CH215404A - Process for the preparation of a phthalocyanine series dye. - Google Patents
Process for the preparation of a phthalocyanine series dye.Info
- Publication number
- CH215404A CH215404A CH215404DA CH215404A CH 215404 A CH215404 A CH 215404A CH 215404D A CH215404D A CH 215404DA CH 215404 A CH215404 A CH 215404A
- Authority
- CH
- Switzerland
- Prior art keywords
- dye
- preparation
- phthalocyanine series
- series dye
- acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims 2
- 238000002360 preparation method Methods 0.000 title description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- GGDRDBJGTHPKIY-UHFFFAOYSA-N 4,5-diphenylphthalic acid Chemical compound C=1C=CC=CC=1C=1C=C(C(O)=O)C(C(=O)O)=CC=1C1=CC=CC=C1 GGDRDBJGTHPKIY-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/062—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide having alkyl radicals linked directly to the Pc skeleton; having carboxylic groups directly linked to the skeleton, e.g. phenyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
Verfahren zur Herstellung eines Farbstoffes der Phthaloeyaninreihe. Es wurde gefunden, dass man neue Phthalocyanine durch Erhitzen solcher Phthalsäuren, welche in 4- und 5-,Stellung durch Arylreste substituiert sind, mit Kup fersalzen und Ammoniak abgebenden Mitteln wie Harnstoff oder amidosulfonsauren Sal zen, zum Beispiel dem Ammoniumsalz her stellen kann.
Vorzugsweise wird bei Gegen wart geringer Mengen von die Reaktion för- .dernden Stoffen wie Phosphaten, Yanadina- ten und Molybdaten ;gearbeitet. Die neuen Phthalocyanine stellen grüne Pigmente dar, die als solche als Pigmentfarbstoffe verwandt werden können.
Durch 'S.ulfieren erhält man wasserlösliche Sulfosäuren.
Die als Ausgangsmaterial benutzten 4;5- Diarylphthals5,uren können auf dem Wege der "Diensynthese" leicht nach folgendem Schema erhalten werden:
EMI0001.0034
Man addiert zu diesem Zweck ein 2,3-Di- arylbutadien (1) an Maleineäureanhydrid (2) und unterwirft das dabei erhaltene 4,5 - Diaryl - tetrahydrophthalsäureanhydrid (3) der Dehydrierung,
beispielsweise durch Erhitzen. mit Schwefel, wobei die 4;5-Di- arylphthalsäuren erhalten werden.
Gegenstand des vorliegenden Patentes ist nun die Herstellung eines speziellen Farb stoffes der Phtha.locyaninreihe durch Er hitzen von 4,5-Diphenylphthalsäure mit Harnstoff und einem Kupfersalz.
Es emp fiehlt sich, in Gegenwart eines Katalysators wie Ammoniummolybdat zu arbeiten. Der erhältliche neue Farbstoff stellt ein grünes bronzierendes Pulver dar, welches in allen organischen Lösungsmitteln praktisch unlös lich und in konzentrierter Schwefelsäure Iös- lich ist. Er kann als Pigmentfarbstoff be nutzt werden.
<I>Beispiel:</I> Man erhitzt ein inniges Gemisch aus 100 Gewichtsteilen 4,5-Diphenylphthalsäure (aus Acetonnitril farblose Prismen vom Schmelzpunkt 221 unter Schäumen), 300 Gewichtsteilen Harnstoff, 20 Gewichtsteilen Kupferchlorid und 2 Gewiehtstei,len Ammo- niummolybdat bis zur Beendigung der Farb- atoffbildung auf 230-250'. Danach kocht,
man die Schmelze mit verdünnter Natron lauge und verdünnter .Salzsäure aus und er hält das Oktophenyl-Kupferphthalocya,nin als grünes bronzierendes Pulver. Das Pro dukt ist in allen organischen Usungsmit- teln nahezu unlöslich.
In konzentrierter Schwefelsäure löst es sich mit braunviolet ter Farbe. Beim Eingiessen dieser Lösung in Wasser erhält man leuchtend grüne Flocken.
Process for the preparation of a dye of the phthaloeyanine series. It has been found that new phthalocyanines can be produced by heating phthalic acids which are substituted in the 4- and 5- positions by aryl radicals with copper salts and ammonia-releasing agents such as urea or amidosulfonic acid salts, for example the ammonium salt.
It is preferable to work in the presence of small amounts of substances that promote the reaction, such as phosphates, yanadinates and molybdates. The new phthalocyanines are green pigments that can be used as such as pigment dyes.
Water-soluble sulfonic acids are obtained by sulfating.
The 4,5-diarylphthalic acids used as starting material can easily be obtained by the "diene synthesis" according to the following scheme:
EMI0001.0034
For this purpose, a 2,3-diarylbutadiene (1) is added to maleic anhydride (2) and the 4,5-diaryl-tetrahydrophthalic anhydride (3) obtained is subjected to dehydrogenation,
for example by heating. with sulfur, the 4; 5-diarylphthalic acids being obtained.
The subject of the present patent is the production of a special dye of the Phtha.locyanin series by heating 4,5-diphenylphthalic acid with urea and a copper salt.
It is recommended to work in the presence of a catalyst such as ammonium molybdate. The new dye available is a green, bronzing powder, which is practically insoluble in all organic solvents and soluble in concentrated sulfuric acid. It can be used as a pigment.
<I> Example: </I> An intimate mixture of 100 parts by weight of 4,5-diphenylphthalic acid (made of acetonitrile colorless prisms with a melting point of 221 with foaming), 300 parts by weight of urea, 20 parts by weight of copper chloride and 2 parts by weight of ammonium molybdate is heated to end the dye formation to 230-250 '. After that cooks
you remove the melt with dilute sodium hydroxide solution and dilute hydrochloric acid and it keeps the octophenyl copper phthalocyanine as a green, bronzing powder. The product is almost insoluble in all organic solvents.
It dissolves in concentrated sulfuric acid with a brown-violet color. When this solution is poured into water, bright green flakes are obtained.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE215404X | 1938-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH215404A true CH215404A (en) | 1941-06-30 |
Family
ID=5823785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH215404D CH215404A (en) | 1938-08-09 | 1939-07-21 | Process for the preparation of a phthalocyanine series dye. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH215404A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2681344A (en) * | 1950-01-12 | 1954-06-15 | Ici Ltd | Coloring matters of the tetra-aza porphin series |
-
1939
- 1939-07-21 CH CH215404D patent/CH215404A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2681344A (en) * | 1950-01-12 | 1954-06-15 | Ici Ltd | Coloring matters of the tetra-aza porphin series |
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