CH362774A - Process for the preparation of acidic monoazo dyes - Google Patents
Process for the preparation of acidic monoazo dyesInfo
- Publication number
- CH362774A CH362774A CH1423461A CH1423461A CH362774A CH 362774 A CH362774 A CH 362774A CH 1423461 A CH1423461 A CH 1423461A CH 1423461 A CH1423461 A CH 1423461A CH 362774 A CH362774 A CH 362774A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid
- monoazo dyes
- acidic
- dyes
- preparation
- Prior art date
Links
- 239000000975 dye Substances 0.000 title claims description 17
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title claims description 10
- 230000002378 acidificating effect Effects 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- -1 aromatic alcohols Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- AFPOMDNRTZLRMD-UHFFFAOYSA-N dodecyl carbonochloridate Chemical compound CCCCCCCCCCCCOC(Cl)=O AFPOMDNRTZLRMD-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- QAOJBHRZQQDFHA-UHFFFAOYSA-N 2,3-dichlorobenzoic acid Chemical class OC(=O)C1=CC=CC(Cl)=C1Cl QAOJBHRZQQDFHA-UHFFFAOYSA-N 0.000 description 1
- LYNDARBQVAIRCT-UHFFFAOYSA-N 2-(2-hydroxyacetyl)oxyhexanoic acid Chemical compound C(CCC)C(C(=O)O)OC(CO)=O LYNDARBQVAIRCT-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- FOWJCNSJFZYQJV-UHFFFAOYSA-N 4-hydroxy-6-(2,4,6-trimethylanilino)naphthalene-2-sulfonic acid Chemical compound CC1=CC(C)=C(NC2=CC3=C(O)C=C(C=C3C=C2)S(O)(=O)=O)C(C)=C1 FOWJCNSJFZYQJV-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- PHRVJZNHPVJYOM-UHFFFAOYSA-N 5-acetamido-2-aminobenzenesulfonic acid Chemical compound CC(=O)NC1=CC=C(N)C(S(O)(=O)=O)=C1 PHRVJZNHPVJYOM-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- VFXVAXFIFHSGNR-UHFFFAOYSA-N octyl carbonochloridate Chemical compound CCCCCCCCOC(Cl)=O VFXVAXFIFHSGNR-UHFFFAOYSA-N 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical group ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 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
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung saurer Monoazofarbstoffe Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung saurer Monoazofarbstoffe der Formel
EMI0001.0003
worin Reinendirekt oder über ein Sauerstoffatom mit dem Kohlenstoffatom der Carbonylgruppe verbun denen, mindestens<B>5,</B> gegebenenfalls durch Sauer stoffatome voneinander getrennte, Kohlenstoffatome aufweisenden organischen Rest und x einen niedrig- molekularen Alkylrest bedeuten,
und worin der Rest R-OC-HN- in 4- oder 5-Stellung steht, oder von Derivaten von solchen Farbstoffen, in denen
EMI0001.0013
die Acetylgruppe durch Hydrolyse abspaltet und die gebildete freie Aminogruppe mit einer Verbindung der Kern<B>A</B> undloder der Kern B weitere Substi- tuenten trägt. Der Kern B kann z. B. niedrigmoleku- lare Alkylreste, vorzugsweise 2 solche Alkylreste, in 4'- und 6-Stellung tragen.
Das erfindungsgemässe Verfahren ist dadurch ge kennzeichnet, dass man in sauren Monoazofarbstoffen der Formel der Formel R-CO-Hal worin Hal Chlor oder Brom bedeutet, verschliesst. Die neuen sauren Monoazofarbstoffe färben Wolle,<B>Seide-,</B> Lederund synthetische Polyamidfascrn aus neutralem bis schwach saurem Bade in reinen, blaustichig roten Tönen von sehr guten Licht- und Nassechthelten.
Die Acylierung kann mit aliphatischen oder aro matischen Säureanhydriden oder Säurehalogeniden, insbesondere mit Säurechloriden, in bekannter Weise durchgeführt werden.
Als Acylierungsmittel kommen beispielsweise in Betracht die Chloride der Capryl- säure, 2-Äthyleapronsäure, Caprinsäure, Laurin- säure, Palmitinsäure, Stearinsäure, Butylglycoloxy- essigsäure, Phenoxy- und Kresoxyessigsäuren, Benzoesäure, Mono- und Dichlorobenzoesäuren,
4-tert.-Butyl-benzoesäure oder Cyclohexylcarbon- säure. Besonders wertvolle Acylierungsmittel sind auch die Chlorameisensäurcester verschiedener ali- phatischer und aromatischer Alkohole, wie beispiels weise des Amyl-, Hexyl-, Octyl-, Decyl-, Lauryl- oder Cetylalkohols sowie der Chlorameisensäure- phenyl-,
-benzyl- oder -cyclohexylester, oder der Chlorameisensäureester des 4-Octyl- oder 4-Cyclo- hexy.1-1-hydroxy-benzols. Ganz vorzügliche, Acylie- rungsmittel sind sodann die Chlorameisensäureester einiger Ätheralkohole, wie beispielsweise des Äthy- lenglycol-monobutyl-, -hexyl-, -octyl- oder -phenyl- äthers,
wie auch des Diäthylen,-,lycol-mono-methyl-, butyl- oder -phenyläthers.
Im nachfolgenden Beispiel bedeuten die Teile Gewichtsteile, die Prozente Gewichtsprozente, und die Temperaturen sind in Celsiusgraden angegeben. <I>Beispiel</I> <B>59,8</B> Teile des durch saures Kuppeln von<B>23</B> Teilen, diazotierter 1-Amino-4-acetylamino-benzol- 2-sulfonsäure mit<B>35,7</B> Teilen 2-(2,4',6-Trimethyl- phenylamino)-8-hydroxy-naphthalin-6-sulfonsäure er hältlichen. Monoazofarbstoffes werden in Form des Dinatriumsalzes in<B>1000</B> Teilen Wasser und<B>1000</B> Teilen Alkohol heiss gelöst.
Nach Zugabe von<B>50</B> Teilen 30%iger Salzsäure wird die Lösung während <B>3</B> Stunden auf<B>950</B> erhitzt, um die Acetylgruppe des Monoazofarbstoffes abzuspalten. Der hydrolysierte Farbstoff fällt vollständig aus; er wird kalt abfiltriert und hierauf in 2000 Teilen Wasser unter Zusatz von <B>10</B> Teilen Natriumcarbonat gelöst.
Zu der<B>500</B> warmen Lösung lässt man im Verlauf von einigen Stunden<B>25</B> Teile Chlorameisensäurelaurylester nach Massgabe des Verbrauches zutropfen. Während der Acylierung streut man<B>10</B> Teile Natriumbiearbonat in kleinen Portionen derart in die Reaktionsmasse, dass deren pH-Wert stets<B>7,5-8</B> beträgt. Der sich bildende Farbstoff fällt vollständig aus; er wird nach dem Erkalten der Reaktion#smasse abgcsaugt und ge trocknet.
Der getrocknete neue Monoazofarbstoff ist ein dunkelrotes Pulver, das auf Wolle, Seide und synthetischen Polyamidfasern aus neutralem bis schwach essigsaurem Bade ein volles Rubin mit sehr guter Licht- und sehr guten Nassechtheiten färbt.
Ersetzt man die<B>25</B> Teile Chlorameisensäure- laurylester durch eine äquivalente Menge Chlor- ameisensäu,reoctylester oder C"hloram#ei,sensäurecatyl- ester, so erhält man ähnliche Farbstoffe.
Process for the preparation of acidic monoazo dyes The present invention provides a process for the preparation of acidic monoazo dyes of the formula
EMI0001.0003
in which pure compounds are connected directly or via an oxygen atom to the carbon atom of the carbonyl group, at least <B> 5 </B>, optionally separated by oxygen atoms, organic radicals containing carbon atoms and x is a low molecular weight alkyl radical,
and in which the radical R-OC-HN- is in the 4- or 5-position, or of derivatives of such dyes in which
EMI0001.0013
the acetyl group is split off by hydrolysis and the free amino group formed with a compound of the core <B> A </B> and / or the core B carries further substituents. The core B can e.g. B. carry low molecular weight alkyl radicals, preferably 2 such alkyl radicals, in the 4'- and 6-position.
The process according to the invention is characterized in that acidic monoazo dyes of the formula of the formula R-CO-Hal where Hal is chlorine or bromine are sealed. The new acidic monoazo dyes dye wool, <B> silk, </B> leather and synthetic polyamide fibers from neutral to weakly acidic baths in pure, bluish red shades of very good light and wet fastness.
The acylation can be carried out in a known manner with aliphatic or aromatic acid anhydrides or acid halides, in particular with acid chlorides.
Suitable acylating agents are, for example, the chlorides of caprylic acid, 2-ethyleapronic acid, capric acid, lauric acid, palmitic acid, stearic acid, butylglycoloxyacetic acid, phenoxy- and cresoxyacetic acids, benzoic acid, mono- and dichlorobenzoic acids,
4-tert-butylbenzoic acid or cyclohexylcarboxylic acid. Particularly valuable acylating agents are also the chloroformic acid esters of various aliphatic and aromatic alcohols, such as amyl, hexyl, octyl, decyl, lauryl or cetyl alcohol and chloroformic acid phenyl,
benzyl or cyclohexyl ester, or the chloroformic acid ester of 4-octyl or 4-cyclohexy.1-1-hydroxy-benzene. Very excellent acylating agents are then the chloroformic acid esters of some ether alcohols, such as ethylene glycol monobutyl, hexyl, octyl or phenyl ether,
as well as diethylen, -, lycol-mono-methyl-, butyl- or -phenylether.
In the following example, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius. <I> Example </I> <B> 59.8 </B> parts of the 1-amino-4-acetylamino-benzene-2-sulfonic acid diazotized by acidic coupling of <B> 23 </B> parts with < B> 35.7 parts 2- (2,4 ', 6-trimethylphenylamino) -8-hydroxynaphthalene-6-sulfonic acid are available. Monoazo dyes are dissolved in the form of the disodium salt in <B> 1000 </B> parts of water and <B> 1000 </B> parts of alcohol while hot.
After adding <B> 50 </B> parts of 30% hydrochloric acid, the solution is heated to <B> 950 </B> for <B> 3 </B> hours in order to split off the acetyl group of the monoazo dye. The hydrolyzed dye precipitates completely; it is filtered off cold and then dissolved in 2000 parts of water with the addition of 10 parts of sodium carbonate.
<B> 25 </B> parts of lauryl chloroformate are added dropwise to the <B> 500 </B> warm solution in the course of a few hours, depending on the consumption. During the acylation, <B> 10 </B> parts of sodium carbonate are sprinkled in small portions into the reaction mass in such a way that its pH value is always 7.5-8. The dye which forms precipitates completely; After the reaction has cooled, it is filtered off with suction and dried.
The dried, new monoazo dye is a dark red powder that dyes a full ruby with very good light and very good wet fastness properties on wool, silk and synthetic polyamide fibers from neutral to weakly acetic acid baths.
If the 25 parts of lauryl chloroformate are replaced by an equivalent amount of octyl chloroformate or catyl chloroformate, similar dyes are obtained.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1423461A CH362774A (en) | 1960-01-22 | 1960-01-22 | Process for the preparation of acidic monoazo dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1423461A CH362774A (en) | 1960-01-22 | 1960-01-22 | Process for the preparation of acidic monoazo dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH362774A true CH362774A (en) | 1962-06-30 |
Family
ID=4399095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1423461A CH362774A (en) | 1960-01-22 | 1960-01-22 | Process for the preparation of acidic monoazo dyes |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH362774A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2168520A1 (en) * | 1972-01-20 | 1973-08-31 | Sandoz Sa |
-
1960
- 1960-01-22 CH CH1423461A patent/CH362774A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2168520A1 (en) * | 1972-01-20 | 1973-08-31 | Sandoz Sa |
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