DE927505C - Process for the production of thiosemicarbazones - Google Patents
Process for the production of thiosemicarbazonesInfo
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- DE927505C DE927505C DEP14595A DEP0014595A DE927505C DE 927505 C DE927505 C DE 927505C DE P14595 A DEP14595 A DE P14595A DE P0014595 A DEP0014595 A DE P0014595A DE 927505 C DE927505 C DE 927505C
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- aldehyde
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- thiosemicarbazide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- 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
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/40—Nitrogen atoms, not forming part of a nitro radical, e.g. isatin semicarbazone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—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
- 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
- C07D215/14—Radicals substituted by oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/14—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hydrocarbon radicals, substituted by nitrogen atoms, attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D307/70—Nitro radicals
- C07D307/71—Nitro radicals attached in position 5
- C07D307/72—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2
- C07D307/74—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2 by hydrazino or hydrazono or such substituted radicals
- C07D307/76—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2 by hydrazino or hydrazono or such substituted radicals having carbonic acyl radicals or their thio or nitrogen analogues directly attached to the hydrazino or hydrazono radical, e.g. semicarbazides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/58—Radicals substituted by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring
- C07D333/66—Nitrogen atoms not forming part of a nitro radical
Description
Verfahren zur Herstellung von Thiosemicarbazonen Es ist bekannt, daß bestimmte Thiosemicarbazone aromatischer Aldehyde und Ketone gegen Tuberkelbakterien wirksam sind (vgl. D o m a g k, B ehn i s ch, Mietzsch, Schmidt, »Naturwissenschaften« 33, 315 [i946]). Es ist ferner im Patent 852, o86 bereits vorgeschlagen worden, heterocyclische Reste an bestimmte Stellen solcher Thiosemicarbazone einzubauen, indem entweder in die .-Stellung des Thiosemicarbazonrestes Pyridin-, Thiazol-, Thiodiazol- bzw. Pyrimidinreste eingeführt werden, oder indem eine aromatisch gebundene Aminogruppe eines aromatischen Aldehyds oder Ketons durch Heteroaryl- und/oder auch Heteroacyl- (z. B. Nikotinsäure-)Reste substituiert wird, oder indem schließlich das Stickstoffatom dieser aromatischen Aminogruppe selbst Glied eines Heterorestes, z. B. eines Pyrrolidyl-, Piperidyl-, Pyridinium-, Chinazolinium- oder Isochinoliniumrestes, ist.Process for the production of thiosemicarbazones It is known that certain thiosemicarbazones of aromatic aldehydes and ketones are effective against tubercle bacteria (cf. D omagk, Bechnisch, Mietzsch, Schmidt, "Naturwissenschaften" 33, 315 [1946]). It has also already been proposed in patent 852, 086 to incorporate heterocyclic radicals at certain points of such thiosemicarbazones either by introducing pyridine, thiazole, thiodiazole or pyrimidine radicals into the. -Position of the thiosemicarbazone radical, or by introducing an aromatically bonded amino group an aromatic aldehyde or ketone is substituted by heteroaryl and / or heteroacyl (z. B. nicotinic acid) radicals, or by finally the nitrogen atom of this aromatic amino group itself being a member of a hetero radical, e.g. B. a pyrrolidyl, piperidyl, pyridinium, quinazolinium or isoquinolinium radical is.
Es wurde nun gefunden, daß man auch dann zu Verbindungen gelangt, die gegen Tuberkuloseinfektionen der Warmblüter ausgezeichnet wirken, wenn man Thiosemicarbazone von heterocyclischen oder aromatisch-heterocyclischen Oxoverbindungen herstellt, die die Oxogruppe am oder im heterocyclischen Rest selbst tragen, oder Thiosemicarbazone von aromatisch-heterocyclischen Oxoverbindungen aufbaut, die durch eine Oxogruppe am aromatischen Ring substituiert sind, wobei dieser aromatische Ring im Gegensatz zu den Verbindungen des Patents 852 o86 mit dem heterocyclischen -Ring nicht durch Substituierung, sondern durch Annellierung verbunden ist. Die Oxogruppe kann in Form einer Aldehydgruppe oder einer Ketogruppe vorliegen. So können z. B. Pyrrole, Pyridine, Indole, Chinoline, Isochinoline, Acridine,- Imidazole, Pyrazole, Pyrimidine, Pyrazine, Pyridazine, Triazole, Triazine, Benzimidazole, Cinnoline, Chinazoline, Chinoxaline, Furane, Benzofurane, Thiophene, Thionaphthene, Oxazole, Thiazole, Thiodiazole, Benzoxazole und Benzthiazole mit Aldehyd- oder Ketogruppen am heterocyclischen Ring als Ausgangsstoffe verwendet werden. Es können aber auch heterocyclische Ringketone, wie Isatin, Oxythionaphthen, Thionaphthenchinon u. a., benutzt werden. Schließlich können aromatisch-heterocyclische Verbindungen, wie z. B. Indole, Carbazole, Chinoline, Isochinoline, Acridine, Benzimidazole, Cinnoline, Chinazoline, Chinoxaline, Benzofurane, Dibenzofurane, Thionaphthene, Diphenylensulfide, Benzoxazole und Benzthiazole, Verwendung finden, die die Aldehyd- oder Ketogruppe am annellierten aromatischenResttragen.Die heterocyclischen bzw. aromatisch-heterocyclischen Ringe können außer der Aldehyd- und Ketogruppe noch andere, in den »Naturwissenschaften« 33, 315 (i946) als günstig bezeichnete Substituenten, wie Nitro-, Amino-, Alkylamino-, Acylamino-, Arylidenamino-, Alkyl-, Cyan-, Carboxyl-, Oxy- sowie Alkoxy-, Alkylmercapto-, Alkylsulfoxyd- und Alkylsulfonreste, tragen. Die Thiosemicarbazone können sich vom unsubstituierten Thiosemicarbazid wie auch von seinen heterocyclisch substituierten Abkömmlingen herleiten.It has now been found that compounds which are excellent against tuberculosis infections in warm-blooded animals are obtained if thiosemicarbazones are prepared from heterocyclic or aromatic-heterocyclic oxo compounds which carry the oxo group on or in the heterocyclic radical itself, or thiosemicarbazones from aromatic-heterocyclic ones Builds up oxo compounds which are substituted by an oxo group on the aromatic ring, this aromatic ring, in contrast to the compounds of the patent 852,086 with the heterocyclic ring is not connected by substitution, but by annealing. The oxo group can be in the form of an aldehyde group or a keto group. So z. B. pyrroles, pyridines, indoles, quinolines, isoquinolines, acridines, - imidazoles, pyrazoles, pyrimidines, pyrazines, pyridazoles, triazoles, triazines, benzimidazoles, cinnolines, quinazolines, quinoxalines, furans, benzofurans, thiophenes, thionaphthenes, oxazoles, thiazoles , Benzoxazoles and Benzthiazoles with aldehyde or keto groups on the heterocyclic ring can be used as starting materials. However, it is also possible to use heterocyclic ring ketones such as isatin, oxythionaphthene, thionaphthenquinone and others. Finally, aromatic heterocyclic compounds, such as. B. indoles, carbazoles, quinolines, isoquinolines, acridines, benzimidazoles, cinnolines, quinazolines, quinoxalines, benzofurans, dibenzofurans, thionaphthenes, diphenylene sulfides, benzoxazoles and benzthiazoles, which carry the aldehyde or the keto group on the aromatic heterocyclic or fused aromatic In addition to the aldehyde and keto groups, heterocyclic rings can contain other substituents which are described as favorable in the "natural sciences" 33, 315 (1946), such as nitro, amino, alkylamino, acylamino, arylideneamino, alkyl, cyano , Carboxyl, oxy and alkoxy, alkyl mercapto, alkyl sulfoxide and alkyl sulfone radicals, carry. The thiosemicarbazones can be derived from the unsubstituted thiosemicarbazide as well as from its heterocyclically substituted derivatives.
Die Herstellung der gekennzeichneten Verbindungen kann man nach verschiedenen üblichen Arbeitsweisen durchführen. Beispielsweise kann man heterocyclische und aromatisch-heterocyclische Verbindungen, die am oder im heterocyclischen Ring eine Oxogruppe tragen, oder aromatisch-heterocyclische Verbindungen, die durch eine Oxogruppe am annellierten aromatischen Ring substituiert sind, mit Thiosemicarbazid oder seinen heterocyclisch-substituierten Abkömmlingen umsetzen. Die Einführung des Thiosemicarbazonrestes kann auch stufenweise geschehen, indem man zunächst diese Oxoverbindungen mit Hydrazin oder seinen Abkömmlingen zu Hydrazinoverbindungen umsetzt und auf diese sodann Rhodanverbindungen oder Senföle einwirken läßt, oder indem man zunächst aus @ diesen Oxoverbindungen und Semi.carbaziden Semicarbazone herstellt und diese sodann mit Schwefelverbindungen reagieren läßt.The production of the marked compounds can be done according to various methods carry out normal working methods. For example, you can heterocyclic and aromatic-heterocyclic compounds on or in the heterocyclic ring Bear oxo group, or aromatic-heterocyclic compounds through an oxo group are substituted on the fused aromatic ring with thiosemicarbazide or its implement heterocyclic-substituted descendants. The introduction of the thiosemicarbazone residue can also be done gradually by first mixing these oxo compounds with hydrazine or its derivatives are converted to hydrazino compounds and then rhodane compounds on these or mustard oils act, or by first starting with these oxo compounds and Semi.carbaziden Semicarbazone produces and then these with sulfur compounds lets react.
An Stelle der Oxoverbindungen selbst kann man in den vorerwähnten Verfahren die funktionellen Derivate der Oxoverbindungen verwenden. Als funktionelle Derivate sind dabei alle diejenigen Abkömmlinge der Oxoverbindungen zu betrachten, die im Rahmen der vorerwähnten Verfahren an die Stelle der Oxoverbindungen zu treten vermögen. Beispiele solcher funktionellen Derivate sind die entsprechenden Thioaldehyde, Thioketone, Acetale, Mercaptale, Diacetate, Halbacetale sowie Bisulfitverbindungen. Auch können die im Patent 838 747 beschriebenen Verfahren sinngemäß angewendet werden, indem an Stelle der Oxoverbindungen deren Abkömmlinge, die an Stelle der C = 0-Bindung eine C = N-Bindung tragen, z. B. Oxime, Anile, Hydrazone, Azine, Imide, Semicarbazone, mit Thiosemicarbazid in saurem Medium umgesetzt werden.Instead of the oxo compounds themselves, one can use the aforementioned Process using the functional derivatives of the oxo compounds. As functional Derivatives are all those derivatives of the oxo compounds to be considered, to take the place of the oxo compounds in the context of the aforementioned processes capital. Examples of such functional derivatives are the corresponding thioaldehydes, Thioketones, acetals, mercaptals, diacetates, hemiacetals and bisulfite compounds. The methods described in patent 838 747 can also be applied accordingly, by replacing the oxo compounds with their derivatives, with those instead of the C = 0 bond carry a C = N bond, e.g. B. oximes, aniles, hydrazones, azines, imides, semicarbazones, be reacted with thiosemicarbazide in acidic medium.
Die so erhaltenen Stoffe können außer zur Bekämpfung von Tuberkuloseinfektionen auch zu anderen Zwecken, z. B. zur Schädlingsbekämpfung, Verwendung finden.The substances obtained in this way can also be used to combat tuberculosis infections also for other purposes, e.g. B. for pest control, use.
Beispiel i 83 g 1,- 2, 3, 4-Tetrahydrochinolin-6-aldehyd werden in Alkohol unter Erwärmen gelöst, eine Lösung von 47 g Thiosemicarbazid in heißem Wasser zugefügt und mit einigen Tropfen Essigsäure versetzt. Nach istündigem Erhitzen auf dem Wasserbad wird abgekühlt und dadurch das Thiosemicarbazon des 1, 2, 3, 4-Tetrahydrochinolin-6-aldehyds abgeschieden. Nach Umkristallisieren aus Butanol erhält man gelbbraune Nadeln, die nach vorheriger Bräunung bei 2i9° unter Aufschäumen zu einer roten Flüssigkeit schmelzen, in einer Ausbeute von 86% der Theorie.Example i 83 g of 1, - 2, 3, 4-tetrahydroquinoline-6-aldehyde are in Alcohol dissolved with warming, a solution of 47 g thiosemicarbazide in hot water added and mixed with a few drops of acetic acid. After heating for one hour the water bath is cooled and thereby the thiosemicarbazone of 1, 2, 3, 4-tetrahydroquinoline-6-aldehyde deposited. After recrystallization from butanol, yellow-brown needles are obtained which after browning at 2 ° to 9 °, melt into a red liquid while foaming, in a yield of 86% of theory.
In gleicher Weise erhält man das Thiosemicarbazon des N-Methyl-i, 2, 3, 4-tetrahydrochinolin-6-aldehyds in gelben Kristallen, die bei igi° unter Aufschäumen zu einer dunkelroten Flüssigkeit schmelzen.The thiosemicarbazone of N-methyl-i is obtained in the same way, 2, 3, 4-tetrahydroquinoline-6-aldehyde in yellow crystals, which at igi ° with foaming Melt to a dark red liquid.
Bei Verwendung des Chinolin-6-aldehyds erhält man ein gelbes Thiosemicarbazon, das bei 226° unter Aufschäumen schmilzt, in einer Ausbeute von fast 9o % der Theorie.When using the quinoline-6-aldehyde, a yellow thiosemicarbazone is obtained, which melts at 226 ° with foaming, in a yield of almost 90% of theory.
In ähnlicher Weise können die Thiosemicarbazone des Chinolin-4-aldehyds, Chinolin-7-aldehyds, Chinolin-8-aldehyds,N-Methyl-chinolon-4-aldehyds, N-Methyl-chinolon-6-aldehyds, 6-Methoxy -chinolin-4-aldehyds, 6-Acetylamino--chinolin-4-aldehyds, 7-Dimethylamino-chinolin-4-aldehyds, 4-Methoxychinolin-6-aldehyds, 4-Amino-chinolin-6-aldehyds, 4-Acetylamino-chinolin-6-aldehy ds und Isochinolini-aldehyds hergestellt werden.The thiosemicarbazones of quinoline-4-aldehyde, Quinoline-7-aldehyde, quinoline-8-aldehyde, N-methyl-quinolone-4-aldehyde, N-methyl-quinolone-6-aldehyde, 6-methoxy-quinoline-4-aldehyde, 6-acetylamino-quinoline-4-aldehyde, 7-dimethylamino-quinoline-4-aldehyde, 4-methoxyquinoline-6-aldehyde, 4-amino-quinoline-6-aldehyde, 4-acetylamino-quinoline-6-aldehyde ds and isoquinolini aldehydes are produced.
Beispiel e Eine Lösung von 5,1 g Indol-3-aldehyd in So ccm Alkohol wird mit einer heißen Lösung von 4 g Thiosemicarbazid in 5o ccm Wasser versetzt und 15 Minuten im Sieden gehalten. Das Thiosemicarbazon scheidet sich bereits in der Hitze kristallin aus und wird nach Abkühlen abgesaugt, mit Alkohol gewaschen und getrocknet. Es bildet bräunlichgelbe, sandige Kristalle, die bei 232° unter Zersetzung schmelzen. Die Ausbeute ist fast quantitativ.Example e A solution of 5.1 g of indole-3-aldehyde in 1 cc of alcohol a hot solution of 4 g of thiosemicarbazide in 5o ccm of water is added and kept boiling for 15 minutes. The thiosemicarbazone already separates into crystalline from the heat and, after cooling, is filtered off with suction and washed with alcohol and dried. It forms brownish-yellow, sandy crystals, which at 232 ° below Melt decomposition. The yield is almost quantitative.
In gleicher Weise kann aus N-Methyl-indol-3-aldehyd das Thiosemicarbazon vom Schmelzpunkt 197° (unter Zersetzung) erhalten werden. Das Thiosemicarbazon des 2-Methyl-indol-3-aldehyds bildet schwachgrünliche Kristalle vom Schmelzpunkt 213° (unter Zersetzung), das Thiosemicaxbazon des 2-Methyl-2, 3-dihydro-indol-5-aldehyds schwachrötliche Kristalle vom Schmelzpunkt 178' (unter Zersetzung), das Thiosemicarbazon des 1, 3, 3-Trimethyl-indol-2-methylen-a)-aldehyds gelbe Kristalle vom Schmelzpunkt 176° (unter Zersetzung ) und das Thiosemicarbazon des 5-Methoxy-1, 3, 3-trimethyl-indol-2-methylen-co-aldehyds gelbe Kristalle vom Schmelzpunkt 178° (unter Zersetzung).In the same way, thiosemicarbazone can be obtained from N-methyl-indole-3-aldehyde with a melting point of 197 ° (with decomposition). The thiosemicarbazone des 2-methyl-indole-3-aldehyde forms pale greenish crystals with a melting point of 213 ° (with decomposition), the thiosemicaxbazon of 2-methyl-2, 3-dihydro-indole-5-aldehyde Pale reddish crystals with a melting point of 178 '(with decomposition), the thiosemicarbazone des 1, 3, 3-trimethyl-indole-2-methylene-a) -aldehyde yellow crystals with a melting point 176 ° (with decomposition ) and the thiosemicarbazone des 5-methoxy-1, 3,3-trimethyl-indole-2-methylene-co-aldehyde yellow crystals with a melting point of 178 ° (with decomposition).
Beispiel 3 50 g Thionaphthen-3-aldehyd werden in Alkohol kochend gelöst und mit einer heißen Lösung von 21 g Thiosemicarbazid in 6o%igem Alkohol versetzt. Fast augenblicklich wird das Thiosemicarbazon des Thionaphthen-3-aldehyds nahezu quantitativ in fast farblosen Kristallen abgeschieden, die bei 217° unter Aufschäumen zu einer hellroten Flüssigkeit schmelzen.Example 3 50 g of thionaphthen-3-aldehyde are dissolved at the boil in alcohol and a hot solution of 21 g of thiosemicarbazide in 60% alcohol is added. Almost immediately, the thiosemicarbazone of thionaphthen-3-aldehyde is deposited almost quantitatively in almost colorless crystals, which melt at 217 ° with foaming to form a light red liquid.
In ähnlicher Weise können die Thiosemicarbazone des Benzthiazol-2-aldehyds, Benzoxazol-2-aldehyds und Benzimidazol-2-aldehyds hergestellt werden.The thiosemicarbazones of benzothiazole-2-aldehyde, Benzoxazole-2-aldehyde and benzimidazole-2-aldehyde are produced.
Beispiel. 2-Dimethylamino-pyridin-5-aldehyd (hergestellt durch Behandlung von 2-Dimethylamino-pyridin mit Formylmethylanilin-Phosphoroxychlorid nach Vilsmeier-Haack) wird, wie in den obigen Beispielen beschrieben, in das Thiosemicarbazon übergeführt. Die neue Verbindung bildet schwachgrünlichgelbe Kristalle, die bei 218° unter Aufschäumen zu einer roten Flüssigkeit schmelzen. Ausbeute: 75% der Theorie.Example. 2-dimethylaminopyridine-5-aldehyde (produced by treatment of 2-dimethylaminopyridine with formylmethylaniline phosphorus oxychloride according to Vilsmeier-Haack) is, as described in the above examples, converted into the thiosemicarbazone. The new compound forms pale greenish-yellow crystals that foam at 218 ° melt to a red liquid. Yield: 75% of theory.
In ähnlicher Weise können die Thiosemicarbazone des 2-Butoxy-py ridin-5-aldehyds, a-Acetylamino - pyridin - 5 - aldehyds, 4. - Butoxy - pyridin-3-aldehyds, 4-Dimethylamino-pyridin-3-aldehyds, 4Acetylamino-pyridin-3-aldehyds sowie der Pyridin-2- bzw. -3- und -4-aldehyde hergestellt werden. Beispiel s 18 g Acridin-9-aldehyd werden in einem Gemisch von 50 ccm Alkohol, 50 ccm Wasser und 5o ccm Essigsäure unter Erwärmen mit-9 g Thiosemicarbazid versetzt. Man läßt i Stunde sieden, kühlt ab, saugt den schon in der Hitze ausfallenden Niederschlag nach Erkalten ab und wäscht mit Alkohol und Wasser. Das Thiosemicarbazon bildet gelbe Kristalle vom Schmelzpunkt 235°. Die Ausbeute ist fast quantitativ, Beispiel 6 73,5 g Isatin werden in 6oo ccm siedendem Alkohol zum größten Teil in Lösung gebracht und mit einer heißen Lösung von :f6 g Thiosemicarbazid in 6o%igem Alkohol versetzt. Es entsteht zunächst eine klare Lösung. Beim weiteren Erwärmen kristallisiert bereits in der Hitze das Isatin-3-thiOsemicarbazon in Form schöner gelber gekrümmter Nadeln in einer Ausbeute von io8 g aus, die mit verdünntem Alkohol gewaschen und getrocknet werden. Nach Umkristallisieren aus Butanol erhält man gelbe, verfilzte Nadeln, die sich beim Erhitzen über 200° allmählich unter Rotfärbung zersetzen.Similarly, the thiosemicarbazones of 2-butoxy-pyridine-5-aldehyde, α-acetylamino-pyridine-5-aldehyde, 4th-butoxy-pyridine-3-aldehyde, 4-dimethylamino-pyridine-3-aldehyde, 4-acetylamino -pyridine-3-aldehydes and pyridine-2- or -3- and -4-aldehydes are produced. Example s 18 g of acridine-9-aldehyde are mixed with 9 g of thiosemicarbazide in a mixture of 50 cc of alcohol, 50 cc of water and 50 cc of acetic acid with heating. The mixture is boiled for 1 hour, cooled, the precipitate which has already separated out in the heat is filtered off with suction after cooling and washed with alcohol and water. The thiosemicarbazone forms yellow crystals with a melting point of 235 °. The yield is almost quantitative, Example 6 73.5 g of isatin are mostly dissolved in 600 cc of boiling alcohol and a hot solution of: f6 g of thiosemicarbazide in 60% alcohol is added. First of all, a clear solution is created. On further heating, the isatin-3-thiOsemicarbazone crystallizes out in the form of beautiful yellow, curved needles in a yield of 108 g, which are washed with dilute alcohol and dried. After recrystallization from butanol, yellow, matted needles are obtained which, when heated above 200 °, gradually decompose, turning red.
Das in ähnlicher Weise hergestellte 3-Thiosemicarbazon aus 3-Oxy-thionaphthen bildet nach dem Umkristallisieren aus Butanol schwachrötlich gefärbte Kristalle vom Schmelzpunkt 193° (unter Aufschäumen).The 3-thiosemicarbazone produced in a similar manner from 3-oxy-thionaphthene forms pale reddish crystals after recrystallization from butanol melting point 193 ° (with foaming).
Das aus 2, 3-Thionaphthenchinon hergestellte 2, 3-Thionaphthenchinon-3-thiosemicarbazon bildet bräunliche, verfilzte Nadeln vom Schmelzpunkt 2030. Beispiel ? 32 g Thiosemicarbazid werden in i5occmWasser durch Erwärmen gelöst und diese Lösung mit einer Lösung von 50 g 5-Nitrofurfurol in 350 ccm Methanol versetzt. DieLösung färbt sich orangegelb, und bald setzt die Abscheidung des Thiosemicarbazons ein. Man kocht noch einige Stunden am Rückfluß, kühlt ab und isoliert die abgeschiedene Substanz durch Absaugen, Waschen und Trocknen. Man erhält ein eigelbes Pulver in fast quantitativer Ausbeute, das von etwa 24.0° an schmilztundgegen245o verpufft.The 2, 3-thionaphthenquinone-3-thiosemicarbazone produced from 2,3-thionaphthenquinone forms brownish, matted needles with a melting point of 2030. Example? 32 g of thiosemicarbazide are dissolved in 15 ounces of water by heating and a solution of 50 g of 5-nitrofurfurol in 350 cc of methanol is added to this solution. The solution turns orange-yellow and the thiosemicarbazone will soon begin to separate out. The mixture is refluxed for a few more hours, cooled and the deposited substance is isolated by suction, washing and drying. An egg-yellow powder is obtained in almost quantitative yield, which melts from about 24.0 ° and evaporates towards 245 °.
In ähnlicher Weise kann man das Thiosemicarbazon des Furfurols vom Schmelzpunkt i55° herstellen.In a similar way, the thiosemicarbazone of furfural can be obtained from Establish melting point of i55 °.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP14595A DE927505C (en) | 1948-10-02 | 1948-10-02 | Process for the production of thiosemicarbazones |
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| Application Number | Priority Date | Filing Date | Title |
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| DEP14595A DE927505C (en) | 1948-10-02 | 1948-10-02 | Process for the production of thiosemicarbazones |
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| DE927505C true DE927505C (en) | 1955-05-09 |
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| DEP14595A Expired DE927505C (en) | 1948-10-02 | 1948-10-02 | Process for the production of thiosemicarbazones |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2940970A (en) * | 1960-06-14 | Isonicotinyl hydrazide derivatives |
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1948
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2940970A (en) * | 1960-06-14 | Isonicotinyl hydrazide derivatives |
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