DE3417651A1 - Betaines of squaric acid and a process for their preparation - Google Patents

Betaines of squaric acid and a process for their preparation

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DE3417651A1
DE3417651A1 DE19843417651 DE3417651A DE3417651A1 DE 3417651 A1 DE3417651 A1 DE 3417651A1 DE 19843417651 DE19843417651 DE 19843417651 DE 3417651 A DE3417651 A DE 3417651A DE 3417651 A1 DE3417651 A1 DE 3417651A1
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betaines
radical
squaric acid
general formula
water
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German (de)
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Arthur H. Prof. Dr. 6200 Wiesbaden Schmidt
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Schmidt arthur H profdr
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Abstract

The invention is betaines of squaric acid of the general formula (I) <IMAGE> in which X is either R3Z, where Z is then N, P, As, S or Se and n where Z = N, P and As denotes three and where Z = S and Se denotes two, and the organic radicals R are identical or different and denote an alkyl radical from C1 to C12, a cycloalkyl radical from C5 to C12, an aryl radical from C6 to C15 or an aralkyl radical from C6 to C15 or in which X is a saturated, unsaturated or aromatic heterocycle whose hetero atom from the group consisting of N, P, As, S and Se is the carrier of the positive partial charge and is directly connected to the 2-hydroxy-3,4-dioxocyclobutenyl betaine radical, 1-(2-hydroxy-3,4-dioxocyclobutenyl)triphenylphosphonium betaine being excluded. A process for the preparation of these betaines is additionally described in which a 1,2-disubstituted 3,4-dioxo-1,2-cyclobutene of the general formula (2) is reacted with a compound of the general formula X, if appropriate in the presence of water, of an inert organic solvent and/or acetic anhydride: <IMAGE>

Description

Betaine der Quadratsäure und ein Verfahren zu derenSquaric acid betaines and a method for their

Darstellung.Depiction.

Die Erfindung betrifft ein Verfahren zur Herstellung von Stickstoff-, Phosphor-, Arsen-, Schwefel- und Selen-Betainen der Quadratsäure und ausserdem ein Verfahren zu deren Herstellung.The invention relates to a method for the production of nitrogen, Phosphorus, arsenic, sulfur and selenium betaines of the squaric acid and also a Process for their manufacture.

Stickstoff-Betaine der Quadrat säure sind seit geraumer Zeit bekannt und eingehend untersucht worden. Sie sind spezielle Vertreter einer Klasse von Verbindungen, die sich in allgemeiner Weise z. B. durch die Formel (4)bzw. ( 5 ) beschreiben lassen, und für die die abkürzende Bezeichnung "Quadraine" vorgeschlagen wurde. (A. H. Schmidt, Synthesis, 1980, 961).Square acid nitrogen betaines have been known for some time and has been thoroughly investigated. They are special representatives of a class of compounds which in a general way z. B. by the formula (4) or. (5) let describe, and for which the abbreviation "Quadraine" has been proposed. (A. H. Schmidt, Synthesis, 1980, 961).

N-Quadraine werden gewöhnlich durch Kondensation von Quadratsäure mit der doppelt-molaren Menge eines primären oder sekundären Amins verhalten. ( G. Manecke und J. Gauger, Tetra hedron Letters 1967, 3509 ; 1968, 1339 . J. Gauger und G.N-Quadraine are usually made by the condensation of squaric acid behave with twice the molar amount of a primary or secondary amine. ( G. Manecke and J. Gauger, Tetra hedron Letters 1967, 3509; 1968, 1339. J. Gauger and G.

Manecke, Chemische Berichte 103, 2696, 3553 (1970 ) ). In entsprechender Weise lassen sich C-Quadraine durch Umsetzung von Quadratsäure mit Pyrrolen ( A. Treibs und K. Jakob, Liebigs Annalen der Chemie 712, 123 (1968) ), Azulenen ( W. Ziegenbein und H. E. Sprenger, Angewandte Chemie, 78 937 (1966) ) und tertiären aromatischen Aminen ( H. E. Sprenger und W. Ziegenbein, Angewandte Chemie, 78, 937 ( 1966 ) ) darstellen. Mehrere Zusammenfassungen (A. H. Schmidt, Synthesis, 1980 , 961. H. E. Sprenger und W. Ziegenbein, Angewandte Chemie, 80, 541 (1968)) geben über Synthese und Reaktionen der Quadraine erschöpfende Auskunft. Manecke, Chemischeberichte 103, 2696, 3553 (1970)). In a corresponding manner, C-quadraine can be prepared by reacting squaric acid with pyrroles (A. Treibs and K. Jakob, Liebigs Annalen der Chemie 712, 123 (1968)), azulenes (W. Ziegenbein and HE Sprenger, Angewandte Chemie, 78 937 ( 1966)) and tertiary aromatic amines (HE Sprenger and W. Ziegenbein, Angewandte Chemie, 78, 937 (1966)). Several abstracts (AH Schmidt, Synthesis, 1980, 961. HE Sprenger and W. Ziegenbein, Angewandte Chemie, 80, 541 (1968)) provide exhaustive information on the synthesis and reactions of the quadraine.

(4) (5) Aus diesen Gründen ist es verwunderlich, dass bisher weitgehend unbeachtet blieb, dass sich von der Quadratsäure formal eine weitere Klasse von Betainen ableiten lässt, deren N-haltigen Vertreter z. B. durch Formel ( 6 ) repräsentiert werden und die in allgemeiner Weise durch Formel ( 1 ) zu beschreiben sind. Die einzige bisher bekannt gewordene Verbindung verwandten Typs ist das 1-(2-Hydroxy-3, 4-dioxocyclobutenyl)-triphenylphosphonium-Betain ( 7a), das von Bestmann et al. (Angewandte Chemie, 89, 275 (1977)) ausgehend von Ketenyliden- triphenylphosphoran erhalten wurde. (4) (5) For these reasons, it is surprising that so far it has largely been ignored that another class of betaines can be formally derived from squaric acid. B. represented by formula (6) and to be described in a general manner by formula (1). The only previously known compound of a related type is 1- (2-hydroxy-3, 4-dioxocyclobutenyl) triphenylphosphonium betaine (7a), which was developed by Bestmann et al. (Angewandte Chemie, 89, 275 (1977)) was obtained starting from ketenylidene triphenylphosphorane.

Aufgabe der vorliegenden Erfindung ist es, einerseits ein neues Basisverfahren zur Herstellung verschiedenster Betaine zu entwickeln, andererseits damit aber auch eine Reihe von neuen Betainen zu synthetisieren.The object of the present invention is, on the one hand, to provide a new basic method to develop a wide variety of betaines, but also to do so on the other hand to synthesize a number of new betaines.

Die Erfindung sind dann Betaine der Quadratsäure der allgemeinen Formel (1), in der X entweder R3Z ist, wobei Z = P, As, S oder Se ist und n bei Z = N, P und As drei und bei Z = S und Se zwei bedeutet und die organischen Reste R gleich oder verschieden sind und einen Alkylrest von C1 bis C12 , einen Cycloalkylrest von C5 bis C12, einen Arylrest von C6 bis C15 bedeuten oder in der X ein gesättigter, ungesättigter oder aromatischer Heterocyclus ist, dessen Heteroatom aus der Gruppe N, P, As, S oder Se der Träger der positiven Partialladung ist und direkt mit dem 2-Hydroxy- 3, 4-dioxocyclobutenyl-betain-Rest verbunden ist, ausgenommen ist das 1 - (2 -Hydroxy- 3, 4-dioxocyclobutenyl)-triphenylphosphonium-Betain.The invention are then betaines of squaric acid of the general formula (1), in which X is either R3Z, where Z = P, As, S or Se and n when Z = N, P and As are three and when Z = S and Se are two and the organic radicals R are the same or are different and an alkyl radical from C1 to C12, a cycloalkyl radical from C5 to C12, an aryl radical from C6 to C15 or in which X is a saturated, is unsaturated or aromatic heterocycle whose heteroatom is selected from the group N, P, As, S or Se is the carrier of the partial positive charge and directly with the 2-Hydroxy-3, 4-dioxocyclobutenyl-betaine radical is connected, with the exception of this 1- (2-hydroxy-3, 4-dioxocyclobutenyl) triphenylphosphonium betaine.

In bevorzugten Ausführungsformen sind in der allgemeinen Formel ( 1 ) bzw. in den Erläuterungen dazu Z = N und n = 3 und die Reste R gleich oder verschieden und bedeuten einen Alkylrest von C1 bis C12 oder einen Aralkylrest von C7 bis C12.In preferred embodiments, the general formula ( 1) or, in the explanations, Z = N and n = 3 and the radicals R are identical or different and denote an alkyl radical from C1 to C12 or an aralkyl radical from C7 to C12.

In einer ganz besonders bevorzugten Ausführungsform ist X ein Heterocyclus aus der Gruppe N-Methyl-morpholin, Pyridin, Picolin, Lutidin, Wert. Butyl-pyridin, Benzylpyridin, Nicotinsäure-alkylester, Nicotinsäureamid, Cyanopyridin, Aminopyri din, Hydroxypyridin, Chinolin, Isochinolin. Es sind aber auch noch Ausführungsformen möglich, in denen X einen Heterocyclus mit mehr als einem Heteroatom darstellt, wie z. B. Imidazol. In weiteren bevorzugten Ausführungsformen ist Z = P oder As und n = 3, und die Reste R sind gleich und bedeuten und bedeuten einen unsubstituierten oder substituierten Phenyl rest. In weiteren bevorzugten Ausführungsformen ist Z = S und n = 2 und die Reste R sind gleich oder verschieden und bedeuten einen Alkylrest von C1 bis C6, oder X bedeutet einen Heterocyclus vom Typ des Tetrahydrothiophens.In a very particularly preferred embodiment, X is a heterocycle from the group N-methyl-morpholine, pyridine, picoline, lutidine, value. Butyl pyridine, Benzylpyridine, nicotinic acid alkyl ester, nicotinic acid amide, cyanopyridine, aminopyri din, hydroxypyridine, quinoline, isoquinoline. But there are also embodiments possible, in which X represents a heterocycle with more than one heteroatom, such as B. imidazole. In further preferred embodiments, Z = P or As and n = 3, and the radicals R are identical and mean and mean an unsubstituted or substituted phenyl radical. In other preferred Embodiments Z = S and n = 2 and the radicals R are identical or different and denote an alkyl radical from C1 to C6, or X denotes a heterocycle from Type of tetrahydrothiophene.

Eine weitere Lösung der gestellten Aufgabe ist auch ein Verfahren zur Herstellung der genannten Betaine, das dadurch gekennzeichnet ist, dass ein 1, 2-disubstituiertes 3, 4-Dioxo-cyclobuten-(1, 2) der allgemeinen Formel ( 2 ) mit einer Verbindung der allgemeinen Formel X, gegebenenfalls in Gegenwart eines inerten organischen Lösungsmittels , Wasser und / oder Acetanhydrid umgesetzt wird. Dabei ist Y gleich oder verschieden und bedeutet -OH ; -OAlkyl (Alkyl = C1 bis C4) oder Hal (Hal = C1 oder Br ). X stellt eine Verbindung dar, wie sie vorstehend definiert wurde - insbesondere kommen in Betracht tertiäre Amine , Pyridin und substituierte Pyridinderivate, N-haltige Heterocyclen mit einem oder mehreren Heteroatomen, tertiäre Phosphine, tertiäre Arsine, Dialkylsulfide, S-haltige Heterocyclen.A further solution to the problem posed is also a method for the production of said betaines, which is characterized in that a 1, 2-disubstituted 3, 4-dioxo-cyclobutene- (1, 2) of the general formula (2) with a compound of the general formula X, optionally in the presence of one inert organic solvent, water and / or acetic anhydride is implemented. Y is identical or different and denotes -OH; -OAlkyl (alkyl = C1 to C4) or Hal (Hal = C1 or Br). X represents a compound as defined above - in particular, tertiary amines, pyridine and substituted ones come into consideration Pyridine derivatives, N-containing heterocycles with one or more heteroatoms, tertiary Phosphines, tertiary arsines, dialkyl sulfides, S-containing heterocycles.

Insbesondere werden dabei als Ausgangsstoffe eingesetzt Quadratsäure, Quadratsäuredichlo rid, Quadrats äur emono chlorid, Quadrat säure diethylester, Quadratsäuredibutylester.In particular, squaric acid is used as starting materials, Square acid dichloride, square acid emono chloride, square acid diethyl ester, Dibutyl squarate.

In den nachfolgenden Ausführungen werden mehrere Varianten des Verfahrens im einzelnen beschrieben Variante 1 Wird zu einer gekühlten Lösung von Quadratsäuredichlorid in Tetrahydrofuran die Lösung eines tertiären Amins ( 1 - 3 molare Menge ) und Wasser ( äquimolare Menge ) in Terahydrofuran getropft ( "Dreikomponentenreaktion" ) , so entstehen die Betaine ( 6 ), die sich aus der Reaktionslösung in Form farbiger Kristalle abscheiden. ( Tabelle 1 ).In the following explanations, several variants of the method described in detail Variation 1 Becomes a chilled solution of squaric acid dichloride in tetrahydrofuran the solution of a tertiary amine ( 1 - 3 molar amount) and water (equimolar amount) in terahydrofuran ("Three-component reaction"), so the betaines (6) arise, which result from the Separate the reaction solution in the form of colored crystals. ( Table 1 ).

Diese Variante eignet sich auch vorzüglich zur Herstellung von P- und As- Betainen. ( Tabelle 2 ).This variant is also ideally suited for the production of P- and as-betaines. (Table 2).

Die Reihenfolge, in der die drei Reaktanden vereinigt werden, ist für einen erfolgreichen Reaktionsverlauf nicht von entscheidender Bedeutung. So erhielten wir die Betaine auch dann in guter Ausbeute, wenn die Vereinigung der Reaktanden in anderer Reihenfolge vorgenommen wurde, wie z. B.The order in which the three reactants are combined is not of critical importance for a successful reaction process. So we received the betaines in good yield even when the union of the Reactants were made in a different order, such as. B.

a) Vorlage von Quadratsäuredichlorid , Zugabe von Wasser sodann Zugabe eines Pyridins, Phosphins oder Arsins.a) Submission of squaric acid dichloride, addition of water then addition a pyridine, phosphine or arsine.

b) Vorlage von Quadratsäuredichlorid, Zugabe eines Pyridins oder Phosphins ; sodann Zugabe von Wasser.b) Submission of squaric acid dichloride, addition of a pyridine or phosphine ; then adding water.

c) Vorlage eines Pyridins , Zugabe von Wasser : sodann Zugabe von Quadratsäuredichlorid.c) Submission of a pyridine, addition of water: then addition of Squaric acid dichloride.

Aus den Tabellen 1 und 2 geht hervor, dass obiges Verfahren zur Darstellung von N- und P-Betainen der Quadratsäure eine grosse Variationsbreite bezüglich der eingesetzten Amine und Phosphine aufweist. Sowohl mit aliphatischen als auch mit cycloaliphatischen Aminen wird glatter Reaktionsablauf beobachtet. Dies gilt auch für Pyridin und eine Vielzahl von Pyridin-Derivaten. Weitgehend unabhängig von der elektronischen Natur der im Pyridinring befindlichen Substituenten ( z. B. Cll3 -CN, CO-NH2, -NR2 ) werden die Betaine in vergleichbarer Ausbeute erhalten.Tables 1 and 2 show that the above method of illustration of N- and P-betaines of squaric acid show a wide range of variation with regard to the Has used amines and phosphines. Both with aliphatic and with cycloaliphatic amines, smooth reaction is observed. this is also valid for pyridine and a variety of pyridine derivatives. Largely independent of the electronic nature of the substituents in the pyridine ring (e.g. Cll3 -CN, CO-NH2, -NR2) the betaines are obtained in comparable yield.

Das Lösungsverhalten der N- und P-Betaine bestätigt die strukturell bedingten Erwartungen. Sie sind in kaltem Wasser nur geringfügig löslich, gehen aber beim Erhitzen glatt in Lösung.The solution behavior of the N- and P-betaines confirms this structurally conditional expectations. They are only slightly soluble in cold water, go but smoothly in solution when heated.

In unpolaren organischen Solventien ( Ether, Chloroform ) sind sind sie auch in der Hitze praktisch unlöslich. In Solventien hoher Polarität ( Dimethylformamid, Dimethylsulfoxid ) lösen sie sich bei Raumtemperatur nur mässig, gehen jedoch schon bei gelindem Erwärmen gut in Lösung. Zur Umkristallisation eignen sich insbesondere Wasser, Ethanol, Acetonitril und Eisessig.In non-polar organic solvents (ether, chloroform) are they are practically insoluble even in the heat. In solvents of high polarity (dimethylformamide, Dimethyl sulfoxide) they only dissolve moderately at room temperature, but they do well in solution with gentle warming. Are particularly suitable for recrystallization Water, ethanol, acetonitrile and glacial acetic acid.

Variante 2 Beim Umsatz von Quadratsäure in Ethanol mit z. B. Pyridin oder einem Pyridinderivat fallen die Monopyridinium-quadratate (3) an. Werden diese in einem inerten organischen Lösungsmittel, vorzugsweise jedoch in Acetanhydrid, erhitzt, so werden unter Abspaltung von Wasser die Betaine ( 6 ) gebildet.Variant 2 When converting squaric acid in ethanol with z. B. pyridine or a pyridine derivative, the monopyridinium squares (3) are obtained. Will this in an inert organic solvent, but preferably in acetic anhydride, heated, the betaines (6) are formed with elimination of water.

( Tabelle 3 ). (Table 3).

(3) (1) Variante 3 Auf präparativ einfachem Wege und zum Teil in vorzüglicher Ausbeute liessen sich die N-Betaine ( 6 ) der Quadratsäure auch durch Vereinigung äquimolarer Mengen eines tertiären Amins und Quadratsäure in Acetanhydrid erhalten. ( Tabelle 3 ).(3) (1) Option 3 In a simple preparative way and some of the N-betaines (6) of squaric acid were found in excellent yields also by combining equimolar amounts of a tertiary amine and squaric acid obtained in acetic anhydride. (Table 3).

In einem repräsentativen Experiment wurden 10, 0 g < 87, 7 mmol ) Quadratsäure in 300 ml Acetanhydrid unter Erwärmung gelöst, 7, 0 g ( 88, 4 mmol ) Pyridin hinzugefügt und zum gelinden Sieden erhitzt. Bereits nach kurzer Zeit setzte die Ausfällung des Betains ein. Nach 30 min. Reaktionszeit wurde abgekühlt, der Niederschlag abgesaugt und aus Wasser umkristallisiert. Gelbe, glänzende Blättchen.In a representative experiment, 10.0 g were <87.7 mmol ) Squaric acid dissolved in 300 ml of acetic anhydride with warming, 7.0 g (88.4 mmol ) Pyridine added and heated to a gentle boil. After a short time began to precipitate the betaine. After a reaction time of 30 minutes, the mixture was cooled, the precipitate is suctioned off and recrystallized from water. Yellow, shiny leaves.

Weiterführende Untersuchungen zeigten, dass dieses neuartige Verfahren zur Herstellung von Monokondensationsprodukten der Quadratsäure verallgemeinerungs fähig ist. So erhielten wir beim kurzzeitigen Erhitzen von Quadratsäure mit der äquimolaren Menge eines Triarylphosphans in Acetanhydrid die Triarylphosphonium-Betaine. ( Tabelle 3 ).Further research showed that this novel process generalization for the production of monocondensation products of squaric acid is capable. Thus, when briefly heating squaric acid with the equimolar amount of a triarylphosphine in acetic anhydride the triarylphosphonium betaine. (Table 3).

Weitergehende Versuche zeigten, dass die N- und P-Betaine auch leicht aus anderen Quadratsäure-derivaten zugänglich gemacht werden können. So erhielten wir beim Erhitzen von Quadratsäure -diethylester bzw. von Quadratsäure- monochlorid mit Pyridin in Acetanhydrid das Pyridinium-Betain. In entsprechender Weise entstand bei der Umsetzung von Quadratsäure-diethylester bzw. von Quadratsäure-monochlorid mit Triphenylphosphan das Triphenylphosphonium -Betain.Further tests showed that the N- and P-betaines were also easy can be made accessible from other squaric acid derivatives. So got we when heating squaric acid diethyl ester or squaric acid monochloride pyridinium betaine with pyridine in acetic anhydride. In a corresponding way arose in the implementation of diethyl squarate or monochloride squarate with triphenylphosphine the triphenylphosphonium betaine.

Variante 4 Zur Herstellung von Schwefel-Betainen ( 9 ) der Quadratsäure wurde Quadratsäuredichlorid in Tetrahydrofuran gelöst, die äquimolare Menge Wasser hinzugegeben und die Lösung 20 min.Variant 4 For the production of sulfur betaines (9) from squaric acid squaric acid dichloride was dissolved in tetrahydrofuran, the equimolar amount of water added and the solution 20 min.

unter Rückfluss erhitzt. Sodann wurde zur Trockne einrotiert.heated under reflux. It was then evaporated to dryness.

Der Rückstand wurde in Acetanhydrid aufgenommen und die äquimolare Menge eines Dialkylsulfides hinzugefügt. Hierbei fielen die Schwefel-Betaine ( 9 ) in mässiger bis guter Ausbeute an. ( Tabelle 2 ).The residue was taken up in acetic anhydride and the equimolar Amount of a dialkyl sulfide added. The sulfur betaines (9 ) in moderate to good yield. (Table 2).

Variante 4 eignet sich auch in vorzüglicher Weise zur Herstellung von N-, P- und As-Betainen.Variant 4 is also ideally suited for production of N-, P- and As-betaines.

Die Betaine der Quadratsäure mit der allgemeinen Formel ( 1 eignen sich als Grundprodukte für Pharmazeutika sowie als Stabilisierungsmittel für Kunststoffe.The betaines of squaric acid with the general formula (1 are suitable as basic products for pharmaceuticals and as stabilizers for plastics.

1 - ( 2-Hydroxy- 3, 4-dioxocyclobutenyl) -ammonium -Betaine ( 6a -u ) ; allgemeine Arbeitsvorschrift Eine Lösung von Quadratsäuredichlorid ( 2, 1 g , 14 mmol in Tetrahydrofuran ( 20 mal ) wird gerührt und auf OOC abgekühlt. Hierzu lässt man eine Lösung des tertiären Amins ( zur Bildung von ( 6a ) 42 mmol ; zur Bildung von ( 6 b und 6c 28 mmol ; zur Bildung von ( 6d - 6u) 14 mmol ) sowie drei Tropfen Wasser ( ca 20 mmol ) in Tetrahydrofuran ( 30 ml ) im Verlauf von 20 min. hinzutropfen. Bereits nach Zugabe weniger Tropfen des Amin/Wasser Gemisches in Tetrahydrofuran setzt die Ausfällung eines farbigen Niederschlages ein. Nach beendeter Vereinigung der Lösungen wird 30 min.1 - (2-Hydroxy-3, 4-dioxocyclobutenyl) -ammonium -Betaine (6a -u ); General working instructions A solution of squaric acid dichloride (2.1 g , 14 mmol in tetrahydrofuran (20 times) is stirred and cooled to OOC. For this a solution of the tertiary amine (to form (6a) 42 mmol; Formation of (6 b and 6c 28 mmol; to form (6d - 6u) 14 mmol) and three Drops of water (approx. 20 mmol) in tetrahydrofuran (30 ml) in the course of 20 min. to drip in. After just adding a few drops of the amine / water mixture in tetrahydrofuran the precipitation of a colored precipitate begins. After the union is over the solutions is 30 min.

am Rückfluss erhitzt, das Betain abgenutscht, mit Ether nachgewaschen und sodann umkristallisiert. ( Solvens : siehe Tabelle 1 Die Betaine ( 6 m ) und ( 6 n ) scheiden sich aus der Reaktionslösung schleimig ab. In diesen Fällen wird mit Ether ( 20 ml versetzt und die Reaktionsmischung noch 2 h gerührt. Sodann wird wie oben weitergearbeitet.heated to reflux, the betaine suction filtered, washed with ether and then recrystallized. (Solvent: see Table 1 The Betaines (6 m) and (6 n) separate from the reaction solution slimy. In these cases it will ether (20 ml is added and the reaction mixture is stirred for a further 2 hours continued as above.

Bei der Herstellung der Betaine ( 6 q - s) wurde die Reaktionslösung 2 h am Rückfluss erhitzt.In the preparation of the betaines (6 q - s) the reaction solution Heated to reflux for 2 h.

Tabelle 1. Pro- X Ausbeute [%] F. [°C] Summenfor- I.R. (KBr) dukt Farbe (Solvens) mel v [cm-1] 6 a (C2H5)3N 78 189 - 191 (Zers.) C10H15NO3 1790, 1730 ; 1650 - 1600 gelbgrün (Ethanol) (197.2) 6 b C6H5 - CH2 - N(CH3)2 37 141 - 143 (Zers.) C13H13NO3 1790, 1730 ; 1670 - 1580 gelb (Wasser) (231.3) 6 c # 35 225 (Zers.) C9H11NO4 1795, 1730 ; 1700 - 1590 gelb (Wasser) (197.2) 6 d # 76 276 - 279 (Zers.) C9H5NO3 1790, 1760, 1740 ; 1860 - 1570 orange (Acetonitril) (175.1) 6e # 46 165 - 195 (Zers.) C10H7NO3 1780, 1760, 1730 ; goldbraun (Ethanol) (189.1) 1660-1570 6f # 50 262 (Zers.) C10H7NO3 1790, 1735 ; orange (Wasser) (189.1) 1660 - 1550 6g # 60 190 (Zers.) C10H7NO3 1785, 1730 ; goldbraun (Acetonitril) (189.1) 1650 - 1560 6h # 32 181 (Zers.) C11H9NO3 1785, 1735 ; 1850 - 1600 dunkelbraun (Ethanol) (203.3) 6i # 34 190 (Zers.) C11H9NO3 1790. 1735 ; braun (Ethanol) (203.3) 1850 - 1580 6j # 44 295 (Zers.) C11H9NO3 1780, 1730 ; 1670 - 1550 orange (Ethanol) (203.3) 6h # 31 287 (Zers.) C10H4N2O3 1790, 1760, 1735 ; rotbraun (Wasser) (202,2) 1660 - 1580 6l # 39 270 (Zers.) C10H6N2O4 1780, 1740 ; 1650 - 1580 orangerot (Wasser) (218.2) 6m # 48 C13H7NO3 1780, 1785, 1735 ; orangerot (225.2) 1650 - 1590 6n # 34 265 (Zers.) 1785, 1740 ; orange (Eisessig) 1640 - 1550 6o Nicotinsäure-methylester 39 230 (Zers.) C11H7NO5 orange-rot (Wasser) (233.18) 6p 3-Hydroxy-pyridin 82 265 - 270 (Zers.) C9H5NO4 goldbraun (Wasser) 191,14 6q 25 238 (Zers.) C8H6N2O8 2-Amino-pyridin (Aus CH3CN mit hellbraun Ether gefällt) 190,12 6r 4-Amino-pyridin 13 290 (Zers.) C9H6N2O3 hellbraun (Wasser) 190.12 6s 4-Amino-pyridin 36 300 (Zers.) C9H6N2O3 orange-rot (Wasser) 190,12 6t Tropin 72 234 - 238 (Zers.) C12H15NO4 hellbraun (Ethanol) 237,28 6u 4-tert. Butyl- 56 232 - 285 (Zers.) C13H13NO3 hellbraun (Wasser) 231.25 1 (2 - Hydroxy 3, 4- dioxo- cyclobutenyl) -triarylphosphonium -Betaine ( 7a - f ) nach Variante 1 ; allgemeine Arbeitsvorschrift Quadratsäuredichlorid ( 2, 26 g; 15 mmol ) wird in Tetrahydrofuran ( 20 mal ) eingetragen und die Lösung auf OOC abgekühlt.Table 1. Pro- X yield [%] F. [° C] Summenfor- IR (KBr) product color (solvent) mel v [cm-1] 6a (C2H5) 3N 78 189-191 (dec.) C10H15NO3 1790, 1730; 1650-1600 yellow-green (ethanol) (197.2) 6b C6H5-CH2-N (CH3) 2 37141-143 (dec.) C13H13NO3 1790, 1730; 1670-1580 yellow (water) (231.3) 6 c # 35 225 (dec.) C9H11NO4 1795, 1730; 1700--1590 yellow (water) (197.2) 6 d # 76 276-279 (dec.) C9H5NO3 1790, 1760, 1740; 1860-1570 orange (acetonitrile) (175.1) 6e # 46 165-195 (dec.) C10H7NO3 1780, 1760, 1730; golden brown (ethanol) (189.1) 1660-1570 6f # 50 262 (dec.) C10H7NO3 1790, 1735; orange (water) (189.1) 1660-1550 6g # 60 190 (dec.) C10H7NO3 1785, 1730; golden brown (acetonitrile) (189.1) 1650 - 1560 6h # 32 181 (dec.) C11H9NO3 1785, 1735; 1850-1600 dark brown (ethanol) (203.3) 6i # 34 190 (dec.) C11H9NO3 1790, 1735; brown (ethanol) (203.3) 1850 - 1580 6j # 44 295 (dec.) C11H9NO3 1780, 1730; 1670-1550 orange (ethanol) (203.3) 6h # 31 287 (dec.) C10H4N2O3 1790, 1760, 1735; red brown (water) (202.2) 1660--1580 61 # 39 270 (dec.) C10H6N2O4 1780, 1740; 1650-1580 orange-red (water) (218.2) 6m # 48 C13H7NO3 1780, 1785, 1735; orange-red (225.2) 1650-1590 6n # 34 265 (dec.) 1785, 1740; orange (glacial acetic acid) 1640-1550 6o methyl nicotinate 39 230 (dec.) C11H7NO5 orange-red (water) (233.18) 6p 3-Hydroxypyridine 82 265-270 (dec.) C9H5NO4 golden brown (water) 191.14 6q 25 238 (dec.) C8H6N2O8 2-Amino-pyridine (From CH3CN with light brown ether precipitated) 190.12 6r 4-Amino-pyridine 13 290 (dec.) C9H6N2O3 light brown (water) 190.12 6s 4-Amino-pyridine 36 300 (dec.) C9H6N2O3 orange-red (water) 190.12 6t tropine 72 234 - 238 (dec.) C12H15NO4 light brown (ethanol) 237.28 6u 4-tert. Butyl- 56 232-285 (dec.) C13H13NO3 light brown (water) 231.25 1 (2 - hydroxy 3, 4 - dioxocyclobutenyl) triarylphosphonium betaines (7a - f) according to variant 1; general working procedure squaric acid dichloride (2.26 g; 15 mmol) is introduced into tetrahydrofuran (20 times) and the solution is cooled to OOC.

Unter Rühren lässt man hierzu die Lösung eines Triarylphosphans (15 mmol ) und drei Tropfen Wasser ( ca 20 mmol ) in Tetrahydrofuran ( 30 ml ) im Verlauf von 20 min. zutropfen.For this purpose, the solution of a triarylphosphine (15 mmol) and three drops of water (approx. 20 mmol) in tetrahydrofuran (30 ml) in the course of 20 min. to be added dropwise.

Nach beendeter Vereinigung der Lösungen wird zum Rückfluss erhitzt und im Verlauf von 2 h noch fünf mal mit je zwei Tropfen Wasser versetzt. Nach Abkühlen der Reaktionsmischung fällt das Betain kristallin aus. Die Reakktionslösung der Betaine ( 5b - f) wird zunächst eingeengt ; nach Abkühlen fallen sodann die Betaine kristallin aus. Die Betaine werden abgesaugt, mit Ether gewaschen und umkristallisiert. ( Solvens siehe Tabelle 2 ).When the combination of the solutions has ended, the mixture is heated to reflux and two drops of water are added five times over the course of 2 hours. After cooling down the betaine precipitates in crystalline form from the reaction mixture. The reaction solution of Betaine (5b - f) is first concentrated; After cooling down, the betaines then fall crystalline. The betaines are filtered off with suction, washed with ether and recrystallized. (Solvent see Table 2).

1 - (2 -Hydroxy- 3, 4-dioxo-cyclobutenyl)-triphenylarsonium-Betain ( 8 ). Die Darstellung erfolgte nach der vorstehend angegebenen "allgemeinen Arbeitsvorschrift" der Variante 1.1 - (2-Hydroxy-3, 4-dioxo-cyclobutenyl) -triphenylarsonium-betaine ( 8th ). The presentation was carried out according to the "general working instructions" given above variant 1.

Bezüglich physikalisch chemischer Eigenschaften von ( 8 ) siehe Tabelle 2, 1 - (2 - Hydroxy- 3, 4- dioxo- cyclobutenyl) -dialkylsulfonium -B eta= ine ( 9 a - c ) nach Variante 4 ; allgemeine Arbeitsvorschrift Quadratsäuredichlorid ( 2, 26 g ; 15 mmol ) wird in Tetrahydrofuran ( 30 ml ) gelöst und die Lösung mit Wasser ( 5 Tropfen ca 25 mmol ) versetzt. Es wird 20 min. unter gelindem Rückfluss erhitzt und sodann das Solvens abrotiert, bis das zurückbleibende Öl erstarrt. Der braune Feststoff < 1, 00 g ) wird in Acetanhydrid ( 10 ml ) gelöst und die Lösung eines Dialkylsulfides ( 7, 5 mmol ) in Acetanhydrid ( 5 ml ) unter Rühren hinzugetropft. Nach wenigen min. setzt die Ausfällung eines gelben Niederschlages ein. Es wird noch 30 min. gerührt, auf O C abgekühlt und der Niederschlag abfiltriert. Es wird mit Ether nachgewaschen und sodann aus Acetanhydrid umkristallisiert.For the physicochemical properties of (8) see table 2, 1 - (2 - hydroxy-3, 4-dioxocyclobutenyl) dialkylsulfonium -B eta = ine (9 a - c) according to variant 4; general working instructions squaric acid dichloride (2.26 g; 15 mmol) is dissolved in tetrahydrofuran (30 ml) and the solution with Water (5 drops approx 25 mmol) are added. It is under gentle reflux for 20 minutes heated and then spun off the solvent until the remaining oil solidifies. Of the brown solid <1.00 g) is dissolved in acetic anhydride (10 ml) and the solution of a dialkyl sulfide (7.5 mmol) in acetic anhydride (5 ml) was added dropwise with stirring. After a few minutes, a yellow precipitate begins to precipitate. It will Stirred for a further 30 min., cooled to OC and the precipitate filtered off. It will washed with ether and then recrystallized from acetic anhydride.

Eigenschaften der Betaine ( 9a - c ) siehe Tabelle 2.For properties of the betaines (9a - c) see Table 2.

Tabelle 2. Pro- R n Z Aus- F. [°C] Summenformel I.R. (KBr) dukt beute (Solvens) v [cm-1] [%] 7a C6H5 3 P 85-96 268 - 270 (Zers.) C22H15O3P 1770, 1755 ; (Eisessig) (358.3) 1660 - 1600 7b 4-CH3-C6H4 3 P 86-91 229 - 231 (Zers.) C25H21O3P 1770, 1755 ; (Ethanol) (400.4) 1680 - 1550 7c 4-CH3O-C6H4 3 P 42-58 194 - 196 (Zers.) C25H21O6P 1765, 1750 (CH2Cl2/Ether) (448.4) 1650, 1620, 1590 7d 4-Cl-C6H4 3 P 85 236 - 237 (Zers.) C22H12Cl3O3P 1785, 1750 ; (Eisessig) (461.7) 1680 - 1590 7e 8-Cl-C6H4 3 P 58 199 - 201 (Zers.) C22H12Cl3O3P 1770, 1755 ; (Ethanol) (461.3) 1680 - 1590 7f 4-F-C6H4 3 P 57 208 - 210 (Zers.) C22H12F3O3P 1770, 1755 ; (Ethanol) (412.3) 1650, 1620, 1585 8 C6H5 3 As 71 256 - 258 (Zers.) C22H15AsO3 1765, 1745 ; (Ethanol) (402.3) 1680 - 1500 9a CH3 2 S 68 157 - 159 (Zers.) C8H6O8S 1775. 1740 ; (Acetanhydrid) (158.2) 1680, 1640 9b CH3-CH2 2 S 78 149 - 151 C8H10O3S 1775, 1740 ; (Acetanhydrid) (186.2) 1660, 1630 9c -(CH2)4- -- S 74 162 - 164 C8H8O3S 1770, 1740 ; (Acetanhydrid) (184.2) 1655, 1630 l-(a-Hydroxy- 3, 4- dioxocyclobutenyl) -pyridinium -Betain ( 6 d nach Variante 2 1, 00 g ( 5, 2 mmol ) Monopyridinium-quadratat ( 3 a ) werden in 30 ml Acetanhydrid eingetragen und die Reaktionsmischung langsam erhitzt. In der Hitze beginnt bereits die Ausfällung des Pyridinium-Betains ( 6 d ). Nach 10 min. Erhitzen wird abgekühlt, der Niederschlag abgesaugt und aus Wasser umkristallisiert. Gelbe. glänzende Kristalle. Ausbeute 0,59 g (65 %). Fp. : 278 - 280°C (Zers.).Table 2. Pro- R n Z Aus F. [° C] Molecular formula IR (KBr) duct prey (solvent) v [cm-1] [%] 7a C6H5 3 P 85-96 268-270 (dec.) C22H15O3P 1770, 1755; (Glacial acetic acid) (358.3) 1660--1600 7b 4-CH3 -C6H4 3 P86-91 229-231 (dec.) C25H21O3P 1770, 1755; (Ethanol) (400.4) 1680-1550 7c 4-CH3O-C6H4 3 P 42-58 194-196 (dec.) C25H21O6P 1765, 1750 (CH2Cl2 / ether) (448.4) 1650, 1620, 1590 7d 4-Cl-C6H4 3 P 85 236-237 (dec.) C22H12Cl3O3P 1785, 1750; (Glacial acetic acid) (461.7) 1680--1590 7e 8-Cl-C6H4 3 P 58 199-201 (dec.) C22H12Cl3O3P 1770, 1755; (Ethanol) (461.3) 1680-1590 7f 4-F-C6H4 3 P 57 208-210 (dec.) C22H12F303P 1770, 1755; (Ethanol) (412.3) 1650, 1620, 1585 8 C6H5 3 As 71 256-258 (dec.) C22H15AsO3 1765, 1745; (Ethanol) (402.3) 1680-1500 9a CH3 2 S 68 157-159 (dec.) C8H6O8S 1775, 1740; (Acetic anhydride) (158.2) 1680, 1640 9b CH3-CH2 2 S 78 149-151 C8H10O3S 1775, 1740; (Acetic anhydride) (186.2) 1660, 1630 9c - (CH2) 4 - S 74 162-164 C8H8O3S 1770, 1740; (Acetic anhydride) (184.2) 1655, 1630 1- (a-Hydroxy- 3, 4- dioxocyclobutenyl) pyridinium betaine (6 d according to variant 2 1.00 g (5.2 mmol) monopyridinium square (3 a) are introduced into 30 ml acetic anhydride and the reaction mixture slowly The precipitation of the pyridinium betaine (6 d) already begins in the heat. After 10 minutes of heating, the mixture is cooled, the precipitate is filtered off with suction and recrystallized from water. Yellow, glossy crystals. Yield 0.59 g (65%). Mp .: 278-280 ° C (dec.).

Weitere Beispiele zur Variante 2 : Siehe Tabelle 3.Further examples for variant 2: See table 3.

1 - (2 - Hydroxy- 3, 4-dioxocyclobutenyl) - (4-carboxy-pyridinium)-Betain nach Variante 3 0, 50g ( 4, 4 mmol) Quadrat säure werden in der Hitze in 20 ml Acetanhydrid gelöst. Sodann weden 0,'54 g ( 4, 4 mmol ) Isonicotinsäure hinzugefügt und gelinde am Rückfluss erhitzt.1 - (2 - Hydroxy-3, 4-dioxocyclobutenyl) - (4-carboxy-pyridinium) -betaine according to variant 3 0, 50g (4, 4 mmol) square acid are in the heat in 20 ml acetic anhydride solved. Then 0.154 g (4.4 mmol) of isonicotinic acid are added and mild heated to reflux.

Nach 20 min Reaktionszeit wird abgekühlt. Der ausgefallene Niederschlag wird abgesaugt und aus Wasser umkristallisiert.After a reaction time of 20 minutes, the mixture is cooled. The precipitate formed is suctioned off and recrystallized from water.

Orange-rote glitzernde Kristalle. Ausbeute 0, 63 g ( 66 % ).Orange-red glittering crystals. Yield 0.63 g (66%).

Fp. 273 OC ( Zers. ) Elementaranalyse : C 1 oH5N O5 ( 219,16 Ber. : C 54,81 H 2,30 N 6,39 Gef. : C 54,81 H 2,21 N 6,23 Weitere Beispiele zur Variante 3 : Siehe Tabelle 3.Mp. 273 OC (dec.) Elemental analysis: C 1 oH5N O5 (219.16 calc. : C 54.81 H 2.30 N 6.39 Found: C 54.81 H 2.21 N 6.23 Further examples of the variant 3: See table 3.

Tabelle 3. Table 3.

Pro- X F(Zers) [°C] Ausbeute % Veriente 2 dukl ( Solvens ) Variante 2 3 3a Pyridin 222 - 225 81-(Ethanol) 6d l'yridin 279 1 -- 65 94 (Wasser) 8b ß-Picolin 175 93-(Ethanol) 6f ß-Picolin 269 -- 66 95 (Wasser) 3c # -Picolin 174 # 96 -- --~ (Ethanol) 6g #-Picoliu 210 -- 48 95 (Wasser) 3d Nicotinsäurem ethyles ter 190 i 44-(Ethanol) 6O Nicolinsäuremethylester 229 1 - 47 70 (Wasser) 3e Chinolin 236 - 238 86-(Ethanol) 6m. Chinolin 273 ' -- 58 82 (Wasser) 6n Isochinolin 264 # - - -- 97 - (Wasser) 6l Nicotinsäureamid 275 -- -- 74 (Wasser) 6c . N-methylmorpholin 255 , -- -- 26 - (Wasser) 7a Triphenylphosphan 268 - 270 -- -- 90 (Eisessig) 7b # fris-(4-methylphenyl)- 228 - 230 -- -- 52 - phosphan (Ethanol) 7f Tris-(4-fluorphenyl)- 208 - 211 -- -- 61 phosphan (Ethanol) 7d Tris-(4-fluorphenyl)- 235 - 237 -- -- 39 phosphan (Eisessig)Pro- X F (Dec) [° C] Yield% Veriente 2 dukl (Solvens) variant 2 3 3a pyridine 222-225 81- (ethanol) 6d l'yridine 279 1-65 94 (water) 8b β-picoline 175 93- (ethanol) 6f β-picoline 269-66 95 (water) 3c # -picoline 174 # 96 - - ~ (Ethanol) 6g # -Picoliu 210-4895 (water) 3d nicotinic acid ethyl ester 190 i 44- (ethanol) 6O methyl nicolinate 229 1 - 47 70 (water) 3e quinoline 236 - 238 86- (ethanol) 6m. Quinoline 273 '- 58 82 (water) 6n isoquinoline 264 # - - - 97 - (water) 6l nicotinic acid amide 275 - - 74 (water) 6c. N-methylmorpholine 255 , - - 26 - (water) 7a triphenylphosphine 268 - 270 - - 90 (glacial acetic acid) 7b # fris- (4-methylphenyl) - 228 - 230 - - 52 - phosphine (ethanol) 7f tris (4-fluorophenyl) - 208 - 211 - - 61 phosphine (ethanol) 7d tris (4-fluorophenyl) - 235 - 237 - - 39 phosphine (glacial acetic acid)

Claims (7)

P a t e n t a n s p r ü c h e : 1. Betaine der Quadratsäure der allgemeinen Formel (1) (1) in der X entweder R3Z ist, wobei dann Z = N, P, As, S oder Se ist und n bei Z = N, P und As drei und bei Z = S und Se zwei bedeutet, und die organischen Reste R gleich oder verschieden sind und einen Alkylrest von C1 bis C12, einen Cycloalkylrest von C5 bis C12, einen Arylrest von C6 bis C15 oder einen Aralkylrest von C6 bis C15 bedeuten oder in der X ein gesättigter, ungesättigter oder aromatischer Heterocyclus ist, dessen Heteroatom aus der Gruppe N, P, As, S oder Se der Träger der positiven Partialladung ist und direkt mit dem 2-Hydroxy-3, 4-dioxocyclobutenyl- Betainrest verbunden ist, ausgenommen ist das 1 - (2 - Hydroxy - 3,4 - dioxocyclobutenyl)-triphenylphosphonium -Betain.P atent claims: 1. Betaines of squaric acid of the general formula (1) (1) in which X is either R3Z, in which case Z = N, P, As, S or Se and n for Z = N, P and As is three and for Z = S and Se is two, and the organic radicals R. are identical or different and represent an alkyl radical from C1 to C12, a cycloalkyl radical from C5 to C12, an aryl radical from C6 to C15 or an aralkyl radical from C6 to C15, or in which X is a saturated, unsaturated or aromatic heterocycle whose heteroatom consists of Group N, P, As, S or Se is the carrier of the positive partial charge and is directly connected to the 2-hydroxy-3, 4-dioxocyclobutenyl betaine residue, with the exception of 1 - (2 - hydroxy - 3,4 - dioxocyclobutenyl) triphenylphosphonium betaine. 2. Betaine nach Anspruch 1, dadurch gekennzeichnet, dass Z = N und n = 3 bedeuten und die Reste R gleich oder verschieden sind und einen Alkylrest von C1 bis C12 oder einen Aralkylrest von C7 bis C15 bedeuten.2. Betaines according to claim 1, characterized in that Z = N and n = 3 and the radicals R are identical or different and are an alkyl radical from C1 to C12 or an aralkyl radical from C7 to C15. 3. Betaine nach Anspruch 1, dadurch gekennzeichnet, dass X ein Heterocyclus aus der Gruppe N-Methyl-morpholin, Pyridin, Picolin, Lutidin, tert.-Butyl-pyridin, Benzylpyridin, Nicotinsäure -alkylester, Nicotinsäureamid, Cyano pyridin, Aminopyridin, Hydroxypyridin, Chinolin , Isochinolin, Imidazol ist.3. Betaines according to claim 1, characterized in that X is a heterocycle from the group N-methyl-morpholine, Pyridine, picoline, lutidine, tert-butyl-pyridine, Benzylpyridine, nicotinic acid alkyl ester, nicotinic acid amide, cyano pyridine, aminopyridine, Is hydroxypyridine, quinoline, isoquinoline, imidazole. 4. Betaine nach Anspruch 1, dadurch gekennzeichnet, dass Z = P oder As und n = 3 bedeuten und die Reste R gleich sind oder verschieden und einen substituierten oder unsubstituierten Phenylrest bedeuten.4. Betaines according to claim 1, characterized in that Z = P or As and n = 3 and the radicals R are identical or different and one is substituted or unsubstituted phenyl radical. 5. Betaine nach Anspruch 1, dadurch gekennzeichnet, dass Z = S oder Se und n = 2 bedeuten und die Reste R gleich oder verschieden sind und einen Alkylrest von C1 bis C6 bedeuten oder dass X ein schwefelhaltiger Heterocyclus ist, wie z. B. Tetrahydrothiophen.5. Betaines according to claim 1, characterized in that Z = S or Se and n = 2 and the radicals R are identical or different and are an alkyl radical from C1 to C6 or that X is a sulfur-containing heterocycle, such as, for. B. tetrahydrothiophene. 6. Verfahren zur Herstellung der Betaine ( 1 ) der Quadratsäure nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass ein 1,2-disubstituiertes 3,4-Dioxo-cyclobuten-(1, 2) der allgemeinen Formel ( 2 ) mit einer Verbindung der allgemeinen Formel X, gegebenenfalls in Gegenwart von Wasser, eines inerten organischen Lösungsmittels und / oder Acetanhydrid umgesetzt wird. 6. Process for the preparation of betaines (1) of squaric acid according to one of claims 1 to 5, characterized in that a 1,2-disubstituted 3,4-dioxocyclobutene (1, 2) of the general formula (2) with a compound of the general formula X, optionally in the presence of water, an inert organic solvent and / or acetic anhydride is reacted. (2) (1) wobei Y gleich oder verschieden ist und -OH , -OAlkyl ( Alkyl = C1 bis C4 ) oder Hal (Hal = C1 oder Br ) bedeutet und X die in den Ansprüchen 1 bis 5 angegebene Bedeutung hat.(2) (1) where Y is the same or different and -OH , -O-alkyl (alkyl = C1 to C4) or Hal (Hal = C1 or Br) and X denotes the has the meaning given in claims 1 to 5. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass als Verbindung ( 2 ) Quadratsäure, Quadratsäuredichlorid, Quadratsäuremonochlorid, Quadratsäuremonobromid, Qua -dratsäurediethylester oder Quadratsäuredibutyle ster einge -setzt wird.7. The method according to claim 6, characterized in that as a connection (2) squaric acid, squaric acid dichloride, squaric acid monochloride, squaric acid monobromide, Diethyl quadrate or dibutyl squarate is used.
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Publication number Priority date Publication date Assignee Title
WO2002010136A1 (en) * 2000-08-02 2002-02-07 Celltech R & D Limited 3-substituted isoquinolin-1-yl derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002010136A1 (en) * 2000-08-02 2002-02-07 Celltech R & D Limited 3-substituted isoquinolin-1-yl derivatives

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