DE852725C - Process for the production of Kuepen dyes - Google Patents
Process for the production of Kuepen dyesInfo
- Publication number
- DE852725C DE852725C DEF3829D DEF0003829D DE852725C DE 852725 C DE852725 C DE 852725C DE F3829 D DEF3829 D DE F3829D DE F0003829 D DEF0003829 D DE F0003829D DE 852725 C DE852725 C DE 852725C
- Authority
- DE
- Germany
- Prior art keywords
- dyes
- copper
- parts
- production
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000975 dye Substances 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000000984 vat dye Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- -1 alkali metal cyanide Chemical class 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001049 brown dye Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical group OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical class C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/12—Perinones, i.e. naphthoylene-aryl-imidazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Küpenfarbstoffen Durch Kondensation von i, .I, 5, 8-Naphthalintetracarbonsäure oder deren An hydrid mit ortho-Diaminen nach dem Verfahren der Patentschrift 43o632 und der Zusätze 438 197, 456236 und 457 980 erhält man Gemische der isomeren Farbstoffe (s. nebenste'hend), worin R den Rest eines substituierten oder nichtsubstituierten aromatischen Kohlenwasserstoffes bedeutet.Process for the preparation of vat dyes By condensation of i, .I, 5, 8-naphthalenetetracarboxylic acid or its anhydride with ortho-diamines according to the process of patent 43o632 and the additives 438 197, 456236 and 457 980 , mixtures of the isomeric dyes are obtained (s . adjacent), in which R denotes the radical of a substituted or unsubstituted aromatic hydrocarbon.
An der Gewinnung der einzelnen Farbstoffe aus den Gemischen der Isomeren besteht ein erhebliches technisches Interesse. In den Patentschriften 536911, 538314, 56721o, 607945 und 638339 sind Verfahren zur Trennung der Isomerengemische beschrieben.There is considerable technical interest in obtaining the individual dyes from the mixtures of isomers. In the patents 536911, 538314, 56721o, 607945 and 638339 processes for separating the isomer mixtures are described.
Es wurde nun gefunden, daß man die in den obigen Formeln gekennzeichneten Farbstoffe je für sich unter Vermeidung der Bildung von Isomeren- gemischen in sehr guter Ausbeute herstellen kann, wenn man i, 5-Dibalogennaphthalin-4, 8-diarylimidazole bzw. i, 4-Dihalogennaphthalin-5, 8-diarylimidazole entweder mit Alkalicyanid und Kupfercyanür in wäßriger Suspension oder mit Kupfercyanür unter Zusatz eines organischen Lösungs- oder Verdünnungsmittels, wie Benzylcyanid, Pyridin, Chinolin, erhitzt und die gegebenenfalls auftretenden Zwischenprodukte durch Behandeln mit verseifenden Mitteln, wie konzentrierter Schwefelsäure, oder mit oxydierenden Mitteln, wie Chlorlauge, in die Farbstoffe überführt. Die Reaktion verläuft wahrscheinlich gemäß den folgenden Formeln: Zwischenverbindung ohne Bildung einer Zwischenverbindung Die als Ausgangsstoffe dienenden Dihalogennaphthalindiarylimidazole können z. B. auf folgende Weise erhalten werden: Es ist nicht immer notwendig, erst das Säurechlorid darzustellen; vielmehr können durch Kondensation der Dihalogennaphthalindicarbonsäuren mit ortho-Diamin direkt die gewünschten Diimidazole erhalten werden.It has now been found that the dyes identified in the above formulas can be used individually, avoiding the formation of isomeric Mixtures can be produced in very good yield if i, 5-dibalogennaphthalene-4, 8-diarylimidazoles or i, 4-dihalogenaphthalene-5, 8-diarylimidazoles either with alkali metal cyanide and copper cyanide in aqueous suspension or with copper cyanide with the addition of an organic solution - Or diluents, such as benzyl cyanide, pyridine, quinoline, and the intermediate products which may occur are converted into the dyes by treatment with saponifying agents, such as concentrated sulfuric acid, or with oxidizing agents, such as sodium chloride solution. The reaction will likely proceed according to the following formulas: Interconnection without the formation of an interconnection Serving as starting materials Dihalogennaphthalindiarylimidazole can, for. B. can be obtained in the following way: It is not always necessary to prepare the acid chloride first; rather, the desired diimidazoles can be obtained directly by condensation of the dihalogenaphthalenedicarboxylic acids with ortho-diamine.
Da die einzelnen bei der Kondensation von 1, 4, 5, 8-Naphthalintetracarbonsäure mit ortho-Diaminen gemäß der Patentschrift 430 632 als Gemisch anfallenden Isomeren eine ganz verschieden große praktische Bedeutung besitzen, kommt dem neuen Verfahren ein erheblicher technischer Wert zu. Beispiele 1. 25 Gewichtsteile i, 4-Dibromnaphthalin-5, 8-dibenzimi,dazol, 2o Gewichtsteile Kupfercyanüt (7oo/oig), 15 Gewichtsteile Kaliumcyanid, Zoo Gewichtsteile Wasser werden im Autoklaven unter Rühren 2 Stunden auf 16o bis 170° geheizt. Nach Erkalten wird mit Salzsäure gesäuert und vom gebildeten Niederschlag abgesaugt. Dieser Niederschlag, der vermutlich eine Zwischenverbindung von der oben angegebenen Formel darstellt, wird zur Entfernung von Kupferverbindungen mit warmer verdünnter Salpetersäure behandelt und abgesaugt. Er stellt ein rotes Pulver dar, das sich in verdünnter Natronlauge mit gelbroter Farbe löst und mit Alkalihydrosulfit eine grünlichrote Küpe mit roter Fluoreszenz bildet. Durch Behandlung mit Chlorlauge erhält man den entsprechenden Küpenfarbstoff. Dieser stimmt in seinen Eigenschaften mit dem blaustichigrot färbenden, im Beispiel i der Patentschrift 536 9i i beschriebenen Farbstoff vollkommen überein.Since the individual in the condensation of 1, 4, 5, 8-naphthalenetetracarboxylic acid isomers obtained as a mixture with ortho-diamines according to patent specification 430 632 have very different levels of practical importance, comes the new process a considerable technical value to it. Examples 1. 25 parts by weight of 1,4-dibromonaphthalene-5, 8-dibenzimi, dazol, 2o parts by weight of copper cyanide (7oo / oig), 15 parts by weight of potassium cyanide, Zoo parts by weight of water are in the autoclave with stirring to 16o for 2 hours 170 ° heated. After cooling, it is acidified with hydrochloric acid and vomited formed precipitate sucked off. This precipitate, which is believed to be an intermediate compound of the above formula is used to remove copper compounds treated with warm dilute nitric acid and suctioned off. He puts a red one Powder that dissolves in dilute caustic soda with a yellow-red color and with Alkali hydrosulfite forms a greenish-red vat with red fluorescence. Through treatment the corresponding vat dye is obtained with sodium chloride solution. This is true in his Properties with the bluish red coloring, in example i of the patent 536 9i i described dye completely match.
2. 26 Teile i, 5-Dichlornaphthalin-4, 8-dibenzimidazol, 18 Teile Kupfercyanür werden in 25o Teilen Benzylcyanid so lange zum Sieden erhitzt, bis (las Kupfercyanür in Lösung gegangen ist. Nach Erkalten wird abgesaugt und der Rückstand wie in Beispiel i mit verdünnter Salpetersäure behandelt. Man erhält ein orangefarbenes Kristallpulver, welches mit dem im Beispiel i der Patentschrift 536 9i i beschriebenen identisch ist.2. 26 parts of i, 5-dichloronaphthalene-4, 8-dibenzimidazole, 18 parts of copper cyanur are heated to boiling in 250 parts of benzyl cyanide until (read copper cyanide has gone into solution. After cooling, it is suctioned off and the residue as in the example i treated with dilute nitric acid. An orange-colored crystal powder is obtained, which is identical to that described in example i of patent 536 9i i is.
3. Verwendet man an Stelle von i, 4-Dibromnaphthalin-5, 8-dibenzimidazol des Beispiels i hier 27,5 Gewichtsteile i, 4-Dibromdi-(4', 4'-diät'hoxy)-benzimidazol und verfährt wie in Beispiel t angegeben, so erhält man einen, blaustichigbraunen Farbstoff, wie er im Beispiel 3 der Patentschrift 567 21o beschrieben ist.3. Is used in place of 1,4-dibromonaphthalene-5, 8-dibenzimidazole of Example i here 27.5 parts by weight of 1,4-dibromodi (4 ', 4'-diet'hoxy) benzimidazole and if you proceed as indicated in example t, you get a blue-tinged brown Dye as described in Example 3 of Patent 567 21o.
4. 28 Gewichtsteile i, 5-Dichlornaphthalin-4, 8-di-(4 , 4 "-diäthoxy)-benzimidazol werden mit 18 Gewichtsteilen Kupfercyanür (7oo/oig) in Zoo Gewichtsteilen Benzylcyanid so lange zum Sieden erhitzt, bis das Kupfercyanür in Lösung gegangen ist. Nach der im Beispiel 2 angegebenen Aufarbeitung erhält man einen gelbstichigbraunen Farbstoff, der mit demjenigen des Beispiels 3 der Patentschrift 567 210 übereinstimmt.4. 28 parts by weight of 1,5-dichloronaphthalene-4, 8-di- (4,4 "-diethoxy) -benzimidazole 18 parts by weight of copper cyanide (7oo / oig) in zoo parts by weight of benzyl cyanide Heated to the boil until the copper cyanur has dissolved. After in Example 2 work-up gives a yellowish brown dye, which corresponds to that of Example 3 of patent 567 210.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF3829D DE852725C (en) | 1941-08-01 | 1941-08-01 | Process for the production of Kuepen dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF3829D DE852725C (en) | 1941-08-01 | 1941-08-01 | Process for the production of Kuepen dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE852725C true DE852725C (en) | 1952-10-16 |
Family
ID=7083986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF3829D Expired DE852725C (en) | 1941-08-01 | 1941-08-01 | Process for the production of Kuepen dyes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE852725C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4181805A (en) * | 1978-03-08 | 1980-01-01 | Hoechst Aktiengesellschaft | Process for the preparation of pure sodium hydroxide addition compounds of cis-isomers of naphthoylene-bis-benzimidazoles |
-
1941
- 1941-08-01 DE DEF3829D patent/DE852725C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4181805A (en) * | 1978-03-08 | 1980-01-01 | Hoechst Aktiengesellschaft | Process for the preparation of pure sodium hydroxide addition compounds of cis-isomers of naphthoylene-bis-benzimidazoles |
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