CH356858A - Process for the preparation of anthraquinone vat dyes - Google Patents
Process for the preparation of anthraquinone vat dyesInfo
- Publication number
- CH356858A CH356858A CH356858DA CH356858A CH 356858 A CH356858 A CH 356858A CH 356858D A CH356858D A CH 356858DA CH 356858 A CH356858 A CH 356858A
- Authority
- CH
- Switzerland
- Prior art keywords
- amino
- atom
- carboxylic acid
- anthraquinone
- radical
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 12
- 239000000984 vat dye Substances 0.000 title claims description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title description 2
- 150000004056 anthraquinones Chemical class 0.000 title description 2
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical compound O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 claims description 8
- -1 carboxylic acid chlorides Chemical class 0.000 claims description 5
- FWEQPMZEKHHFTB-UHFFFAOYSA-N n-(5-amino-9,10-dioxoanthracen-1-yl)benzamide Chemical class C1=CC=C2C(=O)C=3C(N)=CC=CC=3C(=O)C2=C1NC(=O)C1=CC=CC=C1 FWEQPMZEKHHFTB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- PXONUHJWANQSRA-UHFFFAOYSA-N NC1=C(C=CC=2C(C3=C(C=CC=C3C(C12)=O)C(C1=C(C=CC=C1)F)=O)=O)N Chemical compound NC1=C(C=CC=2C(C3=C(C=CC=C3C(C12)=O)C(C1=C(C=CC=C1)F)=O)=O)N PXONUHJWANQSRA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000008425 anthrones Chemical class 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- MMKNBFSDCOALQO-UHFFFAOYSA-N 1-amino-9,10-dioxoanthracene-2-carboxylic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC(C(O)=O)=C2N MMKNBFSDCOALQO-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical class [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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
- C09B1/36—Dyes with acylated amino groups
- C09B1/42—Dyes with acylated amino groups the acyl groups being residues of an aromatic carboxylic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung von Anthrachinonküpenfarbstoffen Es wurde gefunden, dass man zu wertvollen Küpenfarbstoffen gelangt, wenn man Anthronderi- vate, die in mindestens einer der Stellungen 1 :9, 4: 10 oder 5:
10 einen Heteroring und in minde stens einer ss-Stellung des Anthronkernes eine Car- bonsäurehalogenidgruppe aufweisen, mit 1-Amino-5- benzoylaminoanthrachinon en kondensiert, welche mindestens einen Substituenten im Benzoylrest auf weisen.
Die für das vorliegende Verfahren aIs. Ausgangs stoffe in Frage kommenden Carbonsäurehalogenide leiten sich vorzugsweise von Carbonsäuren der Formel
EMI0001.0018
ab, worin X ein N-Atom, Y eine Iminogruppe, ein Schwefelatom, eine -SO-Gruppe oder die Gruppierung
EMI0001.0023
bedeuten, worin R ein H-Atom, einen Alkyl- oder Arylrest bedeuten.
Als Beispiele geeigneter Carbonsäuren, welche der Formel (1) entsprechen, seien genannt: 1,9-Pyrazolanthron-2-carbonsäure, 1,9-Isothiazolanthron-2-carbonsäure, 1,9-Isothiazolanthro#nsulfon-2-carbonsäure, vor allem aber die 1,9-Anthrapyrimidin-2-carbonsäuren der Formel
EMI0001.0032
worin R einen niedrigmolekularen Alkylrest, insbe sondere aber ein H-Atom, bedeutet.
Nebst den bereits genannten, der Formel (1) ent sprechenden Carbonsäuren seien noch die 1,9-Pyrazolanthron-6-carbonsäure und die folgenden genannt:
EMI0002.0001
Alle die genannten Carbonsäuren stellen bekannte Verbindungen dar, und können nach bekannten Ver fahren erhalten werden.
Für die verfahrensgemässe Umsetzung eignen sich insbesondere die Chloride der Anthroncarbonsäuren der angegebenen Art. Diese werden zweckmässig er-. halten aus den entsprechenden Carbonsäuren mittels Thionylchlorid in einem inerten Lösungs- oder Ver teilungsmittel, da die so erhaltenen Gemische nach beendeter Säurehalogenidbildung und Abdestillieren des überschüssigen Thionylchlorids unmittelbar für die Kondensation mit den Aminoanthrachinonen ver wendet werden können.
Die ebenfalls als Ausgangsstoffs dienenden 1-Amino-5-benzoylaminoanthrachinone weisen im Benzoylrest mindestens einen Substituenten auf, bei spielsweise Methoxygruppen oder Trifluormethyl- gruppen, vorzugsweise aber Halogenatome.
Von besonderem Interesse sind jene benzoylamino- gruppenhaltigen Aminoanthrachinone, deren Benzoyl- rest in o-Stellung zur Carbonsäureamidgruppe ein Fluoratom aufweist.
Als Beispiel sei in erster Linie das 1-Amino-5-(o-fluorbenzoyl)@aminoanthrachinon genannt, ferner seien solche Verbindungen erwähnt, die ausser dem Fluoratom noch weitere Halogen atome, insbesondere Chloratome, im Benzoylrest ent halten, beispielsweise das 1-Amino-5-(2'-fluor-4'- oder 5'-chlorbenzoyl)-aminoanthrachinon.
Die Umsetzung der Carbonsäurehalogenide mit den Aminoanthrachinonen erfolgt zweckmässig in Lösungs- oder Verteilungsmitteln von hohem Siede punkt, wie Monochlorbenzol, Di- oder Trichlor- benzolen, Nitrobenzol oder Naphthalin, gegebenen falls unter Zusatz einer tertiären Base, wie Pyridin, bei erhöhter Temperatur.
EMI0002.0046
Die nach dem vorliegenden Verfahren erhält lichen neuen Verbindungen entsprechen z.
B. der Formel A-[CONHA']n worin A den Rest eines in mindestens einer i3-Stel- lung an die CONHA'-Gruppe bzw. Gruppen gebun, denen Anthronderivates darstellt, das in mindestens einer der Stellungen 1 :9, 4:10 oder 5: 10 einen Heteroring aufweist, n eine ganze Zahl im Werte von höchstens 3 und NHA' den Rest eines 1-Amino- 5-benzoylaminoanthrachinons bedeutet, dessen Ben- zoylrest mindestens einen Substituenten aufweist.
Diese Verbindungen, insbesondere jene der allge meinen Formel
EMI0002.0060
worin X und Y die angegebene Bedeutung haben und R1 .einen Benzoylrest, der in o-Stellung zur -CONH-Gruppe ein Fluoratom aufweist, bedeutet, stellen wertvolle Küpenfarbstoffe dar, welche die verschiedensten Fasern, insbesondere aber die Cellu- losefasern, in reinen Gelbtönen von sehr guten Echtheitseigenschaften, insbesondere hoher Licht- echtheit und hoher Farbstärke, färben.
Die neuen Farbstoffe können auch als Pigment verwendet wer den.
Im nachfolgenden Beispiel und in der Färbe vorschrift bedeuten die Teile, sofern nichts anderes angegeben wird, Gewichtsteile, die Prozente Ge wichtsprozente, und die Temperaturen sind in Cel siusgraden angegeben.
<I>Beispiel</I> Eine Mischung von 5 Teilen 1,9-Anthrapyrimidin- 2-carbonsäure, 5 Teile Thionylchlorid und 400 Teile o-Dichlorbenzol werden bis zur vollständigen Lösung bei 125-130 gerührt. Das überschüssige Thionyl- chlorid wird im Vakuum abdestilliert. Zur Lösung gibt man 6,5 Teile 1-Amino-5-(o-fluorbenzoyl)- amino-anthrachinon und 3 Teile Pyridin und rührt das Gemisch etwa 30' bei 125 bis 1300.
Der gebil dete Farbstoff wird warm abfiltriert, mit o-Diehlor- benzol, Alkohol und Wasser gewaschen und getrock net.
Er löst sich in konzentrierter Schwefelsäure orange und färbt Baumwolle aus bordeauxroter Küpe in grünstichiggelben, echten Tönen.
Die in diesem Beispiel verwendete 1,9-Anthra- pyrimidin-2-carbonsäure kann gemäss Beispiel 23 der amerikanischen Patentschrift Nr. 2 212 928 durch Erhitzen von 1-Amino-anthrachinon-2-carbonsäure mit Formaldehyd und Ammoniak in wässeriger Lö sung auf 90 bis 1000 erhalten werden.
<I>Färbevorschrift</I> 1 Teil des nach dem obigen Beispiel erhaltenen Farbstoffes wird in 100 Teilen Wasser unter Zusatz von 4 Raumteilen 30 ,%iger Natriumhydroxydlösung mit 2 Teilen Natriumhydrosulfit bei 450 verküpt. Die so erhaltene Stammküpe gibt man zu einer Lösung von 4 Raumteilen 30 1/aiger Natriumhydroxydlösung und 2 Teilen Natriumhydrosulfit in 2000 Teilen Was ser.
In dem so erhaltenen Färbebad färbt man 100 Teile Baumwolle während einer Stunde bei 40 bis 500 unter Zugabe von 10 Teilen Natriumchlorid. Die Baumwolle wird hierauf abgequetscht, an der Luft oxydiert, gespült, abgesäuert, nochmals gespült und kochend geseift. Sie ist kräftig gelb gefärbt, und die Färbung besitzt sehr gute Echtheitseigenschaften.
Process for the production of anthraquinone vat dyes It has been found that valuable vat dyes are obtained if one uses anthrone derivatives which are in at least one of the positions 1: 9, 4: 10 or 5:
10 have a hetero ring and in at least one ss-position of the anthrone nucleus a carboxylic acid halide group, condensed with 1-amino-5-benzoylaminoanthraquinones which have at least one substituent in the benzoyl radical.
The aIs for the present proceedings. Starting materials suitable carboxylic acid halides are preferably derived from carboxylic acids of the formula
EMI0001.0018
where X is an N atom, Y is an imino group, a sulfur atom, an -SO group or the grouping
EMI0001.0023
denote, in which R denotes an H atom, an alkyl or aryl radical.
Examples of suitable carboxylic acids which correspond to formula (1) are: 1,9-pyrazolanthrone-2-carboxylic acid, 1,9-isothiazolanthrone-2-carboxylic acid, 1,9-isothiazolanthrone-2-carboxylic acid, above all but the 1,9-anthrapyrimidine-2-carboxylic acids of the formula
EMI0001.0032
where R is a low molecular weight alkyl radical, but in particular a special hydrogen atom.
In addition to the already mentioned carboxylic acids corresponding to formula (1), 1,9-pyrazolanthrone-6-carboxylic acid and the following may also be mentioned:
EMI0002.0001
All of the carboxylic acids mentioned are known compounds and can be obtained by known methods.
The chlorides of the anthronecarboxylic acids of the type indicated are particularly suitable for the implementation according to the process. keep from the corresponding carboxylic acids by means of thionyl chloride in an inert solvent or Ver distribution medium, since the resulting mixtures can be used immediately ver for the condensation with the aminoanthraquinones after the acid halide formation and distillation of the excess thionyl chloride.
The 1-amino-5-benzoylaminoanthraquinones, which are also used as starting materials, have at least one substituent in the benzoyl radical, for example methoxy groups or trifluoromethyl groups, but preferably halogen atoms.
Of particular interest are those aminoanthraquinones containing benzoylamino groups whose benzoyl radical has a fluorine atom in the o-position to the carboxamide group.
As an example, the 1-amino-5- (o-fluorobenzoyl) @aminoanthraquinone may be mentioned, and compounds that contain, in addition to the fluorine atom, other halogen atoms, in particular chlorine atoms, in the benzoyl radical, for example 1-amino -5- (2'-fluoro-4'- or 5'-chlorobenzoyl) -aminoanthraquinone.
The reaction of the carboxylic acid halides with the aminoanthraquinones is expediently carried out in solvents or dispersants with a high boiling point, such as monochlorobenzene, di- or trichlorobenzenes, nitrobenzene or naphthalene, if necessary with the addition of a tertiary base such as pyridine, at elevated temperature.
EMI0002.0046
The new compounds obtained by the present process correspond to z.
B. of the formula A- [CONHA '] n in which A is the radical of a bonded in at least one 13-position to the CONHA' group or groups which represent an anthrone derivative which is in at least one of the positions 1: 9, 4 : 10 or 5:10 has a hetero ring, n is an integer not exceeding 3 and NHA 'is the residue of a 1-amino-5-benzoylaminoanthraquinone whose benzoyl radical has at least one substituent.
These compounds, especially those of the general formula
EMI0002.0060
where X and Y have the meaning given and R1 is a benzoyl radical which has a fluorine atom in the o-position to the -CONH group, are valuable vat dyes, which the most diverse fibers, but especially the cellulose fibers, in pure yellow tones dye with very good fastness properties, especially high light fastness and high color strength.
The new dyes can also be used as a pigment.
In the following example and in the dyeing instructions, the parts are parts by weight, unless otherwise specified, the percentages are percentages by weight and the temperatures are given in degrees Celsius.
<I> Example </I> A mixture of 5 parts of 1,9-anthrapyrimidine-2-carboxylic acid, 5 parts of thionyl chloride and 400 parts of o-dichlorobenzene are stirred at 125-130 until completely dissolved. The excess thionyl chloride is distilled off in vacuo. 6.5 parts of 1-amino-5- (o-fluorobenzoyl) -amino-anthraquinone and 3 parts of pyridine are added to the solution, and the mixture is stirred for about 30 'at 125 to 1300.
The dyestuff formed is filtered off while warm, washed with o-diehlorbenzene, alcohol and water and dried.
It dissolves in concentrated sulfuric acid orange and dyes cotton from a burgundy vat in greenish yellow, real shades.
The 1,9-anthrapyrimidine-2-carboxylic acid used in this example can be prepared according to Example 23 of American Patent No. 2,212,928 by heating 1-amino-anthraquinone-2-carboxylic acid with formaldehyde and ammonia in aqueous solution to 90 to 1000 can be obtained.
<I> Dyeing instructions </I> 1 part of the dye obtained according to the above example is vat in 100 parts of water with the addition of 4 parts by volume of 30% strength sodium hydroxide solution with 2 parts of sodium hydrosulfite at 450. The stock vat thus obtained is added to a solution of 4 parts by volume of 30 l / a sodium hydroxide solution and 2 parts of sodium hydrosulfite in 2000 parts of water.
In the dyebath obtained in this way, 100 parts of cotton are dyed for one hour at 40 to 500 times with the addition of 10 parts of sodium chloride. The cotton is then squeezed off, oxidized in the air, rinsed, acidified, rinsed again and soaped at the boil. It is dyed a strong yellow, and the dyeing has very good fastness properties.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH356858T | 1957-05-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH356858A true CH356858A (en) | 1961-09-15 |
Family
ID=4511335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH356858D CH356858A (en) | 1957-05-20 | 1957-05-20 | Process for the preparation of anthraquinone vat dyes |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH356858A (en) |
-
1957
- 1957-05-20 CH CH356858D patent/CH356858A/en unknown
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