DE2333925C2 - Process for the preparation of iron complexes of tetraazaannulenes - Google Patents
Process for the preparation of iron complexes of tetraazaannulenesInfo
- Publication number
- DE2333925C2 DE2333925C2 DE19732333925 DE2333925A DE2333925C2 DE 2333925 C2 DE2333925 C2 DE 2333925C2 DE 19732333925 DE19732333925 DE 19732333925 DE 2333925 A DE2333925 A DE 2333925A DE 2333925 C2 DE2333925 C2 DE 2333925C2
- Authority
- DE
- Germany
- Prior art keywords
- iron
- diamino
- dark brown
- parts
- benzene
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
A einen gegebenenfalls substituierten zweiwertigen Rest bedeutet, der den MolekülteilA denotes an optionally substituted divalent radical which forms the part of the molecule
C = CC = C
zu einem aromatischen oder heterocyclischen Ring vervollständigt und R' und R2 unabhängig voneinander Wasserstoff, Alkyl oder Phenyl sind, dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formelis completed to form an aromatic or heterocyclic ring and R 'and R 2 are independently hydrogen, alkyl or phenyl, characterized in that compounds of the general formula
R2 R 2
mit Verbindungen der allgemeinen Formel NH2 with compounds of the general formula NH 2
-X-X
NH2 und mit Eisen abgebenden Mitteln umsetzt.NH 2 and implemented with iron releasing agents.
Die Erfindung betrifft das im Anspruch gekennzeichnete Verfahren. Reste A sind beispielsweiseThe invention relates to the method characterized in the claim. A radicals are for example
N NN N
und insbesondereand particularly
ClCl
CH3 CH 3
CH3 CH 3
CH3 CH 3
OCH3 OCH 3
BrBr
oderor
65 ι 265 ι 2
Alkylreste R und R sind vorzugsweise Methyl.Alkyl radicals R and R are preferably methyl.
Von besonderer technischer Bedeutung sind erfindungsgemäß herstellbare Verbindungen der Formel IaOf particular technical importance are compounds of the formula Ia which can be prepared according to the invention
(Ia) R4'(Ia) R 4 '
in der ίοin the ίο
R3 Wasserstoff, Chlor, Brom, Methyl, Methoxy oder Äthoxy und
R4 Wasserstoff, Chlor, Brom, Methyl, Methoxy oder ÄthoxyR 3 is hydrogen, chlorine, bromine, methyl, methoxy or ethoxy and
R 4 is hydrogen, chlorine, bromine, methyl, methoxy or ethoxy
bedeuten. ismean. is
Die Verbindungen der Formel I sind wertvoll^ Redox-Katalysatoren, die sich insbesondere als Sauerstoffüberträger
eignen.
Diamine der FormelThe compounds of the formula I are valuable redox catalysts which are particularly suitable as oxygen carriers.
Diamines of the formula
NH2 20 ^NH 2 20 ^
NH2 25 |NH 2 25 |
sind beispielsweise: 2,3-Diaminonaphthalin, 2,3-Diaminochinoxalin, l,2-Diamino-4-nitrobenzol und vorzugsweise o-Phenylendiamin, 4-Methyl-, 4-Chlor-, 4-Brom-, 4-Methoxy-, 4,5-Dichlor- oder 4,5-Dimethyl-l,2-diaminobenzol. are for example: 2,3-diaminonaphthalene, 2,3-diaminoquinoxaline, 1,2-diamino-4-nitrobenzene and preferably o-phenylenediamine, 4-methyl-, 4-chloro-, 4-bromo-, 4-methoxy-, 4,5-dichloro- or 4,5-dimethyl-1,2-diaminobenzene.
Eisen abgebende Mittel sind z. B. Eisensalze schwacher anorganischer oder organischer Säuren, wie Eisencarbonat, Eisenacetat, Eisenlactat, -oxalat, -zitrat, -tartrat oder -gluconat. Besonders sind allgemein Eisensalze mehrbasiger organischer Säuren sowie von Oxycarbonsäuren geeignet. Ferner sind Verbindungen geeignet, die Eisen in komplexer Bindung enthalten, z. B. Eisenacetylacetonate, die wegen der Flüchtigkeit der Liganden bei »Iron releasing agents are z. B. iron salts of weak inorganic or organic acids, such as iron carbonate, Iron acetate, iron lactate, oxalate, citrate, tartrate or gluconate. Iron salts are particularly common polybasic organic acids as well as oxycarboxylic acids are suitable. Furthermore, compounds are suitable that Contain iron in complex bonds, e.g. B. iron acetylacetonate, which because of the volatility of the ligands in »
der Bildung der Annulene besonders brauchbar sind. Weiterhin können auch Eisenhydroxide zur Herstellung !the formation of annulenes are particularly useful. Furthermore, iron hydroxides can also be used for the production!
der Verbindungen der Formel I verwendet werden.of the compounds of the formula I can be used.
Die Herstellung der Eisenkomplexe wird zweckmäßigerweise durch Erhitzen der Isoxazole und Diamine zusammen mit dem eisenabgebenden Mittel auf ungefähr 50 bis 220°C in organischen Lösungsmitteln vorgenommen. Geeignete organische Lösungsmittel sind z. B. Alkohole, Ketone, Phenole, cyclische Äther, beipielsweise Dioxan und Tetrahydrofuran., Glykole, Glykoläther, Carbonsäureamide, z. B. N,N-Dimethylformamid, N-Methylpyrrolidon, Dimethylsulfoxid, alkyl-, halogen- oder nitrosubstituierte Kohlenwasserstoffe sowie Mischungen dieser Lösungsmittel.The iron complexes are conveniently prepared by heating the isoxazoles and diamines carried out together with the iron-releasing agent to about 50 to 220 ° C in organic solvents. Suitable organic solvents are e.g. B. alcohols, ketones, phenols, cyclic ethers, for example dioxane and tetrahydrofuran., glycols, glycol ethers, carboxamides, e.g. B. N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, alkyl, halogen or nitro substituted hydrocarbons and mixtures of these solvents.
Zur Erzielung einer vollständigen Metallisierung muß man das metallabgebende Mittel in mindestens der stöchiometrischen Menge zugeben, das heißt man benötigt für 1 Mol des gebildeten Eisenkomplexes mindestens 1 Grammatom des Metalles in Form des metallabgebenden Mittels; zweckmäßigerweise verwendet man jedoch einen Überschuß an Eisenverbindung.To achieve complete metallization, the metal donor must be in at least the Add a stoichiometric amount, that is, it is required for 1 mol of the iron complex formed at least 1 gram atom of the metal in the form of the metal donor; appropriately used However, you have an excess of iron compound.
Nach beendeter Umsetzung werden die schwerlöslichen Eisenkomplexverbindungen aus dem Reaktionsgemisch abgetrennt und aufgearbeitet; sie können, soweit erforderlich, durch Waschen und Auskochen mit Lösungsmitteln nachgereinigt werden.After the reaction has ended, the sparingly soluble iron complex compounds are separated off from the reaction mixture and worked up; they can, if necessary, by washing and boiling with Be cleaned with solvents.
Einzelheiten der Herstellung sind den Beispielen zu entnehmen.Details of the preparation can be found in the examples.
Die schwerlöslichen, rotbraunen bis schwarzen Eisenkomplexverbindungen fallen bei Verwendung von schwerlöslichen Eisenverbindungen, wie Hydroxiden, Carbonaten, Acetaten oder Oxalaten, in der Regel nicht analysenrein an, die katalytische Aktivität ist jedoch ausgezeichnet.The sparingly soluble, red-brown to black iron complex compounds fall when using poorly soluble iron compounds such as hydroxides, carbonates, acetates or oxalates, as a rule, do not analytically pure, but the catalytic activity is excellent.
Für die Verwendung als Katalysatoren können die neuen Metallkomplexverbindungen noch Formulierungsverfahren unterworfen werden, bei denen Zerkleinerungs-, Dispergier- oder Rekristallisationsprozesse ablaufen. Je nach Verwendungszweck können die Eisenkomplexverbindungen in reiner Form oder in Form von Zubereitungen auf bzw. in Trägermaterialien der verschiedensten Art, z. B. Aktivkohle, Ruß, Kieselgur, Kieselgel, Aluminiumoxid, als Ionenaustauscher verwendeten Stoffen oder Kunststoffen, verwendet werden. Der jeweilige Verwendungbzweck entscheidet dabei über die geeignetste Form.For use as catalysts, the new metal complex compounds can also be used in formulation processes are subjected to grinding, dispersing or recrystallization processes expire. Depending on the intended use, the iron complex compounds can be in pure form or in the form of preparations on or in carrier materials of various kinds, eg. B. activated carbon, soot, kieselguhr, Silica gel, aluminum oxide, substances or plastics used as ion exchangers can be used. The respective purpose of use decides on the most suitable form.
Aus der DE-OS 15 69 667, dem JACS 94,13 (1972), und dem Journal of Catalysis 28,8-19 (1973), sind schon Verfahren zur Herstellung von Metallkomplexen des Tetraazaannulens bekannt, bei denen Propargylaldehyd anstelle von Isoxazol als Ausgangsmaterial verwendet wird. Es hat sich jedoch überraschenderweise gezeigt, daß man mit Isoxazol katalytisch weitaus wirksamere Tetraazaannulen-Fe-Komplexe erhält. Isoxazole sind schon bei der Herstellung von Corrinen und Semicorrinen verwendet worden [C. A. 76,46 359 w und 46 362 s (1972), und 79,13 711 n(1973)]. Diese Verbindungen weichenjedoch strukturell so sehr von den Tetraazaannulenen ab, daß die Verwendung von Isoxazol als Ausgangsmaterial beim erfindungsgemäßen Verfahren nicht nahegelegt wird.From DE-OS 15 69 667, JACS 94.13 (1972), and the Journal of Catalysis 28.8-19 (1973) are already Process for the preparation of metal complexes of tetraazaannulene known in which propargylaldehyde is used as the starting material instead of isoxazole. However, it has surprisingly been found that tetraazaannulene-Fe complexes which are catalytically far more effective with isoxazole are obtained. Isoxazoles are nice has been used in the manufacture of corrines and semicorrines [C. A. 76.46 359 w and 46 362 s (1972), and 79.13,711n (1973)]. Structurally, however, these compounds differ so much from the tetraazaannulenes that that the use of isoxazole as a starting material in the process according to the invention is not suggested will.
Die im folgenden genannten Teile und Prozentangaben beziehen sich auf das Gewicht. Raumteile verhalten sich zu Gewichtsteilen wie das Liter zum Kilogramm.The parts and percentages given below relate to weight. Behave parts of the room to parts by weight like the liter to the kilogram.
1010
1515th
21,6 Teile o-Phenylendiamin werden bei Raumtemperatur in 100 Volumteilen Dimethylformamid gelöst und langsam mit 13,8 Teilen Isoxazol (in alkoholischer Lösung) versetzt. Nach 15 Minuten bei 300C werden 11,6 Teile Eisencarbonal zugefügt und die Mischung 2 Stunden auf 1200C erhitzt Nach dem Absaugen, Auswaschen mit Dimethylformamid ud<h Methanol und Trocknen erhält man 9,2 Teile eines dunkelbraunen Pulvers mit hoher Katalyseaktivität.21.6 parts of o-phenylenediamine are dissolved in 100 parts by volume of dimethylformamide at room temperature and 13.8 parts of isoxazole (in alcoholic solution) are slowly added. After 15 minutes at 30 ° C., 11.6 parts of iron carbonate are added and the mixture is heated to 120 ° C. for 2 hours. After suctioning off, washing with dimethylformamide and methanol and drying, 9.2 parts of a dark brown powder with high catalytic activity are obtained.
24,4 Teile l-Methyl-3,4-diamino-benzoI werden bei Raumtemperatur in 100 Volumteilen Dimethylformamid gelöst und langsam mit 13,8 Teilen Isoxazol (in alkoholischer Lösung) versetzt. Nach 15 Minuten bei 30°C werden 19 Teile bas. Eisenacetat zugesetzt, und die Mischung wird 2 Stunden auf 1200C erhitzt. Nach dem Aufarbeiten wie im Beispiel 12 erhält man ungefähr 6 Teile eines dunkelbraunen Pulvers mit hoher Katalyseaktivität. 24.4 parts of 1-methyl-3,4-diamino-benzoI are dissolved in 100 parts by volume of dimethylformamide at room temperature, and 13.8 parts of isoxazole (in alcoholic solution) are slowly added. After 15 minutes at 30 ° C, 19 parts are bas. Iron acetate was added and the mixture is heated for 2 hours at 120 0 C. After working up as in Example 12, about 6 parts of a dark brown powder with high catalytic activity are obtained.
Analog den Beispielen 1 und 2 erhält man, ausgehend von Isoxazol, folgende weitere Komplexe, die ebenfalls hohe katalvtische Aktivität haben:Analogously to Examples 1 and 2, starting from isoxazole, the following additional complexes are obtained, which are also have high catalvic activity:
2020th
2525th
3030th
3535
Beispiel Aromatisches DiaminExample aromatic diamine
EisenverbindungIron compound
Farbe des
EisenkomplexesColor of
Iron complex
3 o-Phenylendiamin3 o-phenylenediamine
4 o-Phenylendiamin4 o-phenylenediamine
5 4-Chlor-l,2-diamino-benzol5 4-chloro-1,2-diamino-benzene
6 4-Chlor-l, 2-diamino-benzol6 4-chloro-1,2-diamino-benzene
7 4-Chlor-l,2-diamino-benzol7 4-chloro-1,2-diamino-benzene
8 4-Chlor-l,2-diamino-benzol8 4-chloro-1,2-diamino-benzene
9 4-Methyl-l,2-diamino-benzol9 4-methyl-1,2-diamino-benzene
10 4-Methyl-l,2-diamino-benzol10 4-methyl-1,2-diamino-benzene
11 4-Methyl-i,2-diamino-benzoi11 4-methyl-i, 2-diamino-benzenes
12 4,5-Dimethyl-l,2-diamino-benzol12 4,5-dimethyl-1,2-diamino-benzene
13 4,5-Dimethyl-l,2-diamino-benzol.13 4,5-dimethyl-1,2-diamino-benzene.
14 4,5-Dimethyl-l ,2-diamino-benzol14 4,5-dimethyl-1,2-diamino-benzene
15 4,5-Dimethyl-l,2-diamino-benzol15 4,5-dimethyl-1,2-diamino-benzene
16 4,5-Dimethyl-l,2-diamino-benzol16 4,5-dimethyl-1,2-diamino-benzene
bas. Eisenacetatbas. Iron acetate
Eisen(III)-hydroxydIron (III) hydroxide
bas. Eisenacetatbas. Iron acetate
EisencarbonatIron carbonate
Eisen(II, III)-hydroxydIron (II, III) hydroxide
Eisen(III)-hydroxydIron (III) hydroxide
EisencarbonatIron carbonate
Eisen(II, III)-hydroxydIron (II, III) hydroxide
Eisen(III)-hydroxydIron (III) hydroxide
EisenoxalatIron oxalate
bas. Eisenacetatbas. Iron acetate
EisencarbonatIron carbonate
Eisen(II, III)-hydroxydIron (II, III) hydroxide
Eisen(III)-hydroxydIron (III) hydroxide
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
grün-braungreen Brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
dunkelbraundark brown
4040
4545
5050
5555
6060
6565
Claims (1)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732333925 DE2333925C2 (en) | 1973-07-04 | 1973-07-04 | Process for the preparation of iron complexes of tetraazaannulenes |
| CH1028573A CH592640A5 (en) | 1973-07-04 | 1973-07-13 | |
| IT5157773A IT989958B (en) | 1973-07-04 | 1973-07-20 | TETRAAZAAN NULENI IRON COMPLEXES |
| DD17241773A DD107041A5 (en) | 1973-07-04 | 1973-07-20 | |
| FR7328011A FR2237891B1 (en) | 1973-07-04 | 1973-07-31 | |
| BE134170A BE803141A (en) | 1973-07-04 | 1973-08-02 | TETRA-AZA-ANNULENES IRON COMPLEXES, THEIR PREPARATION AND USES |
| JP9007073A JPS5037794A (en) | 1973-07-04 | 1973-08-13 | |
| GB3955873A GB1435760A (en) | 1973-07-04 | 1973-08-15 | Iron complexes of tetraazaannulenes |
| US05/451,034 US3936445A (en) | 1973-07-04 | 1974-03-14 | Process for the production of iron complexes of tetraazaannulenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732333925 DE2333925C2 (en) | 1973-07-04 | 1973-07-04 | Process for the preparation of iron complexes of tetraazaannulenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2333925A1 DE2333925A1 (en) | 1975-01-30 |
| DE2333925C2 true DE2333925C2 (en) | 1986-08-21 |
Family
ID=5885867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19732333925 Expired DE2333925C2 (en) | 1973-07-04 | 1973-07-04 | Process for the preparation of iron complexes of tetraazaannulenes |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5037794A (en) |
| BE (1) | BE803141A (en) |
| CH (1) | CH592640A5 (en) |
| DD (1) | DD107041A5 (en) |
| DE (1) | DE2333925C2 (en) |
| FR (1) | FR2237891B1 (en) |
| GB (1) | GB1435760A (en) |
| IT (1) | IT989958B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722905A (en) * | 1981-12-01 | 1988-02-02 | National Research Development Corporation | Semiconductors |
| DE10142104A1 (en) * | 2001-08-30 | 2003-03-27 | Reiner Sustmann | New dibenzo-tetraaza-14-annulene derivatives and their metal complexes, are peroxide scavengers useful e.g. as drugs for treating inflammation or cancer, as antioxidants or as catalysts |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1569667A1 (en) * | 1967-03-23 | 1971-01-14 | Basf Ag | Process for the production of metal complex dyes |
-
1973
- 1973-07-04 DE DE19732333925 patent/DE2333925C2/en not_active Expired
- 1973-07-13 CH CH1028573A patent/CH592640A5/xx not_active IP Right Cessation
- 1973-07-20 IT IT5157773A patent/IT989958B/en active
- 1973-07-20 DD DD17241773A patent/DD107041A5/xx unknown
- 1973-07-31 FR FR7328011A patent/FR2237891B1/fr not_active Expired
- 1973-08-02 BE BE134170A patent/BE803141A/en unknown
- 1973-08-13 JP JP9007073A patent/JPS5037794A/ja active Pending
- 1973-08-15 GB GB3955873A patent/GB1435760A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH592640A5 (en) | 1977-10-31 |
| IT989958B (en) | 1975-06-10 |
| BE803141A (en) | 1974-02-04 |
| FR2237891A1 (en) | 1975-02-14 |
| DE2333925A1 (en) | 1975-01-30 |
| JPS5037794A (en) | 1975-04-08 |
| DD107041A5 (en) | 1974-07-12 |
| FR2237891B1 (en) | 1983-07-18 |
| GB1435760A (en) | 1976-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2333925C2 (en) | Process for the preparation of iron complexes of tetraazaannulenes | |
| DE2610675C3 (en) | Process for the preparation of cyanazo dyes | |
| DE1770579C3 (en) | Process for the preparation of 3- (4-methyl-1-piperazinyliminomethyl) rifamycin-SV | |
| DE1300948B (en) | Process for the preparation of benzimidazolium compounds | |
| DE2210074B2 (en) | Process for the preparation of oxazine dyes | |
| DE2518587A1 (en) | PROCESS FOR THE PRODUCTION OF BASIC OXAZINE DYES | |
| DE3432015A1 (en) | METHOD FOR PRODUCING AMINES | |
| DE3517273A1 (en) | METHOD FOR PRODUCING AZO COMPOUNDS | |
| DE957506C (en) | Process for the production of cobalt-containing azo dyes | |
| DE2533960A1 (en) | NEW 2-HYDROXYNAPHTHALIN-1-ALDEHYDE, THE METHOD FOR MANUFACTURING IT AND ITS USE | |
| DE2933962A1 (en) | 2-Substd.-4,5-di:chloro-imidazole derivs. - useful as fungicides and antimycotics, prepd. by reacting aldehyde with di:cyanide and hydrogen chloride | |
| DE2617807C2 (en) | 3-Amino-5-nitro-benzisothiazole (2,1) derivatives | |
| DE2329653A1 (en) | NEW 5-NITROFURANIC COMPOUNDS | |
| DE2428452C3 (en) | Process for the preparation of amino-nitro-dihydroxy-anthrachtnonen | |
| DE2413189C2 (en) | Process for the preparation of benzohydroquinones | |
| DE1011546B (en) | Process for the preparation of chromium complex compounds from azo dye mixtures | |
| DE1419334C3 (en) | 4- (2H-Naphtho square brackets on 1,2-square brackets for triazol-2-yl) -2-stilbene carboxylic acid esters and their use as brighteners | |
| AT273106B (en) | Process for the preparation of new benzoxazole compounds | |
| DE2121570A1 (en) | Disperse dyes of the anthraquinone series | |
| AT236383B (en) | Process for the preparation of new benzo-1,3-oxazine-dione (2,4) | |
| AT228214B (en) | Process for the preparation of new benzo-1,3-oxazine-dione (2,4) | |
| DE2423092A1 (en) | PROCESS FOR THE PREPARATION OF THE SHIP'S BASES OF 2-FORMYL-QUINOXALIN-1,4-DIOXYDE | |
| DE1620498C (en) | Pteridines and process for their preparation | |
| DE2621450C3 (en) | Process for the preparation of N-arylaminocarboxylic acid nitriles | |
| AT202150B (en) | Process for the preparation of new phenazine derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OD | Request for examination | ||
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition |