DE1125431B - Process for the preparation of 2, 5-bis-aethyleneimino-3, 6-bis-acylamino-p-benzoquinones - Google Patents
Process for the preparation of 2, 5-bis-aethyleneimino-3, 6-bis-acylamino-p-benzoquinonesInfo
- Publication number
- DE1125431B DE1125431B DEC21498A DEC0021498A DE1125431B DE 1125431 B DE1125431 B DE 1125431B DE C21498 A DEC21498 A DE C21498A DE C0021498 A DEC0021498 A DE C0021498A DE 1125431 B DE1125431 B DE 1125431B
- Authority
- DE
- Germany
- Prior art keywords
- bis
- benzoquinones
- acylamino
- preparation
- 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 2,5-Bis-äthylenimino-3,6-bis-acylaminopbenzochinonen Es ist bereits bekannt, 2,5-Dihalogen-3,6-bis-acylamino-p-benzochinone, in denen die Acylreste solche aliphatischer Carbonsäuren mit 2 bis 6 Kohlenstoffatomen sind, mit Äthyleniminen zu den entsprechenden 2,5-Bis-äthylenimino-3,6-bis-acylamino-p-benzochinonen umzusetzen (österreichische Patentschrift 198747, französische Patentschrift 1163465, USA.-Patentschrift 2 802 001). Process for the preparation of 2,5-bis-ethylenimino-3,6-bis-acylaminopbenzoquinones It is already known 2,5-dihalo-3,6-bis-acylamino-p-benzoquinones, in which the acyl radicals are those of aliphatic carboxylic acids with 2 to 6 carbon atoms, with ethylenimines to the corresponding 2,5-bis-ethylenimino-3,6-bis-acylamino-p-benzoquinones implement (Austrian patent specification 198747, French patent specification 1163465, U.S. Patent 2,802,001).
Die Erfindung betrifft nun ein Verfahren zur Herstellung von 2,5- Bis - äthylenimino -3,6- bis -acylamino - p - benzochinonen, deren Acylgruppen Reste von aliphatischen Carbonsäuren mit 7 bis 18 Kohlenstoffatomen, wie der Önanthsäure, Caprinsäure oder Palmitinsäure, darstellen. Die Äthyleniminogruppen können an den Kohlenstoffatomen alkyliert sein, vorzugsweise durch eine Methylgruppe. The invention now relates to a method for the production of 2.5- Bis - äthylenimino -3,6- bis -acylamino - p - benzoquinones, the acyl groups of which are residues of aliphatic carboxylic acids with 7 to 18 carbon atoms, such as enanthic acid, Represent capric acid or palmitic acid. The ethyleneimino groups can be attached to the Carbon atoms be alkylated, preferably by a methyl group.
Die Erfindung betrifft insbesondere ein Verfahren zur Herstellung von 2,5 - Bis - äthylen -imino - 3,6 - bis - önanthoylamino - p - benzochinon der Formel Die neuen Benzochinonverbindungen sind gegen Amöben, z. B. gegen Entamoeba histolytica, sowie gegen Bakterien wirksam; zudem zeigen sie eine ausgeprägte tumorhemmende Wirkung und vermögen Remissionen zu erzeugen. Sie sind bekannten Verbindungen vergleichbarer Konstitution mit niederen Acylaminoresten in bezug auf ihre therapeutische Anwendbarkeit überlegen, insbesondere ist ihre Antitumorwirkung spezifischer. So ist z. B. das 2,5-Bis-äthylenimino - 3,6 - bis - önanthoylamino -p - benzochinon dem gemäß der österreichischen Patentschrift 198747 erhaltenen 2,5-Bis-äthylenimino-3,6-bis-butyrylamino-pbenzochinon bezüglich seiner hemmenden Wirkung gegenüber auf weiße Mäuse implantiertem Ehrlich Carcinom und bezüglich der therapeutischen Breite überlegen.In particular, the invention relates to a process for the preparation of 2,5-bis-ethylene-imino-3,6-bis-önanthoylamino-p-benzoquinone of the formula The new benzoquinone compounds are against amoebas, e.g. B. effective against Entamoeba histolytica, as well as against bacteria; They also show a pronounced anti-tumor effect and are able to produce remissions. They are superior to known compounds of comparable constitution with lower acylamino residues with regard to their therapeutic applicability, in particular their anti-tumor effect is more specific. So is z. B. the 2,5-bis-ethylenimino-3,6-bis-önanthoylamino-p -benzoquinone obtained according to the Austrian patent 198747 2,5-bis-ethylenimino-3,6-bis-butyrylamino-pbenzoquinone with respect to its inhibitory effect superior to Ehrlich's carcinoma implanted in white mice and in terms of therapeutic index.
Die neuen 2,5-Bis-äthylenimino-3,6-bis-acylaminop-benzochinone werden erfindungsgemäß erhalten, wenn man in an sich bekannter Weise 2,5-Dihalogen-3,6-bis-acylamino-p-benzochinone, deren Acylgruppen Reste von aliphatischen Carbonsäuren mit 7 bis 18 Kohlenstoffatomen darstellen, mit Äthyleniminen umsetzt. Unter den Dihalogenverbindungen eignen sich besonders die Dichlor- und Dibromverbindungen. The new 2,5-bis-äthylenimino-3,6-bis-acylaminop-benzoquinones are obtained according to the invention if in a known manner 2,5-dihalo-3,6-bis-acylamino-p-benzoquinones, their acyl groups are residues of aliphatic carboxylic acids with 7 to 18 carbon atoms represent, reacts with ethylene imines. Among the dihalo compounds are suitable especially the dichloro and dibromo compounds.
Vorzugsweise arbeitet man in indifferenten Lösungsmitteln, wie Dioxan, Benzol, oder auch in Gegenwart von Alkoholen, wie Äthyl-, Isopropyl- oder Butylalkohol, oder Isopropyläther. It is preferred to work in inert solvents such as dioxane, Benzene, or in the presence of alcohols such as ethyl, isopropyl or butyl alcohol, or isopropyl ether.
Bei der Umsetzung mit den Äthyleniminen kann man auch Kondensationsmittel, wie tertiäre Basen, verwenden. Die Reaktion läßt sich bei Zimmertemperatur oder bei erhöhter Temperatur durchführen. When reacting with the ethyleneimines, condensation agents can also be used like tertiary bases. The reaction can take place at room temperature or Perform at elevated temperature.
Die Ausgangsstoffe werden in an sich bekannter Weise, z. B. durch Umsetzung eines 2,5-Dihalogen-3,6-diamino-benzochinons mit einem entsprechenden aliphatischen Carbonsäureanhydrid in Gegenwart von konzentrierter Schwefelsäure hergestellt. The starting materials are in a known manner, for. B. by Implementation of a 2,5-dihalo-3,6-diamino-benzoquinone with a corresponding one aliphatic carboxylic anhydride in the presence of concentrated sulfuric acid manufactured.
Die verfahrensgemäß erhaltenen 2,5-Bis-äthylenimino-3,6-bis-acylamino-p-benzochinone finden als Bakterizide sowie als Heilmittel, besonders bei Krebserkrankungen oder durch Amöben verursachten Erkrankungen, Verwendung. The 2,5-bis-ethylenimino-3,6-bis-acylamino-p-benzoquinones obtained according to the process found as bactericides as well as remedies, especially for cancers or diseases caused by amoeba, use.
Die Erfindung wird in den nachfolgenden Beispielen näher erläutert. The invention is explained in more detail in the following examples.
Beispiel 1 81,7 g 2,5-Dichlor-3,6-bis-önanthoylamino-benzo chinon (F. 225 bis 230"C) werden in 600 cm3 Dioxan suspendiert. Langsam wird ein Gemisch von 29,2 cm3 Äthylenimin und 42 g Triäthylamin in 150 cm3 Dioxan bei 25"C zugetropft und die sich allmählich violett verfärbende Kristallsuspension 7 Stunden im Wasserbad von 45"C gerührt. Das rötliche Reaktionsprodukt wird durch Absaugen isoliert, mit Äthanol gewaschen, in 700 cm3 Wasser suspendiert und wieder abgesaugt, mit Äthanol gewaschen und getrocknet. Example 1 81.7 g of 2,5-dichloro-3,6-bis-oenanthoylamino-benzo quinone (F. 225 to 230 "C) are suspended in 600 cm3 of dioxane. Slowly a mixture of 29.2 cm3 of ethyleneimine and 42 g of triethylamine in 150 cm3 of dioxane were added dropwise at 25 "C. and the crystal suspension, which gradually turns violet, in a water bath for 7 hours of 45 ° C. The reddish reaction product is isolated by suction, with Washed ethanol, suspended in 700 cm3 of water and again suctioned off with ethanol washed and dried.
Das erhaltene 2,5-Bis-önanthoylamino-3,6-bis-äthylenimino-benzochinon schmilzt bei 208 bis 210"C unter Zersetzung. Durch Umlösen aus viel absolutem Alkohol wird ein Schmelzpunkt von 219 bis 221"C erreicht. Die Ausbeute beträgt 830/o. The 2,5-bis-önanthoylamino-3,6-bis-äthylenimino-benzoquinone obtained melts at 208 to 210 "C with decomposition. By dissolving from a lot of absolute alcohol a melting point of 219 to 221 "C is reached. The yield is 830 / o.
Beispiel 2 2,57 g 2,5-Dichlor-3,6-bis-caprinoylamino-benzochinon (F. 200 bis 2Q2°C) werden in 30 cm3 Dioxan suspendiert. Dazu wird ein Gemisch von 1,1 g Triäthylamin und 0,65 g Äthylenimin in 25 cm3 Dioxan zugetropft. Example 2 2.57 g of 2,5-dichloro-3,6-bis-caprinoylamino-benzoquinone (F. 200 to 2Q2 ° C) are suspended in 30 cm3 of dioxane. A mixture of 1.1 g of triethylamine and 0.65 g of ethyleneimine in 25 cm3 of dioxane were added dropwise.
Die Suspension wird nach kurzer Zeit rötlichviolett und wird 7 Stunden im Wasserbad von 45"C gerührt. The suspension turns reddish purple after a short time and becomes 7 hours stirred in a water bath at 45 ° C.
Man isoliert durch Absaugen, wäscht mit Äthanol und Wasser und kristallisiert, wenn nötig, aus 200 cm3 Äthanol um.It is isolated by suction, washed with ethanol and water and crystallized, if necessary, from 200 cm3 of ethanol.
Das erhaltene 2,5-Bis-caprinoylamin-3,6-bis-äthylen imino-benzochinon der Formel schmilzt bei 204 bis 205"C (Zersetzung), Ausbeute 82 0/,.The resulting 2,5-bis-caprinoylamine-3,6-bis-ethylene imino-benzoquinone of the formula melts at 204 to 205 "C (decomposition), yield 82%.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1125431X | 1959-05-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1125431B true DE1125431B (en) | 1962-03-15 |
Family
ID=4558858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEC21498A Pending DE1125431B (en) | 1959-05-15 | 1960-05-11 | Process for the preparation of 2, 5-bis-aethyleneimino-3, 6-bis-acylamino-p-benzoquinones |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1125431B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2802001A (en) * | 1955-11-25 | 1957-08-06 | Ciba Pharm Prod Inc | 2, 5-bis-ethyleneimino-3, 6-bis-acylamino-para-benzoquinones |
AT198747B (en) * | 1956-09-19 | 1958-07-25 | Ciba Geigy | Process for the preparation of new quinone compounds |
FR1163465A (en) * | 1955-11-25 | 1958-09-26 | Ciba Geigy | Process for the preparation of new quinone derivatives |
-
1960
- 1960-05-11 DE DEC21498A patent/DE1125431B/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2802001A (en) * | 1955-11-25 | 1957-08-06 | Ciba Pharm Prod Inc | 2, 5-bis-ethyleneimino-3, 6-bis-acylamino-para-benzoquinones |
FR1163465A (en) * | 1955-11-25 | 1958-09-26 | Ciba Geigy | Process for the preparation of new quinone derivatives |
AT198747B (en) * | 1956-09-19 | 1958-07-25 | Ciba Geigy | Process for the preparation of new quinone compounds |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1201839B (en) | Process for the preparation of aliphatic cyanoic acid esters which are substituted by electron-attracting atoms or groups | |
DE863055C (en) | Process for the preparation of ethyleneimine compounds | |
DE1125431B (en) | Process for the preparation of 2, 5-bis-aethyleneimino-3, 6-bis-acylamino-p-benzoquinones | |
DE1125432B (en) | Process for the preparation of 2, 5-bis-aethyleneimino-3, 6-bis-acylamino-p-benzoquinones | |
AT218511B (en) | Process for the preparation of new quinone compounds | |
CH377823A (en) | Process for the preparation of new quinone derivatives | |
DE1117585B (en) | Process for the preparation of 2,5-bis-AEthylenimino-3,6-bis-acylamino-p-benzoquinones | |
DE1252209B (en) | ||
CH378326A (en) | Process for the preparation of new p-benzoquinones | |
DE1129955B (en) | Process for the preparation of 2, 5-bis-aethyleneimino-3, 6-bis-caproyl-amino-p-benzoquinone | |
DE1044816B (en) | Process for the preparation of ethyleneimine compounds | |
AT239226B (en) | Process for the preparation of new, substituted 2-oxo-tetrahydroquinolines | |
AT235831B (en) | Process for the preparation of new esters of basic carbinols and their acid addition salts | |
AT233586B (en) | Process for the preparation of new 4,4'-disubstituted diphenyl sulfones | |
EP0013034B1 (en) | Process for the preparation of beta-(5-nitro-2-furyl)-acrolein | |
DE1011888B (en) | Process for the preparation of theophylline derivatives | |
DE932910C (en) | Process for the preparation of pteroic acid and its derivatives, in particular folic acid | |
AT274783B (en) | Process for the preparation of new N- (Hydroxycyclohexyl) -halogen-aminobenzylamines and their acid addition salts | |
DE1618375C (en) | Trichlorometylsulfenyl-N- (trifluoromethyl) -N- (2-methyl-5-nitroanilide) and a process for its preparation | |
DE1041964B (en) | Process for the preparation of substituted bis- (aethyleneimino) -p-benzoquinones | |
CH372672A (en) | Process for the production of a new quinone derivative | |
DE960098C (en) | Process for the preparation of 2-benzenesulfonamido-4-methyl-6-oxy-pyrimidines | |
DE1237122B (en) | Process for the preparation of substituted anthrapyrimidines | |
DE1161266B (en) | Process for the preparation of 3, 11-dioxo-17ª ‡ -hydroxy-20ª ‰, 21-dinitrato-í¸-pregnen | |
CH343402A (en) | Process for the production of new quinones |