaseous form diluted with air or as an adduct on pyridine or dioxane, or with chlorosulphonic acid can be carried out in an inert solvent such as chloroform, 1,2-dichlorethane or nitrobenzene at temperatures of 0 to 50C or preferably at l5-30C.
  • an inert solvent such as chloroform, 1,2-dichlorethane or nitrobenzene
  • Normally however concentrated sulphuric acid of about l 00 strength is employed, or oleum with an S0 content of up to about 15 t for reaction at the aforestated temperatures. Under these conditions the benzene nuclei are sulphonated and the aliphatic hydroxyl groups sulphated.
  • sulphation concentrated sulphuric acid can be employed at l0- 20C, whilst for sulphonation at the same temperature it is advisable to employ oleum with an S0 content of 540%.
  • aminosulphonic acid can also be employed with advantage, e.g. at -150C.
  • the sulphonated or sulphated compound can be isolated by running the solutions into water or into a salt solution, with the further addition of salt if necessary,
  • the final compounds are water-soluble dyes containingat least one -SO -,H group and are employed for the exhaustion dyeing, pad dyeing and printing of wool, silk, hair fibres, polyamide and polyurethane fibres and leather.
  • the dyeings and prints obtained on these materials are of brilliant shade and have good to very good wet fastness properties (washing, milling, perspiration, water, sea water), with good rubbing and dry cleaning fastness.
  • wet fastness properties washing, milling, perspiration, water, sea water
  • the light fastness is very good and better than on wool. 1n the Examples the parts and percentages are by weight and the temperatures in degrees Centigrade.
  • EXAMPLE 1 A mixture of 400 parts of water, 40.4 parts of sodium 1-amino-4-bromanthraquinone-2-sulphonate, 20 parts of l-amino-3,5,S-trimethylcyclohexane, 15 parts of 30 sodium hydroxide solution, 50 parts of ethanol and 1 part of copper powder is stirred for 5 hours at 65.
  • the blue dye formed is isolated and dried in the normal way. It is of formula (VI). From aqueous solution it gives dyeings of brilliant reddish blue shade on polyamide fibres which have very good wet fastness properties and outstanding good light fastness.
  • This new dye has far better wet fastness properties on synthetic polyamide fibres than the known commercial dye which bears an unsubstituted cyclohexylamino group in the 4-position.
  • a mixture of 38.1 parts of lamino-2,4- dibromanthraquinone, 160 parts of 3,5,5-trimethylcyclohexylamine, 25 parts of anhydrous potassium ace tate and 0.5 part of copper-lchloride is maintained at -120 until the starting material has disappeared.
  • the mixture is then diluted with methanol and allowed to cool to room temperature.
  • the precipitate is filtered off, washed successively with methanol and water and dried. It may be recrystallized if desired, after which 10 parts are mixed with 50 parts of phenol and 20 parts of 50 potassium sulphite solution in an autoclave and reacted at for 16 hours.
  • the phenol is distilled off with water vapour and the dye salted out, filtered off with suction and washed with salt solution. If necessary it is then dissolved in hot water, filtered while not to free it from water insoluble impurities and salted out, on which it is dried,
  • Dyeing Example H NH2 which are specified by the substituents R present in the 6 and 7 positions and by the shade of the dyeings on wool or synthetic polyamide fibres.
  • This water insoluble dye can be sulphonated in the benzene nucleus by the normal methods, e.g. by treatment with 5 times its amount of 10 "/1 oleum at 510. Sulphonation yields a blue water soluble dye which gives dyeings of attractive blue shade on wool and synthetic polyamide fibres having excellent light and wet fastncss properties.
  • the dyeings are faster to wet tests than comparable dyeings of the dye containing an unsubstituted cyclohexylamino group.
  • EXAMPLE 13 72.4 parts of 1-amino-4-(3,5,5-trimethylcyclohexylamino)-anthraquinone are dissolved in 160 parts of benzyl chloride at room temperature, and after the addition of 18 parts of sodium bicarbonate the temperature is increased to 100. The condensation reaction takes 10 hours. After this time the mixture is cooled to 60 and the dye base precipitated with 300 parts of isopropyl alcohol. On Sulphonation a dye identical with that of Example 12 is obtained.
  • EXAMPLE 14 36.2 parts of l-amino-4-(3,5,5-trimethylcyclohexylamino)-anthraquinone are dissolved at 70 in a mixture of 90 parts of55 sulphuric acid and 14 parts of acrylic acid, and the solution is stirred for a further 4 hours at this temperature. It is then run into 500 parts of water at 60. The crystalline precipitate is filtered off and washed with hot water until the waste water runs virtually colourless and is of almost neutral reaction, on which it is dried at 100. 7
  • the blue crystalline product is of formula CH3 CH3 LII 50.9 parts of this dye base are dissolved at 16 in 100 parts of 100 sulphuric acid and parts of 25 7r oleum. Sulphonation is complete in 5 hours. The solution is then run into a mixture of 150 parts of water. 400 parts of 28 7: aqueous sodium chloride solution and 250 parts of ice. The dye settles out and is filtered off, washed with 10 /1 sodium chloride solution and dried at 100. A brilliant blue dye is obtained which gives dyeings of high light and wet fastness on synthetic polyamide fibres.
  • the acrylic acid employed in this example can be re placed by the equivalent amount of 2-methylacrylic acid, in which case it is preferable to carry out the reac tion in 96 7c sulphuric acid at 100 in the presence of 3-5 of phosphoric acid.
  • EXAMPLE 15 A mixture of 23.1 parts of l-(4'-methyl-4- phenylpentyl-2-amino)-4-bromoanthraquinone, 0.1 part of copper powder and 42 parts of 3,5,5-trimethylcyclohexylamine is reacted at 8085 for 48 hours with stirring. On cooling to 60 parts of methanol are added dropwise. The precipitate formed is filtered off at 20-25, washed with methanol and dried.
  • the 15 parts of 3,5,5-trimethylcyclohexylamine can be replaced by 10 parts of cyclohexylamine or 6 parts of isopropylamine, in which case the reaction can be effected without isopropyl alcohol.
  • the dyes thus obtained give brilliant dyeings of good light and wet fastness on synthetic polyamide fibres.
  • An aromatic amine e.g. 9 parts of aminobenezene or 14 parts of l-amino-4-acetylaminobenzene, can be employed for the condensation reaction, in which case 9 parts of sodium carbonate are used as acid-binding agent and the isopropyl alcohol omitted.
  • the resulting dyes give brilliant blue shades of high light and wet fastness on synthetic polyamide fibres.
  • This same condensation reaction can be carried out with 18 parts of sodium l-aminobenzene-3-sulphonate to give a wool dye.
  • the l-(3',5,5-trimethylcyclohexylaminc)- anthraquinone-6-sulphonic acid employed in the foregoing as starting product is prepared as follows.
  • the filter residue is dissolved in 3600 parts of water at 70, the solution acidified with hydrochloric acid (red to Congo paper) and the product then filtered off, washed with acidified water until the waste water runs colourless, and dried.
  • the 1-(3,5,5- trimethylcyclohexylamino)-anthraquinone-6-sulphonic acid is obtained in the form of red crystals.
  • EXAMPLE 17 173.5 Parts (0.5 mole) of l-(3,5,5-trimethylcyclohexylamino)-anthraquinone are brominated in the 4-position by the method given in Example 16. 42.7 Parts of the resulting l-(3,5,5'- trimethyleyclohexylamino)-4-bromanthraquinone are entered into 250 parts of acetic anhydride. After the addition of 2 parts of anhydrous zinc chloride the mix ture is raised to 90-l00 and held at this temperature until the starting compound has disappeared. On cooling the mixture is poured slowly into 1000 parts of water with vigorous stirring.
  • the temperature is kept below 30 by external cooling and stirring is continued until the acetic anhydride is completely saponified to acetic acid. At this point the precipitated product is filtered offwith suction, washed with water and dried.
  • the l-(3,5,5-trimethylcyclohexylamino)- anthraquinone can be prepared as follows. A mixture of 242.5 parts (1 mole) of l-chloranthraquinone and 1000 parts of 3,5,5-trimethylcyclohexylamine is reacted at until no further l-chloranthraquinone is indicated. The excess amine is driven off with water vapour and the residue introduced into 1000 parts of water with the addition of sufficient concentrated hydrochloric acid to render the solution strongly acid. After stirring at 80 the product is filtered off with suction, washed with water until neutral and dried.
  • EXAMPLE 18 A mixture of 21.4 parts of l-(3',5,5'- trimethylcyclohexylamino)-4-bromanthraquinone, 20 parts of 1-phenyl-3;aminobutane, 5 parts of anhydrous potassium acetate, 0.1 part of copper-[-chloride, 0.1 part of water and 3 parts of 2-ethoxyethanol is reacted at for 48 hours with stirring.
  • EXAMPLE 20 A mixture of 235 parts of l-(N-acetyl-N-3,5,5'- trimethylcyclohexylamino)-4-bromanthraquinone, 0.01 part of copper-l-oxide, 5 parts of potassium acetate, 17.8 parts of 2-amino-lbutanol and 50 parts of nbutanol is reacted for 24 hours at C with stirring. After the addition of 75 parts of methanol at 60 the temperature is allowed to fall to 2025. The product settles out and is filtered off, washed with methanol and dried.
  • EXAMPLE 21 The procedure of Example 20 is followed, employing in place of 2-amino-1-butanol 37 parts of 2-benzylcyclohexylamine and sulphonating the resulting dye base with 5-10 7v oleum.
  • the product is a blue dye which gives dyeings of good light and wet fastness on syn thetic polyamide fibres.
  • EXAMPLE 22 45 parts of l-(2'-pheny1aminocarbonyl-ethylamino)- 4-bromanthraquinone are added to a mixture of 150 parts of 3,5,5-trimethylcyclohexylamine, 7 parts of anhydrous sodium carbonate and 0.5 part of copper-loxide and reacted at 130-135 until no further starting material is indicated.
  • the dye base formed is isolated in the normal way and sulphonated with 6 times its amount of 3 oleum at 18-20 to yield a dye which is identical with that of Example 14.
  • EXAMPLE 23 33.4 parts of 1,4-dihydroxy-5-hydroxyethylamino-8- chloranthraquinone and 20 parts, of anhydrous sodium carbonate are added to 100 parts of nitroben'zene and the temperature raised to 150. Over the following hour 150 parts of 3,5,S-trimethylcyclohexylamine are added, the temperature being kept constant at 150-155 until no further starting material is indicated. Ncthanol is added to the reaction mixture at 60, on which it is cooled to and the product filtered off with suction, washed with methanol and water and dried. On sulphation in accordance with the procedure of Example 20, the product dyes wool and synthetic polyamide fibres in blue-green shades of good light and wet l'astncss.
  • the same dye can be arrived at by reacting parts of l,4-dihydroxy-5,8-dichloranthraquinone with 25 parts of 3,5,5-trimethylcyclohexylamine in 240 parts of nitrobenzene at 150 until the starting products are no longer indicated.
  • the reaction mixture is then treated in the normal way and 12 parts of the isolated 1,4- dihydroxy-5-(3,5,5-trimethylcyclohexylamino)-8- ch'loroanthraquinone are reacted with 6 parts of anhydrous sodium acetate and 75 parts of 4-methyl-1- aminobenzene at 170l75.
  • the dye base is sulphonated.
  • dihydroxyanthraquinone-o-sulphonic acid 40 parts of 3,5,5-trimethylcyclohexylamine, parts of 95 7e ethanol, 0.8 part of Zinc dust and 1,1 parts of 100 acetic acid is reacted at under a nitrogen atmosphere until after about 4 to 6 hours no further starting material is indicated.
  • a jet of air is then directed through the mixture to reoxidize the proportion of dye which is still in the leuco form.
  • the dye is then isolated and purified by the normal method. It is of blue colour and gives dyeings of bright blue shade on wool and synthetic polyamide fibres which have very good light and wet fastness.
  • leuco compound of the 1,4- dihydroxyanthraquinoneo-sulphonic acid instead of forming the leuco compound of the 1,4- dihydroxyanthraquinoneo-sulphonic acid in the reaction mixture, one can start from the pure leuco-1,4- dihydroxyanthraquinone o-sulphonic acid or from a mixture of l,4-dihydroxyanthraquinone-o-sulphonic acid and its leuco compound.
  • npropanol or n-butanol e.g. npropanol or n-butanol
  • an alcohol-water mixture e.g 80 parts of secondary butanol and 20 parts of water
  • EXAMPLE 26 A solution of5.5 parts of potassium hydroxide in 200 parts of glycerol is prepared at 1 10 with vigorous stirring, and 23.2 parts of sodium 1-amino-4-(3,5,5- trimethylcyclohexylamino)-anthraquinone-2- sulphonate and 12 parts of sodium 3-nitrobenzene-lsulphonate are added to it. The solution is reacted for 8 hours at 125 with stirring, after which it is run into 800 parts of water and acidified with hydrochloric acid. The product settles out and is filtered off, washed with water until of neutral reaction and dried.
  • the 23.2 parts of sodium l-amino-4-(3,5',5'- trimethylcyclohexylamino)-anthraquinone-2- sulphonate can be replaced by 28.3 parts of the analogus 2,6-disulphonatc, in which case a violet dye for wool is obtained.
  • EXAMPLE 27 At 100-110 7.5 parts of potassium hydroxide are dissolved in 100 parts of phenol, after which 18 parts of sodium 1-amino-4-(3',5,5'- trimethylcyclohexylamine)-anthraquinone-2- sulphonate are added. The temperature is increased to and this temperature maintained until a sample is insoluble in water. The mixture is then allowed to cool to 100, l50parts of methanol are added and it is allowed to cool further to 20. The dye base is filtered off with suction, washed with methanol and then with water and dried. 10 parts of the dye base are entered into 45 parts of 5-10 /1 oleum and stirred at l525 until fully water soluble. The sulphonated dye is worked up in the normal way. On wool and synthetic polyamide fibres it gives dyeings of brilliant violet shade having good light and wet fastncss.
  • the same dye can be obtained by reacting 16 parts of l-amino-2-bromo-4- (3,5,5'-trimethylcyclohexylamino)-anthraquinone in a mixture of 16 parts of phenol, 50 parts of nitrobenzene and 7.5 parts of potasand synthetic polyamide fibres which are fast and wet treatments.
  • the same dye can be obtained by reacting 1 1.1 parts of l-amino-2-bromo-4-(3',5,5'-trimethylcyclohexto light sium hydroxide at 150 until the starting products have ylamino)-anthraquinone, 50 parts of 2-(2'-methoxydisappeared, and Continuing as stated in the foregoing.
  • H H H H 4 sulpho-4-iso ro yl hen l H H H H H 45 sulpho-4-eth ylpliengll y H H H H H 46 sulpho-4-tert.amylphenyl H H H H H 47 sulpho-4-ethoxycarbonylamino- H H H H H phenyl 48 4-methylphenyl H SOBH H H 49 4-methoxyphenyl H SO;,H H H 50 2-sulphatoethyl H H H H 5 l 2sulphatopropyl-l H H H H H H H H 52 l-sulphatopropyl-Z H H H H H H 53 l-sulphatobutyl-Z H H H H H H 54 4-sulphatobutyl-2 H H H H H 55 3-sulphato-2-hydroxypropyl-l H H H H H 56 do.
  • a compound of the formula R is secondary alkyl of 3 to 6 carbon atoms, cyclohexyl, 3,5,5-trimethylcyclohexyl, or
  • R is hydrogen, lower alkyl, lower alkoxy, halogen or lower acylamino
  • R is hydrogen or alkyl having I to 8 carbon atoms
  • the SO H group in formula (V) being in the 6- or 7- position; the nucleus B bearing optionally a chlorine atom or an SO H group in the 6- or 7-position or two hydroxyl or amino groups or one hydroxyl and one amino group in the and 8-positions, respectively; the nucleus C bearing optionally l to 3 lower alkyl or lower alkoxy groups; all substituents R being the same or different from each other if n stands for 2 or 3, and any acylamino group being acetylamino, propionylamino,
  • Rir R is hydrogen, lower alkyl or lower alkoxy, halogen or lower acylamino
  • Rm is crr3, -CH-CH1JJ, H-CHz-CH CH; 01 n *Cl[CHzC I2'" CHz-CH R is hydrogen or alkyl with l to 8 carbon atoms, R is -CH.
  • -CH -CH or 11 is l to 3, the nucleus C bearing optionally l to 3 lower alkyl or lower alkoxy groups and if n stands for 2 or 3, all substituents R being the same or different from each other.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Water-soluble anthraquinone dyes which bear one or two 3,5,5trimethylcyclohexylamino groups in the 1- and/or 4-positions and one or two -SO3H groups bound either directly to a carbon atom of an aromatic ring or indirectly over an oxygen atom to a carbon atom of an aliphatic chain.

Description

0 United States Patent 1191 [111 3,872,137 Frey et al. 1 Mar. 18, 1975 [54] ANTHRAQUINONE COMPOUNDS 3,420,856 1/1969 Bengueral 260 374 3,499,915 3/1970 S h de tal. 260/371 [751 Inventors: wlfgang FreytMunchePstem/BL; 3,646,071 2/1972 Ffey alffi 260/371 Wolfgang Schoenauer, R1ehen/BS, both of Switzerland FOREIGN PATENTS OR APPLICATIONS [73] Assignee; Fidelity Union Trust Company, 437,202 11/1967 Switzerland 260/374 Executive Trustee under Sandal 1,563,249 3/1969 France 260/371 Trust of May 4, 1955. 22 d: N 17 1971 Primary Examiner-Lorraine A. Weinberger 1 1 6 0V Assistant E.\-anziner-E. Jane Skelly PP 199,811 Attorney, Agent, or FirmGera1d D. Sharkin; Richard Related U.S. Application Data VHai Thomas 0 Doyle [62] Division of Ser. No. 808,322, March 18, 1969, Pat.
No. 3,646,071. [57] ABSTRACT [52 U.S. (:1 260/374, 260/371, 260/372, Water-soluble anthmquinone y which bear one Or 260/373 two 3,5,5-trimethy1cyclohexylamino groups in the l- 511 161. ct. ..C09b1/30,C09b 1/34, C09b 1/52 and/9r 4-p9siti9ns and one or two .-1 g p [58] Field of Search 260/371, 374 bound either directly Carbon atom of an aromatic ring or indirectly over an oxygen atom to a carbon 5 R f e Ci d atom of an aliphatic chain.
UNITED STATES PATENTS 7 Claims N0 Drawings 1,821,043 9/1931 Weinzmd 260/374 1 ANTHRAQUINONE COMPOUNDS CH3 CH3 where A represents one of the radicals NH-Ra (I) o l l kB/ or H0387];
H V II 0 I (I a XM...
ln formulae ([1) to (V) one R stands for a hydrogen,
fluorine, chlorine or bromine atom or a SO H- group and the other R, for a hydrogen atom, or R in each instance stands for a chlorine atom.
A for secondary alkyl having 3 to 6 carbon atoms,
cyclohcxyl, 3,5.5-trimcthylcyclohcxyl, or
R for hydrogen, alkyl or alkoxy having 1 to 9 carbon atoms or halogen, R, for -CH Ch -CH Ch -CH ---on2 on--, -cn-o1n, -o1n-o1r-orr2 nn 6113 on or --CH CH,(OCH CH R for hydrogen or lower alkyl,
R for hydrogen, lower alkyl or alkoxy, halogen or lower acylamino, R for CH CH CH CH CH R for hydrogen or alkyl having 1 to 8 carbon atoms, R for CH -CH -CH -or m for 2 or 2,
n for 1 to 3,
p for l to 9 and r for 1 to 6.
The SO H group in formula (V) may be in the 6' or 7-position; the nucleus B may bear a chlorine atom or an SOgH group in the 6- or 7-position or two hydroxyl or amino groups or one hydroxyl and one amino group in the 5- and 8-positions, respectively; the nucleus C may bear 1 to 3 lower alkyl or alkoxy groups; ifn stands for 2 or 3, every substituent R may have a separate significance.
The preferred compounds are those of formulae (III;
Jilin v n u and Nll--1h 0 Nil carbon atom, or for a radical of formula 2 where m stands for l or 2,
R for hydrogen, methyl or ethyl and R for hydrogen, methyl, ethyl, chlorine, methoxy, ethoxy or acetylamino.
The new compounds are produced by reacting 1 mole of 3,5,S-trimethylcyclohexylamine with 1 mole of an anthraquinone compound of formula (I? NH: NHR13 Hal Hal I Q o NIIR4 l l ll0aS- ll 0 Hill where Hal stands for chlorine, bromine or fluorine,
Y for bromine or SO,-,H,
sln It" for -R9OII, R l (B5) H R11 -alky1ene-COI| I- R1 8 n 3 RaOSO3H, R10 S0311 SO H I (Bat R1 S O II If Y represents bromine, the reaction product is treated with a water soluble neutral sulphite, or if R bears no -SO H group, with sulphur trioxide or an agent yielding sulphur trioxide.
A variation of the process consists in reacting 1 mole of an anthraquinone compound of formula (1? Hal NII I CI I;
em (XII) with l mole of an amine of formula R ','NH- and, if 'the radical R contains no SO;,H group, treating the product with sulphur trioxide or with an agent yielding sulphur trioxide.
A second variation of the process consists in reacting 1 mole of an anthraquinone compound of formula NIIz ( NII II with a compound of formula (XIII) Hal-Ih-OH and treating the product with sulphur trioxide or an agent yielding sulphur trioxide; or reacting 1 mole of the aforesaid compound with 1 mole of an alkylenecarboxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position or with a halogenoacetic acid or with a functional derivative of these acids, and then reacting with an amine of formula s) n r-G R1 (XIV) in the presence of an inorganic acid halogenide and treating the product with sulphur trioxide or an agent yielding sulphur trioxide.
A process for the'production of anthraquinone compounds of formula IIII'I-RI 5 consists in reacting 1 mole of 1,4-dihydroxyanthraqui' none-6- r -7-sulphonic acid with 1 mole of 3,5,5-trimethylcyclohexylamine and 1 mole of an ,amine of formula R NH or reacting 1 mole of a (XVI) consists in reacting 1 mole of an anthraquinone compound of formula (IX) with 1 mole of 3,5,5-trimethylcyclohexylamine and reacting the product with 1 mole of a compound of formula and treating with sulphur trioxide or an agent yielding sulphur trioxide.
Examples of suitable compounds of formula (IX) are l-amino-2,4-dibromoanthraquinone, bromo, l-amino-4,6- and 4,7-dibromo, 1-amino-4- bromo-o-chloroand -7-chloro-, 1-amino'-4-bromo-6- and 7-fluoro, 1-amino-4'bromo-6,7-dichloroanthranquinone-Z-sulphonic acid, l-amino-4- brom0anthraquinone'2,6- and -2,7-disulphonic acid.
The following are examples of suitable compounds of fomula (X): l-phenylamino-4-bromoand -4- chloroanthraquinone, -4,6(7)-di-chloro-, -4-bromo-6- and -7-chloroanthraquinene, -4-chloro-5,8-diamino-,
aminoanthraquinone and -4-bromoanthraquinone-6 and '7-sulphonic acid and their derivatives, which bear in this phenyl nucleus alkyl or alkoxy radicals having 1 to carbon atoms (methyl, ethyl, isopropyl, n-propyl, n-butyl, namyl, tert. butyl, isobutyl, methoxy, ethoxy, n-butoxy, dimethyl, trimethyl, methylethyl, methylmethoxy, dimethoxy, diethoxy, diethyl) halogen atoms, (chlorine, bromine, fluorine or lower acylamino radicals, (acetylamino, propionylamino, n-butyrylamino, methoxycarbonylamino, ethoxycarbonylamino), as well as the corresponding compounds which are sulphonated in the substituted or unsubstituted phenyl radical; l-(2-hydroxyethylamino)-, l-(3-hydroxypropyl-2-amino)-, 1-(2',3-dihydroxypropylamino), 1- (4-hydroxybutyl-3'-amino)-, l-(4-hydroxybutyl-2- amino)-4-chloroand -4-bromoanthraquinone, -4,6(7)-dichloro-, 4-bromo-6- and -7-chloroanthraquinone. -4-chloro-5,8-diamino-, -5,8- dihydroxy-, -5-amino-8-hydroxy-, -5-hydroxy 8- aminoanthraquinone, 4-chloroand 4-bromoanthraquinonofwor -7-sulphonic acid and the corresponding compounds which are sulphated on the hydroxyalkyl group; l-benzylamino, l-(4'-phenyl-4- mcthyl-pcntyl-2'-amino)-, l-(4-phenyl-butyl-2- l-amino-4- 6 amino)- and 1-(6'-phenyl-2-methyl-hexyl-4-amino) 4-chloroand -4bromo-anthraquinone, -4,6- or -4,7- dichloroor -4-bromo-6- 0r -7-chloro-anthraquinone, -4-chl0ro-5,8-diamino-, -5,8-dihydroxy-, -5-amino8- hydroxy-, 5-hydroxy'8-amino-anthraquinone, -4- chloroor -4-bromo-anthraquinonc-6- or J-sulphonic acid; l-(2'-benzyl-cyclohexylamino)-, 142 B- phenylethylcyclohexylamino)-, 1[2-(2"- or 4"- methylbenzyl)- and -ethylbenzyl and n-propyl-benzyl)cyclohexylamino]-, 1-[2-(2-4"- or -(2",6-dimethylbenzyl)- and -diethylbenzyl)- cyclohexylamine]-, l[2-(2,4",6-trimethylbenzyl)- cyclohexylamino]-, l-[2'-(2"-and-4- methoxybenzyl)- or -ethoxybenzyl)- or -n-propoxybenzyl)cyclohexyl-amino], l-[2'-(2",4-dimethoxybenzyl) or -dietnoxybenzyl)-cyclohexyl amino}, 1-(2'-benzyl-4-methyl-, 4-ethyl-, -4'-tert.butyl-, -4-
-tert.amyland -4-isooctylcyclonexylam ino )-4-chloroor -4-bromanthraquinone, -4,6- and -4,7-dichloroand -4-bromo-6- or -7-chloro-anthraquinone, -4-chloro- 5,8-diamino-, -5,8-dihydroxy-, -5-amino-8-hydroxy-, -5-hydroxy-8-amino-anthraquinone and -4-chloroor -4bromo-anthraquinone-6- and -7-sulphonic acid; as well as the corresponding compounds which are sulfonated in the aryl nucleus; 1-(2'- phenylaminocarbonylethylamino), l( 2'- phenylaminocarbonylpropylamino)-, l-( l phenylaminocarbonylpropylQ'-amino)-, lphenylam inocarbonylmethylamino-, l-( 2 '-N-methyl- N-phenylaminocarbonylethylamino)-, l-( 2 -N-ethyl- N-phenylaminocarbonylethylamino) l-N-methyl-N- phenylaminocarbonylmethylamino-, l-N-ethyl-N- phenylaminocarbonylmethylamino-4-chloroand -4- bromo-, -4,6- or -4,7-dichloro-, -4-bromo-6,7-chloroanthraquinone, -4chloro-5,8-diamino-, -5,8- clihydroxy-, -5-amino-8-hydr0xy-, -5-hydroxy-8-aminoanthraquinone and -4-chloroand -4-bromoanthraquinone-6- and -7-sulphonic acid and their derivatives which bear in the phenyl nucleus alkyl or alkoxy radicals having 1 to 5 carbon atoms (methyl, ethyl, isopropyl, n-propyl, n-butyl, n-amyl, tert. amyl, tert. butyl, isobutyl, methoxy, ethoxy, n-butoxy,, dimethyl, trimethyl, methylethyl, methylmethoxy, dimethoxy, diethoxy, diethyl), halogen atoms (chlorine, bromine, fluorine) or lower acylamino radicals (acetylamino, propionylamino, n-butyrylamino, methoxycar bonylamino, ethoxycarbonylamino), and the corresponding compounds which are sulphonated in the substituted or unsubstituted phenyl nucleus.
The compounds of formula (X) can be produced by reacting 1 mole of a compound of formula n Hal (X VII) with 1 mole of an amine R -NH- or by halogenation of a compound of formula The compounds of formula (X), in which R represents a radical of formula (Rah can be obtained by reacting 1 mole of a compound of formula (XVII) with 1 mole ofan aminocarboxylic acid H N-alkylene-COOH and reacting with an amine of formula (XIV) in the presence of an inorganic acid halogenide or alternatively reacting with an amine of formula (XIV) with subsequent sulphonation. Another mode of operation consists in reacting 1 mole ofa compound of formula with 1 mole of an alkylenecarboxylic acid which has 3 or 4 carbon atoms and a double bond in the a-position, or with 1 mole of a halogenoacetic acid or a functional derivative of one of these acids, after which the product is reacted with an amine of formula (XIV) in the presenceof an inorganic acid halogenidc or reacted with an amine of formula (XIV) and sulphonated. Examples of suitable compounds of formula (XI) are l-isopropyl-, l-sec. butyl-, l-sec. amyl-, l-sec. hexyl-, lcyclohexylamino-and l-(3 ,5 ,5 -trimethylcyclohexylamino)-4-chloroor -4-bromanthraquinone-6- or -7- sulphonic acid. They can be prepared by reacting 1 mole of l,4-dihalogenoanthraquinone-6- or -7- sulphonic acid with 1 mole of an amine R NH or by halogenation, preferably bromination, of a l-R NH-anthraquinone-6- or -7-sulphonic acid.
The reaction of the 3,5,5-trimethylcyclohexylamine with the compounds of formulae (IX), (X) or (XI) can be effected at temperatures ranging from 40 to 220C. The water soluble anthraquinone compounds are best reacted in an aqueous or aqueous-organic medium, e.g. at temperatures of 45 to 100C or preferably 45 to 85C for the compounds of formula (IX) in which Y stands for SO H while the water insoluble anthraquinone compounds are best reacted in organic medium,
e.g. at 80 to 200C or preferably 100 to 150C, more particularly 1 10 130C, for the compounds of formula (IX) where Y stands for a bromine atom. Mixtures of water and one or more solvents which are at least partially water soluble and are indifferent to the reactants are employed as aqueous-organic media, e.g. lower alcohols (methanol, ethanol, isopropanol, butanol, ethylene glycol), ethers (dioxan, 1,2-dimethoxyor l,2-diethoxyethane), ether alcohols (2-methoxyor 2- ethoxyethanol, 2-(2 -methoxyethoxy)- or 2-(2'-ethoxyethoxy)-ethanol), ketones (methylethyl ketone), amides (dimethylformamide, dimethylacetamide), sulphoxides and sulphones (dimethylsulphoxide, sulpholan-tetramethylenesulphone). These solvents are used in amounts of up to 25 or preferably 5 7r to l5 on the total weight of the mixture.
It is of advantage to react in the presence of acidbinding agents which impart to the reaction medium a pH of at least 11 (the pH value of a saturated aqueous solution of 3,5,5-trimethylcyclohexylamine) and of a catalyst; for this purpose preference is given to alkali metal hydroxides (sodium or potassium hydroxide) and to copper catalysts (copper powder, copper-l-oxide, copper-I-chloride, copper-II-oxide). To accelerate the reaction it is desirable to employ an excess of 3,5,5- trimethylcyclohexylamine, e.g. 1.3 to 3 moles or preferably' 1.5 to 2 moles, per mole of the halogenanthraquinone compound.
For the reaction in organic medium the 3,5,5- trimethylcyclohexylamine itself is employed as solvent or a solvent is used which is indifferent to the 3,5,5- trimethylcyclohexylamine and of high boiling point, e.g. 130 to 220C, for example monoor dichlorobenzene, dimethylformamide, dimethylacetamide, dimethylsulphoxide, glycol others and in particular nitrobenzene. Examples of suitable acid binding agents are an excess of the amine, a tertiary amine of low volatility and of higher. basicity than 3,5,5- trimethylcyclohexylamine, a basic metal salt such as sodium or potassium carbonate, or an alkali metal hydroxide. If necessary the aforenamed copper catalysts are employed.
The final products are isolated in the normal way, e.g., by evaporation, preferably at reduced pressure, water vapour distillation, or dilution with a suitable agent, e.g. with water when water soluble solvents are used, or with a lower alcohol such as methanol, ethanol or isopropanol or a hydrocarbon such as petroleum ether or ligroin. On isolation they are filtered with suction, washed if necessary and dried.
After condensation of the 3,5,5-trimethylcyclohexylamino with a compound of formula (IX) in which Y stands for a bromine atom the reaction product is reacted with a neutral, water soluble sulphite in aqueousorganic, e.g. aqueous-alcoholic or aqueous-phenolic (phenol itself, a cresol or cresol mixture) medium, in which the concentrated sulphite solution forms the aqueous phase, at 100 to 150C, preferably l20 130C, under pressure.
If the compounds of formula (X) in which R represents an aralkyl radical are acylated 7 prior to condensation with 3,5,5-trimethylcyclohexylamine, the rate of reaction is greatly accelerated so that the temperature can be reduced to, e.g. 60 l30C or preferably C, when the amine itself is used as solvent, and/or the reaction time is shortened or the formation or by-products can be greatly reduced. Ex-
amples of suitable acylating agents are lower alkanesulphonic acid chlorides (methane-and ethanesulphonic acid chlorides), arenesulphonic acid chlorides (benzene or 4-methylbenzenesulphonic acid chlorides), chlorocarbonic acid alkyl esters (chlorocarbonic acid methyl or ethyl esters) and in particular lower carboxylic acid chlorides and anhydrides (propionic acid chloride and anhydride or preferably acetic acid chloride or anhydride). The acetyl compound can be formed by adding the anthraquinone compound to five to ten times its amount of acetic anhydride containing 2-5 zinc chloride on the weight of the anthraquinone compound, raising the mixture from 60 to about l35l40C or preferably 80-l00C and holding it at this temperature until the starting compound has disappeared, on which the mixture is cooled, run into water, the excess acetic anhydride carefully saponified and the precipitated product suctioned off, washed with water, dried and if necessary recrystallized in 100 acetic acid or in an alcohol.
After condensation with the 3,5,5-trimethylcyclohexylamine the acyl group is split off, e.g. by treatment in 55-80 or preferably 6065 sulphuric acid at.
50-80C or preferably 6070C.
The reaction ofthe anthraquinone compounds of formula (Xll) with an amine R -Nil; can be accomplished under the aforestated reaction conditions. Here again prior acylation of the trimethylcyclohexylamino group accelerates the rate of reaction, given a substantial excess of the unsulphonated amine.
If the reaction is conducted in an organic medium an alkali metal acetate, carbonate or hydroxide can be employed for an aromatic amine, depending on the strength of the amine or an alkali metal carbonate or. hydroxide for an amine of different type.
If the anthraquinone compound (XIl) bears an -SO H group in the 6- or 7-position it is advisable to react in aqueous or aqueous-organic medium in the presence of an acid-binding agent, e.g. an alkaline metal acetate, bicarbonate, carbonate or hydroxide when an aromatic amine is employed, or an alkali metal hydroxide in the case of an aromatic-aliphatic amine.
Suitable amines R NH include aminobenzene, l-amino-2-, -3- or -4-methyl-, -ethylor -isopropylbenzene, l-amino-2,4-, -2,5- or -2,6-dimethylor -diethylbenzene, l-amino-2,4,6- or -2,4,,5-trimethylbenzene, l-amino-2-methyl-4,6-diethylbenzene, l-amino-4-nbutyl-, -4-isobutyl-, -4-tert-butyl-, -4-tert-amyl-, -4-namyl-, -4-isooctyl-, -4-tert-octylbenzene, l-amino-2-, 3- or -4-chloroor -bromobenzene, l-amine-2,4- dichlorobenzene, l-amino-2-, -3- or -4-methoxyor -ethoxybenzene, l-amino-2,4-dimethyoxyor -diethoxybenzene, l-amino-2,5-dimethoxyor -diethoxybenzene, l-amino-Z-methoxy-S-methylbenzene, l-amino- 4-acetylamino-, propionylamino-, -butylrylamino-, -mcthoxycarbonylaminoor -ethoxycarbonylaminobenzene, or the monosulphonic acids of these aminobenzenes corresponding to the formulae Z-hydroxy-ethylamine, 3-hydroxypropylaminel; l-hydroxybutylamine-3,
SOall llvN 2,3-dihydroxypropylamine-l or their sulphuric acid esters corresponding to the formulae benzylamine, Z-aminc-4-methyl-4-phenylpentane, 2-amino-4-phenylbutane, 4-amino-2-methyl-6 phenylhexane or their monosulphonic acids corresponding to the formulae SOall 2'benzylor 2-phenylethyl-cyclohexylamine, 2-(2'- methylor -ethylbenzyl)-cyclohexylamine, 2-(4- methyl-, -ethylor -n-propylbenzyl) -cyclohexylamine, 2-(2,4- or 2-(2,6-dimethylor -diethylbenzyl) -cyclohexylamine, 2-(2,4,6-trimethylbenzyl)- cyclohexylamine, 2-(2- or 2-(4'-methoxy-, -ethoxyor -n-propoxybenzyl)-cyclohexylamine, 2-(2',4'- dimethoxyor -diethoxybenzyl)-cyclohexylamine, 2- benzyl-4-methyl-cyclohexylamine or their sulphonic acids corresponding to the formulae SOall aminoacetic acid-, B-aminoor a-aminopropionic acida-amino-methylpropionic acidand ,B-amino-butyric acid-phenylamide, -N-m'ethylor -N-ethyl-N- phenylamide, -(2'-, -3- or -4-methyl-, -methoxy-, -ethoxyor -chlorophenylamide)-, -(2,4'-, -2,5" or -2,6'-dimethylphenylamide), -(2,4,6- or -(2',4,5- trimethylphenylamide), -(4-ethyl-, -(4'-isopropyl-, -(4-n-butyl-, -(4-isobutyl-, -(4'-tert-butyl', -(4'-namyl-, -(4'-isoamyl-, -(4-tert-amyl-, -(4-isooctyl or -(4-tert-octylphenylamide), -(4-bromophenylamide), -(2',5'-dichloro-, -(2',5'-dimethoxyor -(2',5'- diethoxy-phenylamide), -(2-methoxy-5'- methylphenylamide), -(4-acetylamino-, -(4- propionylamino-, (4'-butyrylamino-, -(4-methoxycarbonylam'ino- 0r -(4'-ethoxycarbonylaminophenylamide) or their monosulphonic acids corresponding to the formulae and e) 11 IIQN-aIkyIenQ-UO -III The reaction of the anthraquinone compounds of formula (XIII) with a compound by condensation of bromanic acid or its derivatives with 3,5,5-trimethylcyclohexylamine and desulphonation, or by reaction of 1 mole ofa dihalogen compound of formula (XVII) in either sequence with 1 mole of 3,- 5,5-trimethylcyclohexylamine and .1 mole of ammonia or of an aliphatic or aromatic sulphonic acid amide (CH,-,SO NH C H,-,SO NH in the latter case with subsequent cleavage of the sulphonic acid radicals.
Amongst the halogen compounds suitable for reac-' tion with aminoanthraquinone compounds of formula (XIII) may be mentioned bromobenzene, 1,2-, 1,3- and 1,4-dibromobenzene, l-bromo-2-, -3- and -4-methyland -ethylbenzene, l-bromo-2-, -3- and -4- chlorobenzene, 1-bromo-2-, -3- and -4-methoxyor -ethoxy-benzene, l-bromo-2,4,6-trimethylbenzene, 1- bromo-2-methoxy-5-methy1benzene, l-bromo-4- isopropyl-, 4-nbutyl-, -4-tert-butylbenzene, l-
bromo-4-acetylamino-, -4-propionylaminoand -4- butyrylaminobenzene, corresponding to the formula Rs) n IIal- 2-chloroor 2bromethanol 2-cnloroor 2- bromopropanol-l, l-chloro or l-bromo-2-propanol, 3-chloroor 3-bromopropanol, l-chloroor l-bromo- 2,3-propanediol, corresponding to the formula Hal-R- ,,OH; benzyl chloride or benzyl bromide corresponding to the formula It is of advantage to react the aminoanthraquinone compounds of formula (XIII) with benzyl alcohol in a substantial excess of the alcohol within the temperature range of 80 to 130C or preferably 100- 110C and in the presence of iodine as catalyst, the amount of iodine being about 3 to 15 70 or preferably 8-12 of the aminoanthraquinone compound.
The reaction of aminoanthraquinone compounds of formula (XIII) with alkylencarboxylic acids having 3 or 4 carbon atoms and a double bond in a-position, or with functional derivatives of these acids, e.g. acrylic acid, acrylic acid ester, amide, or nitrile, methacrylic acid, methacrylic acid ester or crotonic acid, can be conveniently effected in sulphuric acid solution using sulphuric acid preferably of 50 to 96 7t strength.
The reaction takes place at temperatures between 40 and 100C or preferably at 60 80C. The amount of alkylenecarboxylic acid employed must be at least 1 mole. It is often of advantage to employ an excess of the alkylenecarboxylic acid in order to achieve good yields. The addition ofa further acid, e.g. concentrated phosphoric acid, can accelerate the reaction. In the course of the reaction the functional derivatives are often hydrolysed to the free acids. Should this not be so, hydrolysis is carried out subsequent to the reaction.
The reaction products can beisolated as described in British Pat. No. 841,927.
The reaction of aminoanthraquinone compounds of formula (XIII) with a halogenoacetic acid can be accomplished in melted bromacetic or chloracetic acid,
if desired in the presence of an alkali metal acetate and I a copper compound, at temperatures of 60 to C or optimally at 8090C, or in an inert organic solvent such as phenol, a cresol or cresol mixture or naphtha in the presence of an alkali metal acetate and a copper compound at temperatures of 100 to C or preferably l00120C. To isolate the product it is best to distill off the solvent, c.g. with water vapour or under reduced pressure; the product is then precipitated by the addition of salt or acid, filtered offwith suction and purified in the normal manner.
For amidation the dry carboxylic acids thus obtained are reacted with an amine of formula (XIV) in the presence of a halide of an acid (thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus pentabromide, or preferably phosphorus trichloride or tribromide) and in an inert organic solvent, e.g. a halogenated or unhalogenated hydrocarbon such as chloroform, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, or in an ether such as dioxane,l,2-dimethoxyor 1,2-diethoxyethane, diisopropyl-, di-n-propylether, or in a tertiary amine (pyridine, a mixture of pyridine bases, quinoline, dimethylaminobenzene or diethylaminobenzene). In place of an inert organic solvent the amine of formula (XIV) itself can be employed as solvent. The reaction is effected at temperatures between 0 and 50C in the presence of one of the aforenamed acid halides and is brought to a close at temperatures of 0 to 100C or preferably 40 to 80C. The resulting carboxylic acid phenylamides can be isolated in the normal way as described in the examples of British Pat. No. 1,061,424.
can be effected in a substantial excess of 3,5,5
trimethylcyclohexylamine or, particularly when condensation with two different amines is involved, in'an inert organic solvent, e.g. an alcohol such as ethanol, n-propanol, nor isobutanol, nor iso-amyl alcohol, a glycol such as ethylene glycol, LIZ-propylene glycol, diethylene glycol, dipropylene glycol, or tripropylene glycol, an ether alcohol such as 2-methoxy-, 2-ethoxyor 2-n-butoxyethanol, 2-(2-methoxy-, ethoxyor -n-butoxyethoxy)-ethanol, or in an ether such as dioxane, and if necessary with the addition of up to 30 water. After the condensation reaction, which takes place preferably in the absence of air, e.g. in a nitrogen or illuminating gas atmosphere, the leuco compound is reoxidized, e.g. by the introduction of air.
The reaction product of formula CH CH at temperatures of e.g. 50 to 200C, preferably at 50 to 150C or optimally at 60 to 120C in the case of the thick compounds, and 100 to 200C or more particularly 110 to 180C in the case of the hydroxyl compounds, and in the presence of acid-binding agents such as alkali metal carbonates or hydroxides. It is advantageous to react in an inert solvent, e.g. an alcohol such as ethanol, butanol, cyclohexanol, an ether alcohol such as 2-methoxy-, 2-ethoxyor 2-butoxyethanol. 2-(2-methoxy-, 2-(2'-ethoxyor 2-(2-butoxy-ethoxy)- ethanol, an ether such as dioxane, or in a hydrocarbon such as cyclohexane, toluene or chlorobenzene, or if the compounds of formula (1X) bear a sulphonic acid group in water in the case of thiol compounds. An excess of the thiol compound may be employed as solvent. Suitable solvents for the reaction with hydroxy compounds include pyridine, a mixture of pyridine bases, quinoline, nitrobenzene, 2,6-di-tert. butyl-4- methylphenol, or a excess of the hydroxy compound itself. Any water present or formed prior to or during the reaction is eliminated. For the reaction of the bromine atom in the 2position it may be of advantage to add a copper catalyst, e.g. copper-l-chloride, especially in the case of thiol compounds. The reaction products are precipitated in the known way, e.g. by dilution with a lower alcohol or, if water-soluble or alkali-soluble hydroxy] or thiol compounds have been employed, with water or with alkali hydroxide solutions, and then fil tcred off with suction, washed and dried.
14 The treatment with sulphur trioxide (in gaseous form diluted with air or as an adduct on pyridine or dioxane, or with chlorosulphonic acid can be carried out in an inert solvent such as chloroform, 1,2-dichlorethane or nitrobenzene at temperatures of 0 to 50C or preferably at l5-30C. Normally however concentrated sulphuric acid of about l 00 strength is employed, or oleum with an S0 content of up to about 15 t for reaction at the aforestated temperatures. Under these conditions the benzene nuclei are sulphonated and the aliphatic hydroxyl groups sulphated. For sulphation concentrated sulphuric acid can be employed at l0- 20C, whilst for sulphonation at the same temperature it is advisable to employ oleum with an S0 content of 540%. For converting the hydroxyalkyl groups into sulphatoalkyl groups aminosulphonic acid can also be employed with advantage, e.g. at -150C. The sulphonated or sulphated compound can be isolated by running the solutions into water or into a salt solution, with the further addition of salt if necessary,
The final compounds are water-soluble dyes containingat least one -SO -,H group and are employed for the exhaustion dyeing, pad dyeing and printing of wool, silk, hair fibres, polyamide and polyurethane fibres and leather. The dyeings and prints obtained on these materials are of brilliant shade and have good to very good wet fastness properties (washing, milling, perspiration, water, sea water), with good rubbing and dry cleaning fastness. On polyamide fibres the light fastness is very good and better than on wool. 1n the Examples the parts and percentages are by weight and the temperatures in degrees Centigrade.
EXAMPLE 1 A mixture of 400 parts of water, 40.4 parts of sodium 1-amino-4-bromanthraquinone-2-sulphonate, 20 parts of l-amino-3,5,S-trimethylcyclohexane, 15 parts of 30 sodium hydroxide solution, 50 parts of ethanol and 1 part of copper powder is stirred for 5 hours at 65. The blue dye formed is isolated and dried in the normal way. It is of formula (VI). From aqueous solution it gives dyeings of brilliant reddish blue shade on polyamide fibres which have very good wet fastness properties and outstanding good light fastness.
This new dye has far better wet fastness properties on synthetic polyamide fibres than the known commercial dye which bears an unsubstituted cyclohexylamino group in the 4-position.
The same dye can be obtained by the following alter= native route. A mixture of 38.1 parts of lamino-2,4- dibromanthraquinone, 160 parts of 3,5,5-trimethylcyclohexylamine, 25 parts of anhydrous potassium ace tate and 0.5 part of copper-lchloride is maintained at -120 until the starting material has disappeared. The mixture is then diluted with methanol and allowed to cool to room temperature. The precipitate is filtered off, washed successively with methanol and water and dried. It may be recrystallized if desired, after which 10 parts are mixed with 50 parts of phenol and 20 parts of 50 potassium sulphite solution in an autoclave and reacted at for 16 hours. The phenol is distilled off with water vapour and the dye salted out, filtered off with suction and washed with salt solution. If necessary it is then dissolved in hot water, filtered while not to free it from water insoluble impurities and salted out, on which it is dried,
Dyeing Example H NH2 which are specified by the substituents R present in the 6 and 7 positions and by the shade of the dyeings on wool or synthetic polyamide fibres.
(XXI) 46.4 parts of the sodium salt of the dye of Example 1 are dissolved in 600 parts of water at 60, with the addition of 46.5 parts of 30 sodium hydroxide solution. Over 1 hour 19 parts of sodium dithionite are sprinkled into the solution. After a further hour at 60 the desulphonation reaction is complete. The water-insoluble compound is filtered off, washed with hot water until A mixture of 36.2 parts of the l-amino-4-(3,5,5- trimethylcyclohexamino)-anthraquinone thus prepared, parts of bromobenzene, 15 parts of anhydrous sodium carbonate and 2 parts of cuprous chlo ride is reacted at l35-l40 for 4 hours. On cooling to the mixture is diluted with parts of ethyl alcohol, causing precipitation of the blue dye formed. This is filtered off, washed with ethyl alcohol and water and dried. It has the structure:
(XXIII) and its melting point (subsequent to recrystallization from toluene and ethyl alcohol) is at 183-184. This water insoluble dye can be sulphonated in the benzene nucleus by the normal methods, e.g. by treatment with 5 times its amount of 10 "/1 oleum at 510. Sulphonation yields a blue water soluble dye which gives dyeings of attractive blue shade on wool and synthetic polyamide fibres having excellent light and wet fastncss properties.
By employing in place of bromobcnzene the equivalent amount of 4-ethoxy-l-bromobenzene a dye base with melting point 191-l92 is obtained. The sulphonated derivative of this gives brilliant greenish blue dyeings on synthetic polyamide fibres which have excellent light and very good wet fastness properties (washing, milling, perspiration, water, sea water), together with very good rubbing and dry cleaning fastness. This dye is of greater brilliance and is faster to washing and perspiration than the analogous dye bearing a cyclohexylamino group.
When other bromobenzenes are employed, the results are as follows;
Table 2 Example Bromobenzene Melting point 01' Shade of aqueous so- No dye base lution of the sulphonated derivative i I 9 l-bromo-4-me- 174 7 175 blue thylbenzene I0 1-bromo-2,4-di 178 179 reddish blue methylbenzenc l1 1-bromo-2,4,6-. 176 177 do.
trimethylbenzene of neutral reaction and dried. It is a dark violet powder EXAMPLE 12 which on recrystallization from toluene melts at 204-205. It has the formula ,dried at 100. It has the formula l i ll 1 2 O N H- II CH3 CH; (XXIV) 45.2 parts of this dye base are dissolved in 135 parts of 100 sulphuric acid and 80 parts of 25 oleum at 5-8. The Sulphonation reaction runs its course in 6 hours, following which the mixture is run into a mixture of 150 parts of water, 400 parts of 28 aqueous sodium chloride solution and 250 parts of ice. The dye settles out. It is filtered off, washed with 10 sodium chloride solution and dried at 100. The dye thus formed dyes synthetic polyamide fibres in brilliant blue shades which are fast to light and wet treatments.
The dyeings are faster to wet tests than comparable dyeings of the dye containing an unsubstituted cyclohexylamino group.
EXAMPLE 13 72.4 parts of 1-amino-4-(3,5,5-trimethylcyclohexylamino)-anthraquinone are dissolved in 160 parts of benzyl chloride at room temperature, and after the addition of 18 parts of sodium bicarbonate the temperature is increased to 100. The condensation reaction takes 10 hours. After this time the mixture is cooled to 60 and the dye base precipitated with 300 parts of isopropyl alcohol. On Sulphonation a dye identical with that of Example 12 is obtained.
EXAMPLE 14 36.2 parts of l-amino-4-(3,5,5-trimethylcyclohexylamino)-anthraquinone are dissolved at 70 in a mixture of 90 parts of55 sulphuric acid and 14 parts of acrylic acid, and the solution is stirred for a further 4 hours at this temperature. It is then run into 500 parts of water at 60. The crystalline precipitate is filtered off and washed with hot water until the waste water runs virtually colourless and is of almost neutral reaction, on which it is dried at 100. 7
43.4 parts of l-(2'-carboxyethylamino)-4- (3",5,5"-trimethylcyclohexylamino)- anthraquinone are dissolved in 150 parts of aniline at room temperature. 14 parts of phosphorus trichloride are dropped in at 40. Subsequently the temperature of the reaction mixture is increased to 60 and it is held at 60-65 for 4 hours. after which time 160 parts ol methyl alcohol are added which causes the dye base to settle out in crystalline form. It is filtered off. washed with methyl alcohol and then with water and dried at 100. The blue crystalline product is of formula CH3 CH3 LII 50.9 parts of this dye base are dissolved at 16 in 100 parts of 100 sulphuric acid and parts of 25 7r oleum. Sulphonation is complete in 5 hours. The solution is then run into a mixture of 150 parts of water. 400 parts of 28 7: aqueous sodium chloride solution and 250 parts of ice. The dye settles out and is filtered off, washed with 10 /1 sodium chloride solution and dried at 100. A brilliant blue dye is obtained which gives dyeings of high light and wet fastness on synthetic polyamide fibres.
The acrylic acid employed in this example can be re placed by the equivalent amount of 2-methylacrylic acid, in which case it is preferable to carry out the reac tion in 96 7c sulphuric acid at 100 in the presence of 3-5 of phosphoric acid.
EXAMPLE 15 A mixture of 23.1 parts of l-(4'-methyl-4- phenylpentyl-2-amino)-4-bromoanthraquinone, 0.1 part of copper powder and 42 parts of 3,5,5-trimethylcyclohexylamine is reacted at 8085 for 48 hours with stirring. On cooling to 60 parts of methanol are added dropwise. The precipitate formed is filtered off at 20-25, washed with methanol and dried. It is of for- 'mula I o Niin 1 (111;; 111:: (XXVI) EXAMPLE 16 42.7 parts of l-(3',3',5-trimethyleyelohcxylamino)- anthraquinonc-( -sulphonic acid are dissolved at 2025 in 220 parts of 100 7r sulphuric acid. with the addition of 16 parts of bromine. The temperature is slowly increased to 75 and this temperature held for about 16 hours. On cooling the reaction mixture is run onto 650 parts of ice. The precipitated 1-(3',3,5'- trimethylcyclohexylamino)-4-bromathraquinone-6- sulphonic acid is filtered off, washed with water until of neutral reaction and dried.
25.3 parts of this compound are suspended in 300 parts of water, on which 15 parts of 30 '/1 sodium hydroxide solution. 1 part of copper-l-chloridc, 20 parts of isopropyl alcohol and 15 parts of 3.5,5-trimethylcyclohexylamine are added. The mixture is maintained at 65-70 until the starting compound has disappeared.
It is then run into a mixture of 100 parts of water and parts of 30 7c hydrochloric acid to form a suspension. This is raised to 80 and the reaction product is filtered at this temperature and washed with acidified water. It is then suspended in 500 parts of water, the suspension raised to 80 and neutralised with sodium carbonate, then the final dye is salted out and isolated.
The 15 parts of 3,5,5-trimethylcyclohexylamine can be replaced by 10 parts of cyclohexylamine or 6 parts of isopropylamine, in which case the reaction can be effected without isopropyl alcohol. The dyes thus obtained give brilliant dyeings of good light and wet fastness on synthetic polyamide fibres.
An aromatic amine, e.g. 9 parts of aminobenezene or 14 parts of l-amino-4-acetylaminobenzene, can be employed for the condensation reaction, in which case 9 parts of sodium carbonate are used as acid-binding agent and the isopropyl alcohol omitted. The resulting dyes give brilliant blue shades of high light and wet fastness on synthetic polyamide fibres.
This same condensation reaction can be carried out with 18 parts of sodium l-aminobenzene-3-sulphonate to give a wool dye.
The l-(3',5,5-trimethylcyclohexylaminc)- anthraquinone-6-sulphonic acid employed in the foregoing as starting product is prepared as follows.
A mixture of 108 parts of sodium anthraquinonel ,6- disulphonate, 50 parts of 3,5,S-trimethylcyclohexylamine. 40 parts of sodium 3-nitrobenzenesulphonate and 1.5 parts of copper sulphate in 360 parts of water is reacted in an autoclave for 36 hours at 160. On cooling the sodium salt of the 1-(3',5,5- trimethylcyclohexylamino)-anthraquinone-6-sulphonic acid is salted out, filtered off with suction and washed with sodium chloride solution until the filtrate runs colourless. The filter residue is dissolved in 3600 parts of water at 70, the solution acidified with hydrochloric acid (red to Congo paper) and the product then filtered off, washed with acidified water until the waste water runs colourless, and dried. The 1-(3,5,5- trimethylcyclohexylamino)-anthraquinone-6-sulphonic acid is obtained in the form of red crystals.
EXAMPLE 17 173.5 Parts (0.5 mole) of l-(3,5,5-trimethylcyclohexylamino)-anthraquinone are brominated in the 4-position by the method given in Example 16. 42.7 Parts of the resulting l-(3,5,5'- trimethyleyclohexylamino)-4-bromanthraquinone are entered into 250 parts of acetic anhydride. After the addition of 2 parts of anhydrous zinc chloride the mix ture is raised to 90-l00 and held at this temperature until the starting compound has disappeared. On cooling the mixture is poured slowly into 1000 parts of water with vigorous stirring.
The temperature is kept below 30 by external cooling and stirring is continued until the acetic anhydride is completely saponified to acetic acid. At this point the precipitated product is filtered offwith suction, washed with water and dried.
23.5 Parts of the l-(N-acetyl-N-3,5',5- trimethylcyclohexylamino)-4-bromanthraquinone thus obtained are added to 19 parts of l-phenyl-3- aminobutane and the mixture is reacted for 20 hours at 1 10 with stirring. It is then run into a mixture of 200 parts of ice, 170 parts of water and parts of 30 hydrochloric acid. The precipitated resinous compound is separated and entered in portions into 175 parts of 65 sulphuric acid. The hydrolyzing mixture is maintained at 60-70 until the red acyl compound is no longer indicated, on which it is run onto ice. The blue dye base can be recrystallized in n-butanol if desired and is then sulphonated with 5-10 oleum at 2030. The dye thus obtained gives blue dyeings of good light and wet fastness on synthetic polyamide fibres.
The l-(3,5,5-trimethylcyclohexylamino)- anthraquinone can be prepared as follows. A mixture of 242.5 parts (1 mole) of l-chloranthraquinone and 1000 parts of 3,5,5-trimethylcyclohexylamine is reacted at until no further l-chloranthraquinone is indicated. The excess amine is driven off with water vapour and the residue introduced into 1000 parts of water with the addition of sufficient concentrated hydrochloric acid to render the solution strongly acid. After stirring at 80 the product is filtered off with suction, washed with water until neutral and dried.
EXAMPLE 18 A mixture of 21.4 parts of l-(3',5,5'- trimethylcyclohexylamino)-4-bromanthraquinone, 20 parts of 1-phenyl-3;aminobutane, 5 parts of anhydrous potassium acetate, 0.1 part of copper-[-chloride, 0.1 part of water and 3 parts of 2-ethoxyethanol is reacted at for 48 hours with stirring. After the addition of EXAMPLE 19 10 parts of 1-cyclophexylamine-4- bromanthraquinone-6-sulphonic acid are entered into a mixture of 200 parts of water, 20 parts of ethyl alcohol, 20 parts of 3,5,5-trimethylcyclohexylamine, 0.5 part of copper bronze and 7 parts of 30% sodium hydroxide solution. The reaction mixture is maintained at 60-70 until no further starting material is present. The resulting compound is worked up as described in Example 16 to give a dye which is isomeric to the dye referred to in the third paragraph of Example 16 and has very similar properties to it.
The use of l-phenylamino-4-bromanthraquinone-6- sulphonic in place of lcyclohexylamino-4- bromanthraquinone-o-sulphonic acid results in a similar dye.
EXAMPLE 20 A mixture of 235 parts of l-(N-acetyl-N-3,5,5'- trimethylcyclohexylamino)-4-bromanthraquinone, 0.01 part of copper-l-oxide, 5 parts of potassium acetate, 17.8 parts of 2-amino-lbutanol and 50 parts of nbutanol is reacted for 24 hours at C with stirring. After the addition of 75 parts of methanol at 60 the temperature is allowed to fall to 2025. The product settles out and is filtered off, washed with methanol and dried. 20 Parts ofthe product are dissolved in 100 parts of 80 7( sulphuric acid and the solution is stirred at 60 for 8 hours, after which it is discharged onto ice. The precipitated dye base is filtered off, washed neutral with water and dried at 60. 10 Parts of this dye base are sulphated in 40 parts of 100 sulphuric acid at room temperature. Subsequently the mixture is run onto ice and the precipitate filtered off, washed with 10 sodium chloride solution and dried. A powder is obtained which dyes wool and synthetic polyamide fibres in brilliant blue shades having good light and wet fastness properties.
EXAMPLE 21 The procedure of Example 20 is followed, employing in place of 2-amino-1-butanol 37 parts of 2-benzylcyclohexylamine and sulphonating the resulting dye base with 5-10 7v oleum. The product is a blue dye which gives dyeings of good light and wet fastness on syn thetic polyamide fibres.
EXAMPLE 22 45 parts of l-(2'-pheny1aminocarbonyl-ethylamino)- 4-bromanthraquinone are added to a mixture of 150 parts of 3,5,5-trimethylcyclohexylamine, 7 parts of anhydrous sodium carbonate and 0.5 part of copper-loxide and reacted at 130-135 until no further starting material is indicated. The dye base formed is isolated in the normal way and sulphonated with 6 times its amount of 3 oleum at 18-20 to yield a dye which is identical with that of Example 14.
EXAMPLE 23 33.4 parts of 1,4-dihydroxy-5-hydroxyethylamino-8- chloranthraquinone and 20 parts, of anhydrous sodium carbonate are added to 100 parts of nitroben'zene and the temperature raised to 150. Over the following hour 150 parts of 3,5,S-trimethylcyclohexylamine are added, the temperature being kept constant at 150-155 until no further starting material is indicated. Ncthanol is added to the reaction mixture at 60, on which it is cooled to and the product filtered off with suction, washed with methanol and water and dried. On sulphation in accordance with the procedure of Example 20, the product dyes wool and synthetic polyamide fibres in blue-green shades of good light and wet l'astncss.
EXAMPLE 24 When the 1,4-dihydroxy--hydroxyethylamino-8 chloranthraquinone employed in the preceding Example is replaced by l,4-dihydroxy-5-(4'- methylphenylamino)-8-chloranthraquinone and sulphonation is carried out in 5 oleum at 25, a dye giving blue-green dyeings is obtained.
The same dye can be arrived at by reacting parts of l,4-dihydroxy-5,8-dichloranthraquinone with 25 parts of 3,5,5-trimethylcyclohexylamine in 240 parts of nitrobenzene at 150 until the starting products are no longer indicated. The reaction mixture is then treated in the normal way and 12 parts of the isolated 1,4- dihydroxy-5-(3,5,5-trimethylcyclohexylamino)-8- ch'loroanthraquinone are reacted with 6 parts of anhydrous sodium acetate and 75 parts of 4-methyl-1- aminobenzene at 170l75. On completion of the reaction the dye base is sulphonated.
EXAMPLE 25 A mixture of 10 parts of 1,4-
dihydroxyanthraquinone-o-sulphonic acid, 40 parts of 3,5,5-trimethylcyclohexylamine, parts of 95 7e ethanol, 0.8 part of Zinc dust and 1,1 parts of 100 acetic acid is reacted at under a nitrogen atmosphere until after about 4 to 6 hours no further starting material is indicated. A jet of air is then directed through the mixture to reoxidize the proportion of dye which is still in the leuco form. The dye is then isolated and purified by the normal method. It is of blue colour and gives dyeings of bright blue shade on wool and synthetic polyamide fibres which have very good light and wet fastness. Instead of forming the leuco compound of the 1,4- dihydroxyanthraquinoneo-sulphonic acid in the reaction mixture, one can start from the pure leuco-1,4- dihydroxyanthraquinone o-sulphonic acid or from a mixture of l,4-dihydroxyanthraquinone-o-sulphonic acid and its leuco compound.
In place of ethanol another alcohol, e.g. npropanol or n-butanol, or an alcohol-water mixture, eg 80 parts of secondary butanol and 20 parts of water, can be employed with equally good success.
EXAMPLE 26 A solution of5.5 parts of potassium hydroxide in 200 parts of glycerol is prepared at 1 10 with vigorous stirring, and 23.2 parts of sodium 1-amino-4-(3,5,5- trimethylcyclohexylamino)-anthraquinone-2- sulphonate and 12 parts of sodium 3-nitrobenzene-lsulphonate are added to it. The solution is reacted for 8 hours at 125 with stirring, after which it is run into 800 parts of water and acidified with hydrochloric acid. The product settles out and is filtered off, washed with water until of neutral reaction and dried.
10 parts of the resulting dye base are stirred in 40 parts of 100 sulphuric acid at 1520 until a sample is completely soluble in water, on which the dye is isolated in the usual way. lts dyeings on wool andsynthetic polyamide fibres are of brilliant violet shade and have good light and wet fastness.
The 23.2 parts of sodium l-amino-4-(3,5',5'- trimethylcyclohexylamino)-anthraquinone-2- sulphonate can be replaced by 28.3 parts of the analogus 2,6-disulphonatc, in which case a violet dye for wool is obtained.
EXAMPLE 27 At 100-110 7.5 parts of potassium hydroxide are dissolved in 100 parts of phenol, after which 18 parts of sodium 1-amino-4-(3',5,5'- trimethylcyclohexylamine)-anthraquinone-2- sulphonate are added. The temperature is increased to and this temperature maintained until a sample is insoluble in water. The mixture is then allowed to cool to 100, l50parts of methanol are added and it is allowed to cool further to 20. The dye base is filtered off with suction, washed with methanol and then with water and dried. 10 parts of the dye base are entered into 45 parts of 5-10 /1 oleum and stirred at l525 until fully water soluble. The sulphonated dye is worked up in the normal way. On wool and synthetic polyamide fibres it gives dyeings of brilliant violet shade having good light and wet fastncss.
The same dye can be obtained by reacting 16 parts of l-amino-2-bromo-4- (3,5,5'-trimethylcyclohexylamino)-anthraquinone in a mixture of 16 parts of phenol, 50 parts of nitrobenzene and 7.5 parts of potasand synthetic polyamide fibres which are fast and wet treatments. I
The same dye can be obtained by reacting 1 1.1 parts of l-amino-2-bromo-4-(3',5,5'-trimethylcyclohexto light sium hydroxide at 150 until the starting products have ylamino)-anthraquinone, 50 parts of 2-(2'-methoxydisappeared, and Continuing as stated in the foregoing. ethoxy)-ethanol, 2 parts of anhydrous sodium carbonate and 5 parts of 4-methyl-l-mercaptobenzene at EXAMPLE 28 80-85 until no further starting material is present, on A mixture of 23.2 parts of sodium l-amino-4- which the product is precipitated with 40 parts of etha- (3,5,5'-trimethylcyclohexylamino)-anthraquinone-2- no], filtered off with suction, washed with ethanol and sulphonate, l3.5 parts of 30 sodium hydroxide soluwater and dried. it is sulphonated as described in the lion, I00 parts of water and 22 parts of foregoing. 4-mcthyll -mercapt0benzene is reacted for 24 hours at The following Table 3 details further dyes Of formula 95-l 00 with reflux. After the addition of 120 parts of 0 Nu R ethanol the reaction mixture is allowed to cool and the H product, having settled out, is filtered off, washed with ethanol and water and dried. 10 parts of the dye base thus formed are dissolved in 50 parts of 100 7c sul- Rn- (an phuric acid at l5-20. 15 parts of 25 oleum are I H I dropped in and the mixture is stirred until a sample is Rm 0 completely soluble in water. It is run onto ice and the "7\ precipitate is filtered off with suction and introduced r (XXVU) again into 200 parts of water. The suspension is neuwhich give dyeings of greenish blue to reddish blue tralized, the dye salted out, filtered off with suction, shade on wool and synthetic polyamide fibres and are washed, dried and ground. It is obtained as a dark powcharacterized in the Table by the meanings of the subder which gives dyeings of greenish blue shade on wool stituents R t0 R Table 3 Example R14 R1:- m n m 29 Sulpho-3-methylphenyl H H H H 30 sulpho-4chlorophenyl H H H H 3 l sulpho-4-methoxyphenyl H H H H 32 sulpho-2,S-dimethylphenyl H H H H 33 sulpho-2-methoxyphenyl H H H H 34 sulpho-2-methoxy-5-methylphenyl H H H H 35 sulphophenyl OH H H OH 36 do. OH H H NH 37 sulpho-4-methylphenyl NH2 H H OH 38 do. NHL, H H NH 39 sulpho-4-acetylaminophenyl H Cl H H 40 sulpho-4-propionylaminophenyl H H H H 41 sulpho-4-bromophenyl H SO;,H H H 42 sulpho-4-n-hutylphenyl H SO;,H H H 23 do. H H H H 4 sulpho-4-iso ro yl hen l H H H H 45 sulpho-4-eth ylpliengll y H H H H 46 sulpho-4-tert.amylphenyl H H H H 47 sulpho-4-ethoxycarbonylamino- H H H H phenyl 48 4-methylphenyl H SOBH H H 49 4-methoxyphenyl H SO;,H H H 50 2-sulphatoethyl H H H H 5 l 2sulphatopropyl-l H H H H 52 l-sulphatopropyl-Z H H H H 53 l-sulphatobutyl-Z H H H H 54 4-sulphatobutyl-2 H H H H 55 3-sulphato-2-hydroxypropyl-l H H H H 56 do. OH H H OH 57 2-sulphato-propyl-l NH: H H NH: 58 2-sulphato-ethyl NHL, H H OH 59 do. H C] H H 60 do. H H Cl H 6] 4-(sulphophenyl)-4-methyl- H H H H pentyl-2 62 do. OH H H OH 63 do. H SO3H H H 64 4-(sulphophenyl)-butyl-2- H H H H 65 o-(sulphophenyl)-2-methyl- H H H H hexyl-4 66 do. H SOHH H H 67 do. H H S0,,H H 68 do. OH H H OH 69 do. NH H H NH 70 4-(sulphophenyl)-butyl-2 NH2 H H OH 7l do. H Cl H H 72 sulphobenzyl H Cl H H 73 do. OH H H OH 74 do. NH2 H H NH2 75 2-(sulphophenylethyl)-cyclohexyl H H H H 76 2-(sulpho-4'-methylbenzyl)- H H H H cyclohexyl Example 8 S 03H 0 NH( 5 ll OH; H 0 NH- H C I; OH;
Examples 12 and 13- S 03H $1) NH-CH2- CH; 1| '2 O NH H C 3 CH3 Examples 14 and 22-.. s 0 H NHCHzCHzC 0NH CH; II I O NH H CH3 CHa Example 15 CH: (I311; S 0 131 H NH-CH--CHz-(l3 5 NH- H a CH:
Examples 16 and 25. CH;
O N H- H I I CH CH3 H02 S CH3 II I O N H H CH CH Examples 17 and 18.. S 0 H (1? N HC H-CHr-CHr- CH3 I 2 l) N1I- H CH3 CH1 Examplo lfl O NII- II II I IIOaS- CH3 l NH- H 2 CH: CH:
Having thus disclosed the invention what we claim is: l. A compound of the formula R is secondary alkyl of 3 to 6 carbon atoms, cyclohexyl, 3,5,5-trimethylcyclohexyl, or
R is hydrogen, lower alkyl, lower alkoxy, halogen or lower acylamino,
R, is hydrogen or alkyl having I to 8 carbon atoms,
the SO H group in formula (V) being in the 6- or 7- position; the nucleus B bearing optionally a chlorine atom or an SO H group in the 6- or 7-position or two hydroxyl or amino groups or one hydroxyl and one amino group in the and 8-positions, respectively; the nucleus C bearing optionally l to 3 lower alkyl or lower alkoxy groups; all substituents R being the same or different from each other if n stands for 2 or 3, and any acylamino group being acetylamino, propionylamino,
n-butyrylamino, methoxycarbonylamino or ethoxycarbonylamino.
2. A compound according to claim 1 wherein R when alkyl or alkoxy contains 1 to 5 carbon atoms, and 5 any alkyl or alkoxy group on the nucleus C contains 1 to 3 carbon atoms.
3. A compound according to claim 1 of the formula o gala; 10 l l on 3 ll 1 I l5 0 NH- 1-1 CH:\CH3 (VIII) wherein R is soar:
soar 1o E Rr2- C Q 503E H Rir R is hydrogen, lower alkyl or lower alkoxy, halogen or lower acylamino,
CH: om Rm is crr3, -CH-CH1JJ, H-CHz-CH CH; 01 n *Cl[CHzC I2'" CHz-CH R is hydrogen or alkyl with l to 8 carbon atoms, R is -CH. -CH -CH or 11 is l to 3, the nucleus C bearing optionally l to 3 lower alkyl or lower alkoxy groups and if n stands for 2 or 3, all substituents R being the same or different from each other.
4. A compound according to claim 3 wherein R when alkyl or alkoxy contains 1 to 5 carbon atoms, and 5 any alkyl or alkoxy group on the nucleus C contains 1 to 3 carbon atoms.
5. A compound according to claim 3 of the formula (Vlll), wherein R is a sulphonated benzene radical 35 36 hearing optionally l to 3 lower alkyl groups, a lower 7, A compound according to claim 3 ol thc form ulzi zilkoxy or a lower acylamino group. (VlIl) wherein R is u radical 6. The anthraquinone compound according to claim 5 of the formula Rm- 5 s03]! OaII ([Jlri 02H all being o112-, -p1rc1I2-c, CllCJIg -Cl[- or 0115 cm cm CHOII2CII:- 0113 l l CIIC6 0 NII II ll l} all;

Claims (7)

1. A COMPOUND OF THE FORMULA
2. A compound according to claim 1 wherein R8 when alkyl or alkoxy contains 1 to 5 carbon atoms, and any alkyl or alkoxy group on the nucleus C contains 1 to 3 carbon atoms.
3. A compound according to claim 1 of the formula
4. A compound according to claim 3 wherein R8 when alkyl or alkoxy contains 1 to 5 carbon atoms, and any alkyl or alkoxy group on the nucleus C contains 1 to 3 carbon atoms.
5. A comPound according to claim 3 of the formula (VIII), wherein R3 is a sulphonated benzene radical bearing optionally 1 to 3 lower alkyl groups, a lower alkoxy or a lower acylamino group.
6. The anthraquinone compound according to claim 5 of the formula
7. A compound according to claim 3 of the formula (VIII), wherein R3 is a radical
US199811A 1968-04-08 1971-11-17 Anthraquinone compounds Expired - Lifetime US3872137A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US199811A US3872137A (en) 1969-03-18 1971-11-17 Anthraquinone compounds
US05/931,753 US4267115A (en) 1968-04-08 1978-08-07 Anthraquinone compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80832269A 1969-03-18 1969-03-18
US199811A US3872137A (en) 1969-03-18 1971-11-17 Anthraquinone compounds

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US80832269A Division 1968-04-08 1969-03-18

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US52929374A Division 1968-04-08 1974-12-04

Publications (1)

Publication Number Publication Date
US3872137A true US3872137A (en) 1975-03-18

Family

ID=26895183

Family Applications (1)

Application Number Title Priority Date Filing Date
US199811A Expired - Lifetime US3872137A (en) 1968-04-08 1971-11-17 Anthraquinone compounds

Country Status (1)

Country Link
US (1) US3872137A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2404030A1 (en) * 1977-09-21 1979-04-20 Sandoz Sa NEW ANTHRAQUINONIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS COLORANTS
US4267115A (en) * 1968-04-08 1981-05-12 Sandoz Ltd. Anthraquinone compounds
US4405524A (en) * 1978-04-07 1983-09-20 Sandoz Ltd. Anthraquinone dyes and method of use
US20060094776A1 (en) * 2003-04-30 2006-05-04 George Theodoridis Insecticidal (dihalopropenyl) phenylalkyl substituted dihydrobenzofuran and dihydrobenzopyran derivatives

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1821043A (en) * 1925-11-24 1931-09-01 Gen Aniline Works Inc Hydroaryl amino anthraquinone compounds and process of making the same
US3420856A (en) * 1963-09-24 1969-01-07 Sandoz Ag Sulfonated 1-cyclohexylamino-4-anilino-anthraquinones
US3499915A (en) * 1964-12-22 1970-03-10 Geigy Ag J R Sulfonated 1 - alkylamino - 4 - acylaminomethylaralkylamino-anthraquinones
US3646071A (en) * 1968-04-08 1972-02-29 Sandoz Ltd Anthraquinone compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1821043A (en) * 1925-11-24 1931-09-01 Gen Aniline Works Inc Hydroaryl amino anthraquinone compounds and process of making the same
US3420856A (en) * 1963-09-24 1969-01-07 Sandoz Ag Sulfonated 1-cyclohexylamino-4-anilino-anthraquinones
US3499915A (en) * 1964-12-22 1970-03-10 Geigy Ag J R Sulfonated 1 - alkylamino - 4 - acylaminomethylaralkylamino-anthraquinones
US3646071A (en) * 1968-04-08 1972-02-29 Sandoz Ltd Anthraquinone compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267115A (en) * 1968-04-08 1981-05-12 Sandoz Ltd. Anthraquinone compounds
FR2404030A1 (en) * 1977-09-21 1979-04-20 Sandoz Sa NEW ANTHRAQUINONIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS COLORANTS
US4405524A (en) * 1978-04-07 1983-09-20 Sandoz Ltd. Anthraquinone dyes and method of use
US20060094776A1 (en) * 2003-04-30 2006-05-04 George Theodoridis Insecticidal (dihalopropenyl) phenylalkyl substituted dihydrobenzofuran and dihydrobenzopyran derivatives

Similar Documents

Publication Publication Date Title
US3646071A (en) Anthraquinone compounds
US3320287A (en) 1-amino-4-[aroylaminomethyl-alkylsubstituted-amino]-anthraquinone-2-sulfonic acids
US3872137A (en) Anthraquinone compounds
US2242760A (en) Organic dyestuffs and process of producing same
US2859221A (en) Acid anthraquinone dyestuffs
US3491126A (en) Sulfonated 1-alkylamino-4-tolylaminoanthraquinones
US3882150A (en) Anthraquinone compounds
US2236672A (en) Brominated arylaminoanthraquinone compounds
US3823168A (en) Anthraquinone dyestuffs containing sulphonic acid groups
US2204749A (en) Anthraquinone dyestuffs
US2845443A (en) Acid anthraquinone dyestuffs
US2357176A (en) Anthraquinone compounds
US3778453A (en) 1-amino-4-(4',5'-dilower alkyl-3-sulphamoylphenylamino)anthraquinone-2-sulfonic acids
US3065191A (en) Disulpho-1-amino-4-(oxy-, thio-, or aminosubstituted-monohalogenotriazinylamino-aryl-or arylazo-amino) anthraquinone dyestuffs
US3657284A (en) Dyestuffs
US2744914A (en) Dyestuffs of the phthalocyanine series and their production
US3211757A (en) Symmetrical 4-halogeno-4', 4"-diarylamino-triphenylmethane dyestuffs
USRE27413E (en) Chz-chj
US2059476A (en) Dyestuffs of the anthraquinone series
US1014204A (en) Dye.
US3549664A (en) Anthraquinone dyestuffs
US3842101A (en) Blue anthraquinoid acid dyes
US3704252A (en) Anthraquinone dyes
US3980677A (en) Anthraquinone dyestuffs containing sulphonic acid groups
US3801606A (en) Anthraquinone dyes