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Patent US4088651 - Acylamino quinophthalone compounds - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsAcylamino quinophthalone compounds which are free from sulfonic acid groups and correspond to the formula ##STR1## in which R.sub.1 and R.sub.2 are hydrogen, halogen, acylamino or lower alkoxy with the proviso that one of the residues R.sub.1 and R.sub.2 denotes acylamino while the other residue stands...http://www.google.com/patents/US4088651?utm_source=gb-gplus-sharePatent US4088651 - Acylamino quinophthalone compoundsAdvanced Patent SearchPublication numberUS4088651 APublication typeGrantApplication numberUS 05/568,858Publication dateMay 9, 1978Filing dateApr 17, 1975Priority dateDec 10, 1968Publication number05568858, 568858, US 4088651 A, US 4088651A, US-A-4088651, US4088651 A, US4088651AInventorsDietmar Kalz, Gerhard WolfrumOriginal AssigneeBayer AktiengesellschaftExport CitationBiBTeX, EndNote, RefManPatent Citations (8), Referenced by (3), Classifications (13) External Links: USPTO, USPTO Assignment, EspacenetAcylamino quinophthalone compoundsUS 4088651 AAbstract Acylamino quinophthalone compounds which are free from sulfonic acid groups and correspond to the formula ##STR1## in which R.sub.1 and R.sub.2 are hydrogen, halogen, acylamino or lower alkoxy with the proviso that one of the residues R.sub.1 and R.sub.2 denotes acylamino while the other residue stands for hydrogen, halogen or a lower alkoxy; R.sub.3 is hydrogen, halogen or a lower alkoxy; X is a substituent; and n is a number from 0 to 3; are disclosed. The compounds useful as dyestuffs for hydrophobic fiber materials, e.g. polyester, are prepared by reacting an acylamino phthalic acid, the anhydride thereof, or mixtures of acylamino phthalic acids or the anhydrides thereof with a 3-hydroxy-quinalide.
We claim: 1. The compound having the formula ##STR12##
2. The compound having the formula ##STR13##
This is a continuation of application Ser. No. 782,731, filed Dec. 10, 1968 now abandoned.
The object of the present invention comprises quinophthalone dyestuffs which are free from sulphonic acid groups and correspond to the formula ##STR2## in which R.sub.1 and R.sub.2 stand for hydrogen, halogen, an acylamino group or a lower alkoxy group with the proviso that one of the residues R.sub.1 and R.sub.2 denotes an acylamino group while the other residue stands for hydrogen, halgen or a lower alkoxy group and R.sub.3 stands for hydrogen, halogen or a lower alkoxy group; X is a substituent; and n means a number from 0 to 3,
Including, in particular, mixtures of dyestuffs of the formula (I) in which R.sub.1 stands for an acylamino group and R.sub.2 for hydrogen with dyestuffs of the formula (I) in which R.sub.1 stands for hydrogen and R.sub.2 for an acylamino group, while R.sub.3 has the meaning given above, as well as a process for their production and use for the dyeing of hydrophobic fibre materials.
A special object of the present invention comprises quinophthalone dyestuffs which are free from sulphonic acid groups and correspond to the formula ##STR3## in which R.sub.1 and R.sub.2 stand for hydrogen or an acylamino group but cannot simultaneously represent hydrogen or acylamino groups; X is a substituent; and n means a number from 0 to 3, including, in particular, mixtures of dyestuffs of the formula (Ia) in which R.sub.1 stands for an acylamino group and R.sub.2 for hydrogen with dyestuffs of the formula (Ia) in which R.sub.1 stands for hydrogen and R.sub.2 for an acylamino group, as well as a process for their production and use for the dyeing of hydrophobic fibre materials.
Within the framework of the present application, the term acylamino groups groups primarily includes formyl-amino groups, optionally substituted alkylcarbonyl-, cycloalkylcarbonyl-, arylcarbonyl-, aralkylcarbonyl-, alkylsulphonyl-, arylsulphonyl-, aminocarbonyl-, alkoxycarbonyl-, aralkoxycarbonyl- and aryloxycarbonyl-amino groups.
Suitable alkyl radicals are primarily those with 1 - 4 carbon atoms, such as methyl, ethyl or butyl radicals, which may carry substituents, for example, methoxy, ethoxy or butoxy groups.
Suitable halogen atoms are, for example Cl, Br, F.
Suitable lower alkoxy groups are, for example OCH.sub.3, OC.sub.2 H.sub.5 and OC.sub.4 H.sub.9.
Suitable cycloalkyl radicals are, for example, cyclohexyl radicals.
Suitable aryl radicals are primarily phenyl radicals which may carry substituents, such as F, Cl, Br or I; nitro groups; alkyl groups with 1 - 4 carbon atoms; alkoxy groups with 1 -4 carbon atoms; and carbalkoxy groups, especially those with 1 - 4 carbon atoms in the alkoxy radical, for example methoxy-carbonyl or butoxy-carbonyl groups. Any substituents, with the exception of sulphonic acid groups, can serve as substituents X, especially halogen atoms, such as chlorine or bromine, and ethyl groups.
The dyestuffs of the formula (I) according to the invention are prepared in that acylamino-phthalic acids of formula ##STR4## wherein R.sub.1 and R.sub.2 stand for hydrogen, an acylamino group, a lower alkoxy group or halogen with the proviso that one of the residues R.sub.1 and R.sub.2 denotes an acylamino group whereas the other residue stands for hydrogen, halogen or a lower alkoxy group, R.sub.3 denotes hydrogen, halogen or a lower alkoxy group or their anhydrides or mixtures of dicarboxylic acids of the formula ##STR5## wherein R.sub.1 ' stands for an acylamino group, R.sub.2 ' and R.sub.3 ' denote hydrogen, halogen or a lower alkoxy group and dicarboxylic acids of the formula ##STR6## wherein R.sub.2 " stands for an acylamino group, R.sub.1 " and R.sub.3 " denote hydrogen, halogen or a lower alkoxy group or anhydrides of compounds (IIa) and (IIb), are reacted with 3-hydroxy-quinaldines of the formula ##STR7##
in which X stands for a substituent and n for a number from 0 to 3, and Y represents hydrogen or a carboxyl group which is split off in the course of the reaction, the starting components being so chosen that the final products are free from sulphonic acid groups.
Accordingly the dyestuffs of the formula (Ia) according to the invention are prepared in that acylamino-phthalic acids of formula ##STR8## in which R.sub.1 and R.sub.2 stand for hydrogen or an acylamino group but cannot simultaneously represent hydrogen or acylamino groups, or their anhydrides, or mixtures of dicarboxylic acids of the formula (IIc) in which R.sub.2 stands for hydrogen and R.sub.1 for an acylamino group, or of their anhydrides, with dicarboxylic acids of the formula (IIc), in which R.sub.2 stands for an acylamino group and R.sub.1 for hydrogen, or their anhydrides, are reacted with 3-hydroxy-quinaldines of the formula (III).
Suitable starting compounds of the formula (II) are for example: 3-acetylamino-phthalic acid, 3-methoxy-acetylamino-, 3-ethoxy-acetylamino-, 3-hydroxy-acetylamino-, 3-cyclohexane-carbonylamino-, 3-benzoyl-amino-, 3-(2'-chlorobenzoyl-amino)-, 3-(3'-chloro-benzoyl-amino)-, 3-(4'-chloro-benzoyl-amino)-, 3-(2"-methyl-benzoyl-amino)-, 3-(3'-methylbenzoyl-amino)-, 3-(4-'-methyl-benzoyl-amino)-, 3-(2'-methoxy-benzoyl-amino)-, 3-(3'-methoxy-benzoyl-amino)-, 3-(4'-methoxy-benzoyl-amino)-, 3-(3'-carbethoxy-benzoyl-amino)-, 3-(4'-carbethoxy-benzoyl-amino)-, 4-acetylamino-, 4-methoxy-acetyl-amino-4-ethoxy-acetylamino-, 4-hydroxy-acetylamino-, 4-cyclohexane-carbonylamino-, 4-benzoyl-amino-, 4-(2'-chloro-benzoyl-amino)-, 4-(3'-chloro-benzoyl-amino)-, 4-(4'-chloro-benzoyl-amino)-, 4-(2'-methyl-benzoyl-amino)-, 4-(3'-methyl-benzoyl-amino)-, 4-(4'-methyl-benzoyl-amino)-, 4-(2'-methoxy-benzoyl-amino)-, 4-(3'-methoxy-benzoyl-amino)-, 4-(3'-methoxy-benzoyl-amino)-, 4-(4'-methoxy-benzoyl-amino)-, 4-(3'-carbethoxy-benzoyl-amino)-, 4-(4'-carbethoxy-benzoyl-amino)-phthalic acid, 4-acetylamino-5-methoxy-, 4-acetylamino-5-ethoxy-, 4-acetyl-amino-5-chloro-, 4-acetylamino-5-bromophthalic acid or mixtures of the aforesaid 3- or 4-acylamino-dicarboxylic acids, especially those containing identical acylamino radicals in the 3- or 4-position.
Mixtures of such dicarboxlic acids are obtained in known manner, for example, by the nitration of phthalic acid anhydride with nitric acid in sulphuric acid, reduction of the resultant mixture of 3-nitro-phthalic acid and 4-nitrophthalic acid to form the mixture of the corresponding aminophthalic acids and subsequent acylation.
Suitable starting compounds of the formula (III) are, for example:
3-hydroxy-quinaldine, 3-hydroxy-quinaldine-carboxylic acid-4,3 -hydroxy-5,7-dimethyl-quinaldine, 3-hydroxy-6,8-dichloro-quinaldine, 3-hydroxy-6-bromo-quinaldine, 3-hydroxy-6,8-dibromo-quinaldine.
The reaction of (II) with (III) is preferably carried out in a molar ratio of 1 : 1 in inert high-boiling organic solvents, such as chlorobenzene, at temperatures above 100 C. The yellow dyestuffs thus obtained can easily be isolated by filtering off with suction. They are eminently suitable for dyeing and printing hydrophobic synthetic fibre materials such as polyester fibres, especially fibres consisting of polyethylene terephthalate or of condensation products of bis-hydroxy-methylcyclohexane an terephthalic acid, as well as fibres of cellulose triacetate or polyolefines and superpolyamides and -urethanes. The dyestuffs are particularly suitable for the dyeing of polyester fibres by the so-called "thermosol" process.
Yellow dyeings of good fastness to sublimation, light and rubbing are obtained on the said materials by the dyeing methods customarily used for these materials.
The parts given in the following Examples are parts by weight, the temperatures are given in degrees Centigrade.
EXAMPLE 1 20.3 Parts 3-hydroxy-quinaldine-carboxylic acid-4and 20.5 parts 3-acetylamino-phthalic acid anhydride are suspended in 300 parts 1,2,4-trichlorobenzene and the mixture is heated at 200 stirring until a formation of CO.sub.2 and water can no longer be detected after about 2 hours. The mixture is cooled, suction-filtered, and the filter residue is washed with benzene. The yield amounts to 32.2 parts = 93% of theory of a yellow dyestuff of the formula ##STR9##
EXAMPLE 2 20.3 Parts 3-hydroxy-quinaldine-carboxylic acid-4 and 20.5 parts 4-acetylamino-phthalic acid anhydride are suspended in 300 parts 1,2,4-trichlorobenzene and heated at 200 formation of CO.sub.2 and water can no longer be detected after about 2 hours. The mixture is cooled, the precipitated dyestuff is filtered off with suction, and the filter residue is washed with benzene. The yield amounts to 31 parts = 90% of theory of a dyestuff of the formula ##STR10##
In an analogous manner, condensation of 3-hydroxy-quinaldine or 3-hydroxy-quinaldine-carboxylic acid-4 with the following 3-acylamino-phthalic acids or 4-acylamino-phthalic acids yields yellow dyestuffs which give yellow dyeings of good fastness properties on polyester fibres by the thermosol method: 3-ethoxy-acetyl-amino-phthalic acid, cyclohexane-carbonyl-amino-phthalic acid, 3-benzoyl-amino-phthalic acid, 3-(2'-chloro-benzoyl-amino)-phthalic acid, 3-(4'-chloro-benzoyl-amino)-phthalic acid, 3-(4'-methyl-benzoyl-amino)-phthalic acid, 3-(2'-methoxy-benzoyl-amino)-phthalic acid, 3-(3'-methoxy-benzoyl-amino)-phthalic acid, 3-(4'-methoxy-benzoyl-amino)-phthalic acid, 3-(4'-carbethoxy-benzoyl-amino)-phthalic acid, 4-ethoxy-acetyl-amino-phthalic acid, 4-cyclo-hexane-carbonyl-amino-phthalic acid, 4-benzoyl-amino-phthalic acid, 4-(2'-chloro-benzoyl-amino)-phthalic acid, 4-(4'-chloro-benzoyl-amino)-phthalic acid, 4-(4'-methyl-benzoyl-amino)-phthalic acid, 4-(2'-methoxy-benzoyl-amino)-phthalic acid, 4-(3'-methoxy-benzoyl-amino)-phthalic acid, 4-(4'-methoxy-benzoyl-amino)-phthalic acid, 4-(4'-carbethoxy-benzoyl-amino)-phthalic acid, 4-acetylamino-5-methoxy-phthalic acid, 4-acetyl-amino-5-ethoxy-phthalic acid, 4-acetylamino-5-chloro-phthalic acid, 4-acetylamino-5-bromo-phthalic acid.
EXAMPLE 3 Phthalic acid anhydride is nitrated in known manner in sulphuric acid with nitric acid, the resultant mixture of 3-nitro-phthalic acid and 4-nitro-phthalic acid is reduced in known manner to form the mixture of the amino-phthalic acids and this is converted in the usual way into the mixture of the acetylamino compounds. 22.3 Parts of this mixture of 3-acetylamino-phthalic acid and 4-acetylamino-phthalic acid are heated at boiling temperature under reflux in 200 parts o-dichlorobenzene while stirring. As soon as a clear solution has formed, 20.3 parts 3-hydroxy-quinaldine-carboxylic acid-4are added and heating is continued at 170 filtered hot, the filtrate is cooled, and the dyestuff mixture is isolated by filtering off with suction. It consists of a mixture of dyestuffs of the formulae ##STR11## which are present in a proportion of 1 : 1 to about 1 : 2. This mixing proportion can be varied within wide limits, depending on the method applied for nitrating the phthalic acid anhydride. The dyestuff mixture yields dyeings of very good fastness to wet processing, sublimation and light on polyester fibres.
EXAMPLE 4 25 Parts of the dyestuff mixture obtained according to Example 1 are ground with 75 parts of a condensation product obtained from p-naphthalene-sulphonic acid and formaldehyde and with 120 parts of water in a ball mill for 24 hours. The paste is subsequently dried in a vacuum at 50
1 Part of this dyestuff powder is stirred into 2000 parts of hot water which contains 8 - 10 parts of a carrier, e.g. o-phenyl-phenol, and which has been adjusted to a pH value of about 4.5 by means of sulphuric acid. A very fine dyestuff suspension is obtained, into which 50 parts of polyester fibres are introduced at 40 heated to boiling point within 20 minutes and kept at this temperature for 1 - 11/2 hours. The dyed material is then thoroughly rinsed with water and dried. A yellow dyeing of very good fastness to wet processing, sublimination and light is obtained. Compared with the pure dyestuffs, the dyestuff mixture used above has a noticeably improved drawing power.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2006022 *Nov 14, 1933Jun 25, 1935Gen Aniline Works IncDyestuff of the quinophthalone series of good fastness to lightUS2818410 *Feb 23, 1956Dec 31, 1957Du PontDyes of the quinophthalone seriesUS3023212 *Jun 30, 1960Feb 27, 1962Du PontBasic dyes of the quinophthalone seriesUS3122533 *Sep 13, 1960Feb 25, 1964Sandoz LtdAzo disperse dyestuffs of low water solubilityUS3687929 *May 26, 1969Aug 29, 1972Liechti Hans WilhelmBasic dyestuffs containing a quaternized pyridine or quinoline radicalUS3788810 *Jul 16, 1971Jan 29, 1974Bayer AgProcess for the dyeing of synthetic fibre materials with quinophthalone dyestuffs from organic solventsDE1644680A1 *Dec 19, 1967Jul 22, 1971Bayer AgChinophthalonfarbstoffeDE1769789A1 *Jul 12, 1968Oct 28, 1971Bayer AgChinophthalonfarbstoffe* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5468862 *Apr 25, 1994Nov 21, 1995Warner-Jenkinson CompanySynthesis of Solvent Yellow 33 (D & C Yellow 11) with excess phthalic anhydride acid as a solventUS6121452 *Aug 28, 1997Sep 19, 2000Bayer AktiengesellschaftProcess for the preparation of quinophthalonesUS7147704 *Mar 20, 2006Dec 12, 2006Tokyo Ink Mfg. Co., LtdPigment dispersing agent, pigment composition and pigment dispersion* Cited by examinerClassifications U.S. Classification546/154, 8/922, 562/455, 560/48, 8/657, 562/458, 8/524, 562/457, 562/456International ClassificationC09B25/00Cooperative ClassificationC09B25/00, Y10S8/922European ClassificationC09B25/00RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google