CH282940A - Process for the production of dyes and intermediates. - Google Patents
Process for the production of dyes and intermediates.Info
- Publication number
- CH282940A CH282940A CH282940DA CH282940A CH 282940 A CH282940 A CH 282940A CH 282940D A CH282940D A CH 282940DA CH 282940 A CH282940 A CH 282940A
- Authority
- CH
- Switzerland
- Prior art keywords
- parts
- production
- sulfur trioxide
- leuco
- dyes
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000975 dye Substances 0.000 title description 4
- 239000000543 intermediate Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000001180 sulfating effect Effects 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 230000019635 sulfation Effects 0.000 claims description 3
- 238000005670 sulfation reaction Methods 0.000 claims description 3
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001000 anthraquinone dye Substances 0.000 claims description 2
- 239000000984 vat dye Substances 0.000 claims description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000003857 carboxamides Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 1
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- IOAWPHRYPNVCHV-UHFFFAOYSA-N 4-pentan-3-ylbenzenesulfonamide Chemical compound C(C)C(C1=CC=C(C=C1)S(=O)(=O)N)CC IOAWPHRYPNVCHV-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent 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
- C09B9/00—Esters or ester-salts of leuco compounds of vat dyestuffs
- C09B9/02—Esters or ester-salts of leuco compounds of vat dyestuffs of anthracene dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Zusatzpatent zum Hauptpatent Nr. 261369. <B>Verfahren zur Herstellung von Farbstoffen und Zwischenprodukten.</B> Im Schweiz. Patent Nr. 261369 ist ein Verfahren zur Herstellung von Leukoschwe- felsäureesternvon verküpbarenVerbindungen durch Behandeln der entsprechenden Leuko- verbindung mit einem Sulfatierungsmittel be schrieben, welches dadurch gekennzeichnet ist, dass die Sulfatierung in Gegenwart eines organischen, sich von einem sekundären Amin ableitenden Amids erfolgt,
wobei man in Ge genwart oder Abwesenheit von Verdünnungs mitteln arbeiten kann und als Sulfatierungs- mittel zweckmässigerweise Schwefeltrioxyd oder die Additionsverbindung von Schwefel- trioxyd mit einem organischen Amid, wie z. B. Dimethylformamid, oder mit einer tertiären Base, wie z. B. Picolin, oder einen Ester der Chlorsulfonsäure verwenden kann.
Als ±ür die Durchführung des im genannten Patent beschriebenen Verfahrens verwende ten Amide sind Dimethylformamid, Diäthyl- formamid, Dimethylacetamid, Formylpipe- ridid, Tetramethylharnstoffund Diäthyl-p-to- luol-sulfonamid zu nennen. Als Beispiele ge eigneter Verdünnungsmittel,, die gewünsch- tenfalls zugesetzt werden können, sind Aceton und Nitrobenzol zu nennen.
Wenn das ver wendete Amid bei der angewandten Reak tionstemperatur fest ist, sollte vorzugsweise ein Verdünnungsmittel zugesetzt werden, in welchem das Amid löslich ist.
Die vorliegende Erfindung betrifft eine Variante der Erfindung des Schweiz. Paten tes Nr. 261369 und ist gekennzeichnet durch die Verwendung gewisser cyclischer Amide, nämlich von N-Alkylphthalimidinen, an Stelle der im genannten Patent angeführten Amide.
Das vorliegende Verfahren zur Herstel lung von Schwefelsäureestern der Leukoderi- vate von Küpenfarbstoffen und Anthrachi- nonfarbstoffzwischenprodukten durch Behan deln der entsprechenden Leukoverbindung mit einem Sulfatierungsmittel ist dadurch ge kennzeichnet, dass die Sulfatierung in Gegen wart eines N-Alkylphthalimidins erfolgt.
Die N-Alkylphthalimidine können allge mein durch Reduktion der entsprechenden N-Alkylphthalimide hergestellt werden.
Als Beispiele geeigneter N-Alkylphthali- midine können die N-Äthyl- oder N-Methyl- phthalimidine genannt werden.
Die Erfindung ist in folgenden Beispielen, in welchen die Teile Gewichtsteile sind, aus führlicher erläutert.
<I>Beispiel 1:</I> Man trägt 3,3 Teile 4,5'-Dibenzoylamino- 1,1'-dianthrimid-2,2'-carbazol in eine Lösung von 10 Teilen N-Methyl-phthalimidin in 15 Teilen Acetonitril ein und versetzt hierauf mit 0,5 Teil Methyltriäthylammoniumchlorid und 1,5 Teilen Zinkstaub. Das Gemisch wird in einer Stickstoffatmosphäre bei 50 C während mehrerer Stunden gerührt, bis die Reduktion des Leukosalzes beendet ist. Das Reaktions gemisch wird hierauf in Eis abgekühlt und mit 12 Teilen N - Methylphthalimidin - Schwefel- trioxyd versetzt.
Das Gemisch wird bei 0-5 C während i/2 Stunde gerührt und dann in eine Lösung von 10 Teilen Natriumcarbonat in 250 Teilen Wasser eingegossen. Man entfernt die metallischen Rückstände durch Filtration und destilliert die gelben Filtrate im Vakuum zur Entfernung des Acetonitrils. Der Leuko- schwefelsäureester des Farbstoffes wird mit tels Kaliumchlorid ausgesalzen.
Die N - Methylphthahmidin - Schwefeltri- oxyd - Additionsverbindung kann beispiels weise durch allmähliches Eintragen von flüs sigem Schwefeltrioxyd in eine Lösung von N-Methylphthalimidin in Äthylendichlorid und Isolierung der Additionsverbindung durch Filtration hergestellt werden.
An Stelle des N - Methylphthalimidin- Schwefeltrioxyds kann man das auf ähn liche Weise erhältliche N-Äthylphthalimidin- Schwefeltrioxyd verwenden.
<I>Beispiel 2:</I> Ein Gemisch von 38 Teilen Äthylendi- chlorid, 4,1 Teilen Terephthal-di-4,4'-benzoyl- amino - 1,<B>l'-</B> anthrachinonylamid, <B>3,2</B> Teilen Methyltriäthylammoniumchlorid, 1, 8 Teilen Phenol und 1,5 Teilen Zinkstaub wird in einer Stickstoffatmosphäre bei<B>36'</B> C während 3 %2 Stunden gerührt. Das Gemisch wird hierauf auf 0 C abgekühlt und mit 16 Teilen N-Me- thylphthalimidin - Schwefeltrioxyd versetzt.
Das Gemisch wird bei 0 C während % Stunde gerührt, um das Leukosalz zu verestern. Das Gemisch wird in eine Lösung von 12 Teilen Natriumcarbonat in 250 Teilen Wasser ein getragen. Das Lösungsmittel wird durch De stillation unter vermindertem Druck entfernt. Der Farbstoff wird durch Aussalzen mit Na triumchlorid in Form eines gelben, flockigen Niederschlages erhalten. Wird an Stelle von N - Methylphthalimidin - Schwefeltrioxyd die entsprechende Menge an N-Äthylphthalimi- din-Schwefeltrioxyd verwendet, so gelangt man zum gleichen Resultat.
Additional patent to main patent No. 261369. <B> Process for the production of dyes and intermediate products. </B> In Switzerland. Patent No. 261369 describes a process for the preparation of leuco-sulfuric acid esters of linkable compounds by treating the corresponding leuco compound with a sulfating agent, which is characterized in that the sulfation takes place in the presence of an organic amide derived from a secondary amine,
where you can work in the presence or absence of diluents and the sulfating agent conveniently sulfur trioxide or the addition compound of sulfur trioxide with an organic amide, such as. B. dimethylformamide, or with a tertiary base, such as. B. Picoline, or an ester of chlorosulfonic acid can be used.
The amides used for carrying out the process described in the cited patent include dimethylformamide, diethylformamide, dimethylacetamide, formylpiperidide, tetramethylurea and diethyl-p-toluene-sulfonamide. Examples of suitable diluents which can be added if desired are acetone and nitrobenzene.
If the amide used is solid at the reaction temperature used, a diluent in which the amide is soluble should preferably be added.
The present invention relates to a variant of the invention of Switzerland. Patent No. 261369 and is characterized by the use of certain cyclic amides, namely of N-alkylphthalimidines, in place of the amides mentioned in the patent mentioned.
The present process for the production of sulfuric acid esters of the leuco derivatives of vat dyes and anthraquinone dye intermediates by treating the corresponding leuco compound with a sulfating agent is characterized in that the sulfation takes place in the presence of an N-alkylphthalimidine.
The N-alkylphthalimidines can generally be prepared by reducing the corresponding N-alkylphthalimides.
Examples of suitable N-alkylphthalimidines are the N-ethyl- or N-methyl-phthalimidines.
The invention is illustrated in more detail in the following examples in which parts are parts by weight.
Example 1: 3.3 parts of 4,5'-dibenzoylamino-1,1'-dianthrimide-2,2'-carbazole are added to a solution of 10 parts of N-methyl-phthalimidine in 15 parts Acetonitrile and then mixed with 0.5 part of methyltriethylammonium chloride and 1.5 parts of zinc dust. The mixture is stirred in a nitrogen atmosphere at 50 ° C. for several hours until the reduction of the leuco salt has ended. The reaction mixture is then cooled in ice and 12 parts of N-methylphthalimidine-sulfur trioxide are added.
The mixture is stirred at 0-5 ° C. for 1/2 hour and then poured into a solution of 10 parts of sodium carbonate in 250 parts of water. The metallic residues are removed by filtration and the yellow filtrates are distilled in vacuo to remove the acetonitrile. The leuco-sulfuric acid ester of the dye is salted out with potassium chloride.
The N - methylphthahmidine - sulfur trioxide addition compound can, for example, be prepared by gradually introducing liquid sulfur trioxide into a solution of N-methylphthalimidine in ethylene dichloride and isolating the addition compound by filtration.
Instead of the N-methylphthalimidine-sulfur trioxide, the N-ethylphthalimidine-sulfur trioxide which can be obtained in a similar way can be used.
<I> Example 2: </I> A mixture of 38 parts of ethylene dichloride, 4.1 parts of terephthal-di-4,4'-benzoylamino-1, <B> l'- </B> anthraquinonylamide, 3.2 parts of methyltriethylammonium chloride, 1.8 parts of phenol and 1.5 parts of zinc dust are stirred in a nitrogen atmosphere at 36 ° C. for 3% for 2 hours. The mixture is then cooled to 0 ° C. and 16 parts of N-methylphthalimidine-sulfur trioxide are added.
The mixture is stirred at 0 C for ½ hour in order to esterify the leuco salt. The mixture is carried into a solution of 12 parts of sodium carbonate in 250 parts of water. The solvent is removed by distillation under reduced pressure. The dye is obtained in the form of a yellow, flaky precipitate by salting out with sodium chloride. If the corresponding amount of N-ethylphthalimidine-sulfur trioxide is used instead of N-methylphthalimidine-sulfur trioxide, the same result is obtained.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB282940X | 1949-03-14 | ||
| CH261369T | 1950-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH282940A true CH282940A (en) | 1952-05-15 |
Family
ID=25730466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH282940D CH282940A (en) | 1949-03-14 | 1950-03-11 | Process for the production of dyes and intermediates. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH282940A (en) |
-
1950
- 1950-03-11 CH CH282940D patent/CH282940A/en unknown
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