DE594084C - Process for the preparation of condensation products of quaternary pyridine compounds - Google Patents
Process for the preparation of condensation products of quaternary pyridine compoundsInfo
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- DE594084C DE594084C DEC47084D DEC0047084D DE594084C DE 594084 C DE594084 C DE 594084C DE C47084 D DEC47084 D DE C47084D DE C0047084 D DEC0047084 D DE C0047084D DE 594084 C DE594084 C DE 594084C
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
Description
Verfahren zur Darstellung von Kondensationsprodukten quaternärer Pyridinverbindungen Es wurde gefunden, daß gewissen a- oder y-Derivaten des Pyridins in Form ihrer quaternären Salze eine bisher unbekannte Kondensationsfähigkeit gegenüber Stoffen mit beweglichen, an Kohlenstoff gebundenen Wasserstoffatomen zukommt.Process for the preparation of condensation products of quaternary pyridine compounds It has been found that certain a- or y-derivatives of pyridine in the form of their quaternary Salts a previously unknown ability to condense towards substances with mobile, carbon-bonded hydrogen atoms.
Diese Kondensationsfähigkeit ist dann vorhanden, wenn eine Verbindung, die den Pyridinkern enthält, . in o- oder p-Stellung zum quaternären Ringstickstoff Halogenatome oder solche Substituenten trägt, wie sie z. B. durch den bekannten Austausch von Halogen eingeführt werden können, z. B. Hydroxyl-, Alkoxyl-, Sulfhyd'ryl- oder Sulfonsäüregruppen. Mit den letztgenannten Stoffen kann man die Kondensation auch so vornehmen, daß man die Stoffe über die quaternären Verbindungen der entsprechenden o- oder p-Halogenpyridine darstellt und die so entstandenen quaternären Verbindungen, gegebenenfalls ohne sie abzutrennen, verwendet.This ability to condense is present when a connection, which contains the pyridine nucleus,. in o- or p-position to the quaternary ring nitrogen Carries halogen atoms or such substituents as they are, for. B. by the well-known Replacement of halogen can be introduced, e.g. B. hydroxyl, alkoxyl, sulfhyd'ryl or sulfonic acid groups. With the latter substances, one can condensation also make so that one of the substances via the quaternary compounds of the corresponding represents o- or p-halopyridines and the quaternary compounds formed in this way, possibly used without separating them.
Als zweite Komponente kommen Stoffe der allgemeinen Formel in Frage, wobei von. den Substituenten R1, R= und R3 einer oder zwei durch Wasserstoff vertreten sein können, vorausgesetzt, daß die übrigen Reste entweder in ihrer Gesamtheit oder einzeln die an das zentrale C-Atom gebundenen Wasserstoffatome in reaktionsfähige Form versetzen. Als Beispiele für solche kondensationsfähigen Stoffe seien genannt: Malonsäurediäthylester, Acetessigester, Acetophenon, Aceton., Fluoren u. a. m.Substances of the general formula can be used as the second component, where from. one or two of the substituents R1, R = and R3 can be represented by hydrogen, provided that the remaining radicals either in their entirety or individually convert the hydrogen atoms bonded to the central carbon atom into reactive form. Examples of such condensable substances are: diethyl malonate, acetoacetate, acetophenone, acetone, fluorene and many others
Die Kondensation besteht in der Abspaltung des o- oder p-ständigen Halogens bzw. des Substituenten der obengenannten Art zusammen mit einem Wasserstoffatom der kon= densationsfähigen Verbindung, z. B. als Halogenwasserstoffverbindung bei den Halogenverbindungen, als Wasser bei den Oxyverbindungen, als Alkohol bei den Alkoxyverbindungen usw.The condensation consists in splitting off the o- or p-position Halogen or the substituent of the type mentioned above together with a hydrogen atom the condensation-capable connection, e.g. B. as a hydrogen halide compound the halogen compounds, as water in the oxy compounds, as alcohol in the Alkoxy compounds, etc.
Ist an der reaktionsfähigen Verbindung noch ein zweites Wasserstoffatom frei, so kann sich dieses mit dem Säurerest des quaternären Stickstoffes unter Bildung einer Doppelbindung abspalten, so daß sich in diesem Fall für den gesamten Kondensationsverlauf folgendes formale Schema ergibt (z. B, für o-ständigen Substituenten Su). Beispiel i Kondensation von 2-Chlorpyridindimethylsulfat mit Malonester 25 g 2-Chlorpyridin werden tropfenweise mit 28g Dimethylsulfat versetzt, dann noch i Stunde auf dem Wasserbad erwärmt. Die zähe Masse wird in 2o ccm absolutem Äthylalkohol aufgenommen und tropfenweise unter gutem Rühren in eine Lösung von 1o,5 g Natrium in 15o ccm absolutem Alkohol, die mit 35 g Malonsäurediäthylester vermischt ist, einfließen gelassen. Die Lösung färbt sich beim Eintropfen der quaternären Verbindung sofort kräftig gelb. Nach dem Vermischen wird noch i Stunde auf dem Wasserbad gekocht, dann vom Alkohol ab- gedampft, in Wasser aufgenommen, mit starker Lauge versetzt und erschöpfend mit viel Benzol ausgezogen. Das Benzol nimmt das gebildete Kondensationsprodukt mit kräftig gelber Farbe auf. Es wird daraus mit einer benzolischen Lösung von Pikrinsäure als öliges, beim Reiben bald kristallinisch erstarrendes Pikrat gefällt. Nach zweimaliger Kristallisation aus Alkohol bildet das Pikrat derbe gelbe Kristalle vom F. 95 bis 9G°. Die Ausbeute ist sehr gut.If a second hydrogen atom is still free on the reactive compound, this can split off with the acid residue of the quaternary nitrogen to form a double bond, so that in this case the following formal scheme results for the entire course of condensation (e.g. for o-position Substituents Su). Example i Condensation of 2-chloropyridine dimethyl sulfate with malonic ester 28 g of dimethyl sulfate are added dropwise to 25 g of 2-chloropyridine, and the mixture is then heated on the water bath for a further hour. The viscous mass is taken up in 2o ccm of absolute ethyl alcohol and allowed to flow dropwise with thorough stirring into a solution of 1o.5 g of sodium in 15o ccm of absolute alcohol, which is mixed with 35 g of diethyl malonate. The solution immediately turns bright yellow when the quaternary compound is added dropwise. After mixing, boil for another hour on the water bath, then remove the alcohol. steamed, taken up in water, mixed with strong lye and exhausted exhaustively with a lot of benzene. The benzene absorbs the condensation product formed with a bright yellow color. It is precipitated from it with a benzene solution of picric acid as an oily picrate that soon solidifies in a crystalline manner when rubbed. After two crystallizations from alcohol, the picrate forms solid yellow crystals with a melting point of 95 to 9 °. The yield is very good.
Wird das Pikrat mit Lauge zersetzt und mit Benzol ausgeschüttelt, so nimmt das Benzol die Base mit kräftig ,hellgelber Farbe auf. Wasser löst die Base aus der Benzollösung fast farblos heraus. Ist keiner der drei Substituenten R1, P,°-und R3 Wasserstoff, so bleibt die Kondensation auf Stufe 3 stehen.If the picrate is decomposed with lye and shaken out with benzene, so the benzene takes up the base with a strong, light yellow color. Water dissolves the Base almost colorless out of the benzene solution. Is not one of the three substituents R1, P, ° - and R3 are hydrogen, the condensation on stage 3 stops.
Als Kondensationsmittel wirken basische Stoffe, wie z. B. Alkali- oder Erdalli:alialkoholate bzw. die Metallverbindungen der kondensationsfähigen Stoffe, ferner Alkali- oder Erdalkalihydroxyd oder -carbonat oder tertiäre Basen. Die Kondensation erfolgt meist schon bei gewöhnlicher Temperatur und kann gegebenenfalls bei erhöhter Temperatur, z. B. Wasserbadteinperatur, zu Ende geführt werden. Man benutzt zweckmäßigerweise Lösungs- oder Verdünnungsmittel.Basic substances act as condensation agents, such as B. Alkali or Erdalli: alialkoholate or the metal compounds of the condensable Substances, also alkali or alkaline earth hydroxide or carbonate or tertiary bases. The condensation usually already takes place at normal temperature and can, if necessary at elevated temperature, e.g. B. Wasserbadteinperatur to be completed. Man expediently uses solvents or diluents.
Kondensationen dieser Art sind bisher nicht bekanntgeworden. Man hat lediglich Verbindungen mit sehr reaktionsfähigem Halogenatom, z. B. 2-Chlor-5-nitropyridin (österreichische Patentschrift 1-27 795, Beispiel 1o) und 3-Nitro-4-chlorpyridin (Chem. Zentralblatt 1927, 1I, S.2758), mit Malonester zur Umsetzung gebracht, wobei die eritsprechenden Nitropyridylmalonester entstehen. Vorliegende Arbeitsweise unterscheidet sich von diesen bekannten Verfahren vor allem dadurch, daß hiernach auch wenig bewegliches Halogen, wie z. B. das Chlor im 2-Chlorpyridin, und außerdem eine Reihe anderer Substituenten, wie z. B. Alkoxygruppen, zur Kondensation geeignet sind. Beispiele Kondensation von 2-Äthoxypyridindilnetllylsulfat mit Malonester 25 g 2-Äthoxypyridin wird tropfenweise lnit 25,5 g Dimethylsulfat versetzt und i Stunde auf dem Wasserbad erwärmt. Die Verbindung wird in 2o ccm Alkohol aufgenommen und tropfenweise unter Rühren oder Schütteln zu der Lösung von 4,7 g .Natrium in i oo ccm absolutem Alkohol, die mit 35 g Malonsäurediäthylester vermischt ist, zugesetzt. Die Lösung wird zunehmend kräftig gelb. Nach 2stündigem Erhitzen auf dein Wasserbad wird wie bei Beispiel i aufgearbeitet. Man erhält dasselbe Produkt in gleicher Ausbeute und Reinheit.Condensations of this type have not yet become known. One has only compounds with a very reactive halogen atom, e.g. B. 2-chloro-5-nitropyridine (Austrian patent specification 1-27 795, example 1o) and 3-nitro-4-chloropyridine (Chem. Zentralblatt 1927, 1I, p.2758), brought to reaction with malonic ester, whereby the erit-speaking nitropyridyl malonic esters arise. The present working method differs differs from these known processes mainly in that there is little movement afterwards Halogen such as B. the chlorine in 2-chloropyridine, and also a number of others Substituents such as B. alkoxy groups, are suitable for condensation. Examples Condensation of 2-Äthoxypyridindilnetllylsulfat with malonic ester 25 g of 2-Äthoxypyridin 25.5 g of dimethyl sulfate are added dropwise and placed on a water bath for 1 hour warmed up. The compound is taken up in 20 cc of alcohol and added drop by drop Stir or shake to the solution of 4.7 g of sodium in 100 cc of absolute alcohol, which is mixed with 35 g of diethyl malonate, added. The solution is growing strong yellow. After 2 hours of heating on your water bath, it becomes as in the example i worked up. The same product is obtained in the same yield and purity.
Beispiel 3 Kondensation von 2-Oxypyridindimethylsulfat mit Malonester 3.- a-Pyridon werden mit q. g Dimethylsulfat vermischt und i Stunde auf dem Wasserbad erwärmt. Die zähe Masse wird in absolutem Alkohol aufgenommen und zu der Lösung von o,8 g Natrium und 5 g Malonsäurediäthylester in absolutem Alkohol zugesetzt. Anfänglich ist keine Veränderung oder Färbung zu bemerken. Die Lösung wird dann auf dem Dampfbad unter Rückfiuß erhitzt, wobei sie zunehmend kräftig hellgelb. wird. Nach 5 bis 6 Stunden wird abgebrochen und wie bei Beispiel i aufgearbeitet. Es wird dasselbe Pikrat wie in Beispiel i und 2 erhalten.Example 3 Condensation of 2-oxypyridinedimethyl sulfate with malonic ester 3.- a-pyridone are obtained with q. g of dimethyl sulfate mixed and heated on a water bath for 1 hour. The viscous mass is taken up in absolute alcohol and added to the solution of 0.8 g of sodium and 5 g of diethyl malonate in absolute alcohol. Initially, no change or color is noticeable. The solution is then refluxed on the steam bath, becoming increasingly bright pale yellow. will. After 5 to 6 hours, the process is terminated and worked up as in Example i. The same picrate as in example i and 2 is obtained.
Beispiel q.Example q.
Umsetzung von 2-Chlorpyridindilnetllylsulfat mit Natriumstilfit und anschließender Kondensation mit Malonester 25 g 2-Chlorpyridin und 28 g Dimethylsulfat werden wie üblich vereinigt. Die Additionsverbindung wird in Wasser gelöst und zu der Lösung von 6o g kristallisiertem Natriumsulfat zugesetzt. Dabei tritt ziemlich starke Erwärmung auf, und es bildet sich wahrscheinlich die leicht wasserlösliche Verbindung Die wässerige Lösung wird weitgehend eingeengt, wobei der größte Teil des gebildeten Natriumsalzes der Methylschwefelsäure ausfällt und abgesaugt wird. Die konzentrierte Lösung des Reaktionsproduktes wird mit36gMalonsäurediäthylester versetzt. Dann tropft man langsam unter sehr guter Durchmischung der beiden ineinander schwer löslichen Schichten. die Lösung von 57 g Kaliumcarbonat in wenig Wasser zu. Die Masse färbt sich zunehmend kräftig orangegelb. Nach beendeter Zugabe wird mit Lauge alkalisch gemacht und mit Benzol ausgeschüttelt. Es wird dasselbe Pikrat erhalten wie in Beispiel i.Reaction of 2-Chlorpyridindilnetllylsulfat with sodium stilfit and subsequent condensation with malonic ester 25 g of 2-chloropyridine and 28 g of dimethyl sulfate are combined as usual. The addition compound is dissolved in water and added to the solution of 60 g of crystallized sodium sulfate. In the process, the heating is quite strong, and the easily water-soluble compound is likely to be formed The aqueous solution is largely concentrated, with most of the sodium salt of methylsulfuric acid formed precipitating and being filtered off with suction. 36 g of diethyl malonate are added to the concentrated solution of the reaction product. Then the two layers, which are difficult to dissolve in one another, are slowly added dropwise with very thorough mixing. the solution of 57 g of potassium carbonate in a little water. The mass becomes increasingly bright orange-yellow. When the addition is complete, it is made alkaline with lye and extracted with benzene. The same picrate is obtained as in example i.
Beispiel s Kondensation von 2-Chlorpyridindimethylsulfat mit Acetessgester 25 g 2-Chlorpyridin und 28g Dilnethylsulfatwerden umgesetzt wie üblich, in 30 ccm absolutem Alkohol gelöst und langsam zu der Lösung von io g Natrium in i So ccm absolutem Alkohol, die mit 29 g Acetessigester ver- . mischt ist, zugetropft. Die Lösung färbt sich kräftig gelb. Die Umsetzung wird durch istündiges Erhitzen auf dem Dampfbad vervollständigt. Dann wird der Alkohol abgetrieben, der Rückstand mit Wasser- aufgenommen, mit Lauge versetzt und mit Benzol erschöpfend ausgezogen. Die stark dunkelgelbe Benzolschicht wird mit Pikrinsäure gefällt. Das ölige Pikrat kristallisiert bald. Es wird in der 5fachen Menge Alkohol gelöst, vom, Ungelösten abfiltiert und in die q.- bis 5fache Menge (bezogen auf den Alkohol) heißes Wasser eingerührt. Beim Reiben und Schütteln kristallisieren daraus feine gelbe Blättchen vom F. 114 bis I15°, die schon ziemlich rein sind. Sie können aus Alkohol kristallisiert werden. Die Ausbeute ist sehr gut.Example s Condensation of 2-chloropyridine dimethyl sulfate with acetessgester 25 g of 2-chloropyridine and 28 g of dilute ethyl sulfate are reacted as usual, dissolved in 30 cc of absolute alcohol and slowly added to the solution of 10 g of sodium in 1 cc of absolute alcohol, which is mixed with 29 g of acetoacetic ester. . is mixed, added dropwise. The solution turns bright yellow. The reaction is completed by heating on the steam bath for 1 hour. The alcohol is then driven off, the residue is taken up in water, alkali is added and the residue is exhaustively extracted with benzene. The very dark yellow benzene layer is precipitated with picric acid. The oily picrate soon crystallizes. 5 times the amount of alcohol is dissolved, the undissolved material is filtered off and hot water is stirred into q to 5 times the amount (based on the alcohol). On rubbing and shaking, fine yellow leaves crystallize from it, with a temperature of 114 to 15 °, which are already fairly pure. They can be crystallized from alcohol. The yield is very good.
Aus dem Pikrat macht Lauge die stark gelbe, in Benzol lösliche Base frei. Aus der Benzollösung geht die Base beim Schütteln mit Wasser fast farblos in wässerige Lösung über.Lye turns the picrate into a strong yellow base, which is soluble in benzene free. The base turns almost colorless from the benzene solution when shaken with water in aqueous solution.
Beispiel 6 Kondensation von 2-Äthoxypyridindimethylsulfat mit Acetessigester Die Kondensation wird mit 25 g 2-Äthoxypyridin, 23,5 wDimethylsulfat, 4,7 g Natrium, 28 g Acetessigester in Alkohol entsprechend den übrigen Beispielen ausgeführt. Man erhält dasselbe Pikrat wie in Beispiel 5 in ähnlich guter Ausbeute.Example 6 Condensation of 2-ethoxypyridine dimethyl sulfate with acetoacetic ester The condensation is with 25 g of 2-ethoxypyridine, 23.5 w-dimethyl sulfate, 4.7 g of sodium, 28 g of acetoacetic ester in alcohol carried out according to the other examples. Man receives the same picrate as in Example 5 in a similarly good yield.
Beispiel ? Kondensation von 2-Äthoxypyridindimethylsulfat mit Acetopherlon io g 2-Äthoxypyridin und 1o,5 g Dimethylsulfat werden, wie üblich, umgesetzt. Die Masse wird in 20 ccm absolutem Alkohol gelöst und zu der Lösung von 2 g Natrium in So ccm absolutem Alkohol, die mit ii g Acetophenon vermischt ist, zugesetzt. Die Lösung wird rasch kräftig rötlichgelb und färbt sich nach 2stündigem Erhitzen auf dem Wasserbad dunkelrotgelb. Der Alkohol wird abgedampft, der Rückstand mit Wasser und Lauge versetzt und erschöpfend mit Benzol ausgezogen.. Aus der Benzollösung wird durch Pikrinsäure ein sofort kristallisierendes Pikrat gefällt. Nach zweimaliger Umkristallisation aus wenig Aceton bildet es derbe dunkelgelbe Kristalle vom F. 125 bis 126°. Die Ausbeute ist gut.Example ? Condensation of 2-ethoxypyridinedimethyl sulfate with acetopherlone 10 g of 2-ethoxypyridine and 1o.5 g of dimethyl sulfate are reacted as usual. The mass is dissolved in 20 cc of absolute alcohol and added to the solution of 2 g of sodium in 50 cc of absolute alcohol, which is mixed with ii g of acetophenone. The solution quickly turns bright reddish-yellow and turns dark red-yellow after heating for 2 hours on a water bath. The alcohol is evaporated off, the residue is mixed with water and alkali and exhaustively extracted with benzene. A picrate which crystallizes immediately is precipitated from the benzene solution by means of picric acid. After two recrystallization from a little acetone, it forms solid dark yellow crystals with a melting point of 125 to 126 °. The yield is good.
Das Pikrat liefert nach dein Zersetzen mit Alkali eine in Benzol mit kräftig hellgelber Farbe lösliche Base, die mitWasser eine farblose Lösung gibt.After decomposing with alkali, the picrate supplies one in benzene strong pale yellow color soluble base, which gives a colorless solution with water.
Beispiel 8 Kondensation von 2-Äthoxypyridindimethylsulfat mit Fluoren 7,5 g 2-Äthoxypyridin und 7,6 g Dimethylsulfat werden umgesetzt, wie üblich, und zu der Lösung von 44 9 Natrium und io g Fluoren in absolutem Alkohol zugesetzt. Die Lösung wird zunehmend kräftig dunkelblutrot. Nach 3stündigem Erhitzen auf dem Dampfbad wird der Alkohol abgedampft, der Rückstand mit Wasser und Alkali versetzt und mit Benzol ausgezogen. Die dunkelrote Benzollösung wird so lange mit Pikrinsäurelösung versetzt, bis die Farbe in Gelb umschlägt. Der körnige Niederschlag wird atis_ Aceton umkristallisiert, er bildet dunkelgelbe, derbe Nadeln. F. 179 bis i8o° C. Die Ausbeute ist sehr gut.Example 8 Condensation of 2-ethoxypyridine dimethyl sulfate with fluorene 7.5 g of 2-ethoxypyridine and 7.6 g of dimethyl sulfate are reacted as usual, and added to the solution of 44% sodium and 10 g fluorene in absolute alcohol. The solution becomes increasingly dark blood red. After 3 hours of heating on the In the steam bath, the alcohol is evaporated, the residue is mixed with water and alkali and extracted with benzene. The dark red benzene solution is so long with picric acid solution staggered until the color turns yellow. The granular precipitation will atis_ acetone recrystallized, it forms dark yellow, tough needles. F. 179 to 180 ° C. The yield is very good.
Lauge macht aus dem gelben Pikrat einen stark dunkelblutroten Stoff frei, der in Benzol löslich ist. Wasser löst die Base aus dem Benzol farblos heraus.Lye turns the yellow picrate into a very dark blood-red substance free, which is soluble in benzene. Water dissolves the base from the benzene colorless.
Statt Dimethylsulfat kann man in obigen Beispielen auch reaktionsfähige Halogenide, wie z. B. Jodmethyl u. dgl., verwenden.Instead of dimethyl sulfate, reactive ones can also be used in the above examples Halides such as B. iodomethyl and the like., Use.
Beispiel 9.Example 9.
- Kondensation von N-Methyl-a-pyridondimethvlsulfat mit Malonester 509 N-Methyl-a-pyridon werden auf dem Wasserbad vorsichtig mit 58g Dimethylsulfat umgesetzt. Die entstandene quaternäre Verbindung wird wie bei Beispiel i mit 75 g Malonester und i0,5 g Natrium umgesetzt. Das Kondensationsprodukt stimmt mit dem nach Beispiel i erhaltenen überein und entsteht in vorzüglicher Ausbeute.- Condensation of N-methyl-a-pyridone dimethyl sulfate with malonic ester 509 N-methyl-a-pyridone are carefully reacted with 58 g of dimethyl sulfate on a water bath. The resulting quaternary compound is reacted as in Example i with 75 g of malonic ester and i0.5 g of sodium. The condensation product agrees with that obtained according to Example i and arises in excellent yield.
Beispiel io " Kondensation von N-Methyl-a-thiopyridon mit Malonester 5 g N-Methyl-a-thiopyridon und 5 g Dimethylsulfat werden auf dem Dampfbad umgesetzt und, wie üblich; mit 6,5 g Malonester und i,o g Natrium kondensiert. Die entstehende Verbindung ist wesensgleich mit der nach Beispiel i erhaltenen. Die Ausbeute ist ausgezeichnet.Example io "Condensation of N-methyl-a-thiopyridone with malonic ester 5 g of N-methyl-a-thiopyridone and 5 g of dimethyl sulfate are reacted on the steam bath and, as usual; condensed with 6.5 g of malonic ester and 1.0 g of sodium. The emerging Compound is essentially identical to that obtained according to Example i. The yield is excellent.
Beispiel ii Kondensation von N-Methyl-a-py rdondimethylsulfat mit a-Picolindimethylsulfat 25 g N-Methy1-a-pyridon werden mit 29 g Dimethylsulfat umgesetzt. Ebenso werden 2 i g a-Picolin mit 29 g Dimethylsulfat in die quaternäre Verbindung übergeführt. Beide Mischungen werden in wasserfreiem Alkohol gelöst und mit der Lösung von 5,3 g Natrium in Alkohol versetzt. Die Masse wird kräftig rotgelb. Nach Beendigung der Kondensation auf dem Dampfbad wird der Alkohol abgetrieben, der entstandene Farbstoff im Wasser gelöst und mit Jodkalium als Jodid gefällt. Er bildet ockerfarbene Kristalle vom F. 24q.° bis 2q.6°.Example ii Condensation of N-methyl-a-py rdondimethyl sulfate with a-picoline dimethyl sulfate 25 g of N-methyl-a-pyridone are reacted with 29 g of dimethyl sulfate. Likewise, 2 μg of a-picoline are converted into the quaternary compound with 29 g of dimethyl sulfate. Both mixtures are dissolved in anhydrous alcohol and a solution of 5.3 g of sodium in alcohol is added. The mass becomes bright red-yellow. After the condensation on the steam bath has ended, the alcohol is driven off, the resulting dye is dissolved in the water and precipitated as iodide with potassium iodide. It forms ocher-colored crystals from 24q. ° to 2q. 6 °.
Beispiel I2 Kondensation von 1\T-Metliyl-a-pyridondimethylsulfat finit Chinaldindiinethylsulfat 25 g N-Methyl-a-pyridon und 30 g Chinaldin werden mit 58 g Dirnethylsulfat umgesetzt, dann in Alkohol gelöst und mit der Lösung von 5,3 g Natrium in Alkohol verinischt. Die Lösung wird gelbrot. Nach Beendigung der Kondensation wird wie bei Beispiel i i aufgearbeitet. Das Kondensationsprodukt ist ein Farbstoff und bildet als Jodid braunrote Nadeln vom F. 23o bis 232°.Example I2 Condensation of 1 \ T-Methyl-a-pyridondimethylsulfat finite Quinaldindiinethylsulfat 25 g of N-methyl-a-pyridone and 30 g of quinaldine are reacted with 58 g of dimethyl sulfate, then dissolved in alcohol and with the solution of 5.3 g of sodium in Alcohol mixed. The solution turns yellow-red. After the condensation has ended, work-up is carried out as in Example ii. The condensation product is a dye and, as iodide, forms brown-red needles with a temperature of 23o to 232 °.
Die Verbindungen aus Beispiel ii und 12 sind Farbstoffe aus der Reihe der 7p-Cyanine und können nach Art solcher Verbindungen, z. B. als Photosensibilisatoren, verwendet werden.The compounds from Example ii and 12 are dyes from the series of the 7p-cyanines and can in the manner of such compounds, eg. B. as photosensitizers, be used.
Beispiel 13 Kondensation von N-Methyl-a-chinolondimethylsulfat mit Malonester Die Kondensation verläuft ganz entsprechend derjenigen in Beispiel i. Das Pikrat bildet gelbe Kristalle vom F.88 bis 114'. Die freie Base ist in Benzol mit kräftig gelber Farbe löslich.Example 13 Condensation of N-methyl-a-quinolone dimethyl sulfate with malonic ester The condensation proceeds exactly as in Example i. The picrate forms yellow crystals from F.88 to 114 '. The free base is soluble in benzene with a bright yellow color.
Beispiel 14 Kondensation von 4-Broinpyridindimethylstilfat mit Malonester 15 g der kristallisierten Anlagerungsverbindung von Dimethylsulfat an 4-Brompyridin und g g Malonsäurediäthylester werden in wasserfreiem Alkohol gelöst und unter Schütteln mit der Lösung von :2,49 Natrium in Alkohol vermischt. Unter Erwärmung tritt eine kräftig purpurrote Färhung ein. Nach istündigem Stehen wird mit Wasser versetzt und mit Chloroform ausgezogen. Der Chloroformrückstand ist zum Teil kristallinisch. Der kristallinische Anteil besteht aus gelblichen Kristallen vom F. 96 bis 98°. Der tiefrote, nicht kristallisierte Anteil gibt mit Säuren hellgelbe Salze, aus denen Alkalien wieder die tiefrote, benzollösliche Base freimachen entsprechend den tiefgelben Basen der a-Reihe.Example 14 Condensation of 4-brominpyridinedimethylstilfate with malonic ester 15 g of the crystallized addition compound of dimethyl sulfate and 4-bromopyridine and g g of diethyl malonate are dissolved in anhydrous alcohol and shaken mixed with the solution of: 2.49 sodium in alcohol. When heated, a strong purple color. After standing for one hour, water is added and extracted with chloroform. The chloroform residue is partly crystalline. The crystalline part consists of yellowish crystals with a temperature of 96 to 98 °. The deep red, non-crystallized part gives off light yellow salts with acids which alkalis again release the deep red, benzene-soluble base accordingly the deep yellow bases of the a-series.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC47084D DE594084C (en) | 1932-10-29 | 1932-10-29 | Process for the preparation of condensation products of quaternary pyridine compounds |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC47084D DE594084C (en) | 1932-10-29 | 1932-10-29 | Process for the preparation of condensation products of quaternary pyridine compounds |
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| Publication Number | Publication Date |
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| DE594084C true DE594084C (en) | 1934-03-12 |
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| DEC47084D Expired DE594084C (en) | 1932-10-29 | 1932-10-29 | Process for the preparation of condensation products of quaternary pyridine compounds |
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| DE (1) | DE594084C (en) |
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1932
- 1932-10-29 DE DEC47084D patent/DE594084C/en not_active Expired
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