DE1041964B - Process for the preparation of substituted bis- (aethyleneimino) -p-benzoquinones - Google Patents
Process for the preparation of substituted bis- (aethyleneimino) -p-benzoquinonesInfo
- Publication number
- DE1041964B DE1041964B DEC12949A DEC0012949A DE1041964B DE 1041964 B DE1041964 B DE 1041964B DE C12949 A DEC12949 A DE C12949A DE C0012949 A DEC0012949 A DE C0012949A DE 1041964 B DE1041964 B DE 1041964B
- Authority
- DE
- Germany
- Prior art keywords
- benzoquinones
- bis
- preparation
- ethyleneimino
- aethyleneimino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
- C07D203/14—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom with carbocyclic rings directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von substituierten Bis-(äthylenimino)-p-benzochinonen Es ist bekannt, daß durch Umsetzung von Chinonen mit Aminen Aminochinone erhalten werden. Bisher war es aber noch nicht gelungen, 2,6-Bis-(äthylenimino)-p-benzochinone herzustellen. Setzt man z. B. 2,6-Dichlorp-benzochinon mit Äthylenimin um, so erhält man 3,6-Bis-(äthylenimino)-2-chlor-p-benzochinon (Petersen, Gauss und Urbschat, Angewandte Chemie, Bd.67 [1955], S. 227). Auch in dem deutschen Patent 967 794 sind keine 2,6-Bis-(äthylenimino)-p-benzochinone beschrieben. In diesem Patent wird zwar erwähnt, daß sich auch 2,6-Dimethoxy- bzw. 2,6-Diäthoxy-benzochinone-(1,4) mit Alkyleniminen umsetzen lassen, jedoch ist nicht ersichtlich, ob dabei 2,6-Bis-(äthylenimino)-p-benzochinone entstehen. Es wird dort weiter angedeutet, daß die Ausgangsstoffe auch Halogenatome enthalten können; der Verlauf der Reaktion in einem solchen Fall wird aber als unvoraussehbar bezeichnet und nicht erläutert.Process for the preparation of substituted bis (ethyleneimino) p-benzoquinones It is known that amino quinones are obtained by reacting quinones with amines will. So far, 2,6-bis- (ethyleneimino) -p-benzoquinones had not yet been produced to manufacture. If you put z. B. 2,6-dichlorop-benzoquinone with ethylene imine to get it one 3,6-bis- (ethyleneimino) -2-chloro-p-benzoquinone (Petersen, Gauss and Urbschat, Angewandte Chemie, Vol. 67 [1955], p. 227). Also in the German patent 967 794 are no 2,6-bis- (ethyleneimino) -p-benzoquinones described. In this patent, it is true mentions that 2,6-dimethoxy- or 2,6-diethoxy-benzoquinone- (1,4) with alkylenimines let convert, but it is not clear whether this is 2,6-bis- (ethyleneimino) -p-benzoquinones develop. It is further indicated there that the starting materials also contain halogen atoms may contain; however, the course of the reaction in such a case becomes unpredictable designated and not explained.
Es wurde nun gefunden, daß substituierte 2,6-Bis-(äthylenimino)-p-benzochinone erhalten werden, wenn man 3,5-Dihalogen-p-benzochinone, die in den 2- und 6-Stellungen niedere Alkoxygruppen aufweisen, mit unsubstituiertem oder an einem Kohlenstoffatom einen niederen Alkylrest, vorzugsweise einen Methylrest, tragendem Äthylenimin umsetzt.It has now been found that substituted 2,6-bis (äthylenimino) -p-benzoquinones be obtained if one uses 3,5-dihalo-p-benzoquinones, which are in the 2- and 6-positions have lower alkoxy groups, with an unsubstituted or on a carbon atom ethyleneimine carrying a lower alkyl radical, preferably a methyl radical.
Vorzugsweise arbeitet man in Lösungsmitteln, wie Dioxan, Äthyl-, Isopropyl-, Butylalkohol oder Isopropyläther, und gegebenenfalls in Gegenwart von Kondensationsmitteln, wie tertiären Basen.It is preferable to work in solvents such as dioxane, ethyl, isopropyl, Butyl alcohol or isopropyl ether, and optionally in the presence of condensing agents, like tertiary bases.
Die so erhaltenen 3,5-Dihalogen-2,6-bis-(äthylenimino)-p-benzochinone, deren Äthylenreste unsubstituiert sind oder je einen niederen Alkylrest, vorzugsweise einen Methylrest, aufweisen und in denen die Halogenatome vorzugsweise Chlor-, Brom- oder Jodatome sind, in erster Linie das Chinon der Formel besitzen eine tumorhemmende Wirkung; zudem weisen sie bakterizide Eigenschaften auf und sind wirksam gegenüber Amoeben, z. B. gegen Entamoeba histolytica.The 3,5-dihalo-2,6-bis- (äthylenimino) -p-benzoquinones, the ethylene radicals of which are unsubstituted or each have a lower alkyl radical, preferably a methyl radical, and in which the halogen atoms are preferably chlorine, bromine or Iodine atoms are primarily the quinone of the formula have an anti-tumor effect; they also have bactericidal properties and are effective against amoebas, e.g. B. against Entamoeba histolytica.
Die verfahrensgemäß erhaltenen Chinone können als Bakterizide sowie als Heilmittel, besonders bei Krebserkrankungen oder durch Amoeben verursachten Erkrankungen, Verwendung finden.The quinones obtained according to the process can be used as bactericides as well as a remedy, especially in cancer or caused by amoeba Diseases, find use.
Die Erfindung wird in den nachfolgenden Beispielen erläutert. Beispiel 1 48,9g 3,5-Dibrom-2,6-dimethoxy-p-benzochinon werden in 600 cm3 Dioxan gelöst. Dazu wird bei Zimmertemperatur ein Gemisch von 33,5 g Triäthylamin und 13,6 g Äthylenimin in 100 cm3 Dioxan zugetropft. Anschließend rührt man 12 Stunden bei Zimmertemperatur. Von den ausgeschiedenen, violetten Nadeln des 3,5-Dibrom-2,6-bis-(äthylenimino)-p-benzochinons der Formel wird abgesaugt. Aus der Mutterlauge wird beim Einengen eine weitere Menge der Verbindung erhalten, welche nach dem Umkristallisieren aus Chloroform-Methanol bei 175'C unter Zersetzung schmilzt. Die Ausbeute beträgt 920/,. Beispiel 2 65,2g 3,5-Dibrom-2,6-dimethoxy-p-benzochinon werden in 600 cm3 Dioxan gelöst, und zu dieser Lösung wird ein Gemisch von 44,5g Triäthylamin und 24,0 g C-Methyläthylenimin in 100 cm3 Dioxan zugetropft. Die Temperatur wird während der Zugabe und während weiterer 5 Stunden bei 50°C gehalten. Die klare Lösung wird im Vakuum zur Trockne verdampft, der kriställine Rückstand mit Methanol stehengelassen, vom Methanol abgesaugt und aus heißem Methanol umkristallisiert. Das so in einer Ausbeute von 72 % erhaltene 3,5-Dibrom-2,6-bis-(methyläthylenimino)-p-benzochinon -schmilzt -bei 128°C und zersetzt sich explosiv bei 195°C. Es besitzt die Formel The invention is illustrated in the following examples. Example 1 48.9 g of 3,5-dibromo-2,6-dimethoxy-p-benzoquinone are dissolved in 600 cm3 of dioxane. To this end, a mixture of 33.5 g of triethylamine and 13.6 g of ethyleneimine in 100 cm3 of dioxane is added dropwise at room temperature. The mixture is then stirred for 12 hours at room temperature. From the excreted, violet needles of 3,5-dibromo-2,6-bis- (ethyleneimino) -p-benzoquinone of the formula is sucked off. On concentration, the mother liquor gives a further amount of the compound which, after recrystallization from chloroform-methanol, melts at 175.degree. C. with decomposition. The yield is 920%. Example 2 65.2 g of 3,5-dibromo-2,6-dimethoxy-p-benzoquinone are dissolved in 600 cm3 of dioxane, and a mixture of 44.5 g of triethylamine and 24.0 g of C-methylethyleneimine in 100 cm3 is added to this solution Dioxane was added dropwise. The temperature is kept at 50 ° C. during the addition and for a further 5 hours. The clear solution is evaporated to dryness in vacuo, the crystalline residue is left to stand with methanol, the methanol is suctioned off and recrystallized from hot methanol. The 3,5-dibromo-2,6-bis (methylethyleneimino) -p-benzoquinone thus obtained in a yield of 72% melts at 128.degree. C. and decomposes explosively at 195.degree. It has the formula
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1041964X | 1955-05-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1041964B true DE1041964B (en) | 1958-10-30 |
Family
ID=4554346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEC12949A Pending DE1041964B (en) | 1955-05-13 | 1956-04-28 | Process for the preparation of substituted bis- (aethyleneimino) -p-benzoquinones |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1041964B (en) |
-
1956
- 1956-04-28 DE DEC12949A patent/DE1041964B/en active Pending
Non-Patent Citations (1)
Title |
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None * |
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