DE1795085A1 - Tris-aziridinomethanes and process for their preparation - Google Patents
Tris-aziridinomethanes and process for their preparationInfo
- Publication number
- DE1795085A1 DE1795085A1 DE19681795085 DE1795085A DE1795085A1 DE 1795085 A1 DE1795085 A1 DE 1795085A1 DE 19681795085 DE19681795085 DE 19681795085 DE 1795085 A DE1795085 A DE 1795085A DE 1795085 A1 DE1795085 A1 DE 1795085A1
- Authority
- DE
- Germany
- Prior art keywords
- tris
- preparation
- mol
- general formula
- aziridinomethanes
- 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
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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
- C07D203/16—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 acylated ring nitrogen atoms
- C07D203/18—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 acylated ring nitrogen atoms by carboxylic acids, or by sulfur or nitrogen analogues thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Tris-aziridinomethane und Verfahren zu ihrer Herstellung Es ist bekannt, daß sekundäre aliphatische und cycloaliphatische Amine mit Chloroform in Gegenwart von Alkalihydroxiden oder -alkoholaten in die entsprechenden Formamide überführt werden können (M.Tris-aziridinomethane and process for their preparation It is known that secondary aliphatic and cycloaliphatic amines with chloroform in the presence converted from alkali hydroxides or alcoholates into the corresponding formamides can be (M.
B. Frankel, H. Feuer, J. Bnnk: Tetrahedron Letters 7. 5. (1959); M. Saunders, R.W. Murray: Tetrahedron 11. 1. (1960)).B. Frankel, H. Feuer, J. Bnnk: Tetrahedron Letters May 7 (1959); M. Saunders, R.W. Murray: Tetrahedron January 11 (1960)).
Es wurde nun überraschenderweise gefunden, daß Aziridine unter diesen Bedingungen nicht zu den entsprechenden N-Formylaziridinen, sondern zu Trisaziridinomethanen reagieren.It has now surprisingly been found that aziridines among these Conditions not for the corresponding N-formylaziridines, but for trisaziridinomethanes react.
Gegenstand der Erfindung ist demnach ein Verfahren zur Herstellung von Tris-azlridinomethanen der allgemeinen Formel in der R1 - R4 gleich oder verschieden sein können und Wasserstoffatoie oder niedere Alkylreste bedeuten, das dadurch gekennzeichnet ist, daß man ein Trihalogenmethan der allgemeinen Formel X3CH (II) in der X ein Halogenatom, vorzugsweise Chlor oder Brom, bedeutet, auf ein Aziridin der allgemeinen Formel in Gegenwart von wasserfreiem Alkalihydroxid oder Alkaliamid, vorzugswerise Natrium- oder Kaliumhydroxid, einwirken läßt.The invention accordingly provides a process for the preparation of tris-azlridinomethanes of the general formula in which R1 - R4 can be identical or different and denote hydrogen atoms or lower alkyl radicals, which is characterized in that a trihalomethane of the general formula X3CH (II) in which X denotes a halogen atom, preferably chlorine or bromine, represents an aziridine general formula in the presence of anhydrous alkali hydroxide or alkali amide, preferably sodium or potassium hydroxide, allowed to act.
Gegenstand der Erfindung sind ferner die erfindungsgemäß erhaltenen Tris-aziridinomethane der Formel I.The invention also relates to those obtained according to the invention Tris-aziridinomethane of the formula I.
Bei dem erfindungsgemäßen Verfahren können die Re-Aktionspartner ii stöchiometrischen Verhältnis eingesetzt werden, zweckmäßigerweise verwendet man jedoch einen Überschuß an Aziridin und Alkalihydroxid.In the method according to the invention, the re-action partners ii stoichiometric ratio are used, is expediently used however, an excess of aziridine and alkali hydroxide.
Die Reaktion verläuft im Temperaturebereich von 20° -80°C mit erheblicher Wärmetönung. Zur Abführung der Reaktionswärme verwendet man zweckmäßigerwese ein Kühlbad, so daß die Reaktionstemperatur vorzugsweise zwischen 200 und 400 beträgt. Eine bessere Durchmischung der Alkalihydroxid-Suspension wird durch Ver@@dang einen @nerten Losungsmittels wie Äther @@@ @@@@ eliphatislchen oder aromatischen Kohlenwasse@@geffes gewährleistet. Auf das Lnsungsmittel kann verzichtet werden, wenn das entsprechende Aziridin @@ Spreichendem Überschuß verwandt wird.The reaction takes place in the temperature range of 20 ° -80 ° C with considerable Heat tint. To remove the heat of reaction, it is expedient to use a Cooling bath, so that the reaction temperature is preferably between 200 and 400. A better mix the alkali hydroxide suspension is through Ver @@ dang an @nert solvent such as ether @@@ @@@@ eliphatic or aromatic Kohlwasse @@ geffes guaranteed. The solvent can be dispensed with, if the appropriate aziridine is used.
Die erfindungsgemäß hergestellten Tris-aziridinomethano besitzen tumorhemmende Eigenschaften und eing @aher als Cytostatika geeignet, beispielsweise b1 er postoperativen Behandlung von Krebskranken.The tris-aziridinomethano produced according to the invention have tumor-inhibiting properties Properties and also suitable as cytostatics, for example b1 er postoperative Treatment of cancer patients.
Beispiel 1 Zu einer Suspension von 90,0 g (2,3 Mol) fein pulverisiertem Natriumhydroxid in 129,0 g (3,0 Mol) Aziridin und 100 ml Benzol tropft man unter Rühren während 1 Std. 59,7 g (0,5 Mol) Chloroform. Die Reaktionstemperatur wird durch Kühlen im Eisbad auf 400 gehalten. Man rührt 12 Stdn. bei 250 nach, filtriert vom Unlöslichen ab und destilliert das Filtrat bei maximal 70° - 80° Badtemperatur. Als Endfraktion werden 45,5 g (65 % der Theorie) Trisaziridinomethan erhalten. Kp0,5 = 47°, Fp: 25°. Mit gleichem Ergebnis verläuft die Reaktion ohne Verwendung eines Lösungsmittels; zweckmäßigerweise werden dann Jedoch 172,0 g (4,0 Mol) Äthylenimin eingesetzt, Beispiel 2 Zu einer Suspension von 45,0 (1,1 Mol) pulverisiertem Natriumhydroxid in 65,0 g (1,5 Mol) Aziridin und 50 ml Äther tropft man während 40 Min. 63,0 g (0,25 Mol) Bromform. Die Reaktion wird wie in Beispiel 1 beechrieben ausgeführt. Es werden 13,8 g (40 % der Theorie) Trisaziridinomethan erhalten.Example 1 To a suspension of 90.0 g (2.3 mol) of finely powdered Sodium hydroxide in 129.0 g (3.0 mol) of aziridine and 100 ml of benzene is added dropwise Stir for 1 hour. 59.7 g (0.5 mol) of chloroform. The reaction temperature becomes kept at 400 by cooling in an ice bath. The mixture is stirred for 12 hours at 250 and filtered from the insoluble and the filtrate is distilled at a maximum of 70 ° - 80 ° bath temperature. 45.5 g (65% of theory) of trisaziridinomethane are obtained as the end fraction. Kp0.5 = 47 °, mp: 25 °. With the same result, the reaction proceeds without using one Solvent; However, it is expedient to use 172.0 g (4.0 mol) of ethyleneimine used, Example 2 To a suspension of 45.0 (1.1 mol) powdered sodium hydroxide 65.0 g (1.5 mol) of aziridine and 50 ml of ether are added dropwise over 40 minutes. 63.0 g (0.25 Mole) bromine form. The reaction is carried out as described in Example 1. It will 13.8 g (40% of theory) of trisaziridinomethane were obtained.
Beispiel 3 70,0 g (1,8 Mol) pulverisiertes Natriumhydroxid werden in einer Mischung aus 90,0 g (1,6 Mol) 2-Methylaziridin und 100 al Benzol suspendiert. Unter RUhren werden im Verlauf von 1 8td. 59,7 g (0,5 Mol) Chloroform eingetropit.Example 3 70.0 g (1.8 moles) of powdered sodium hydroxide are used suspended in a mixture of 90.0 g (1.6 mol) of 2-methylaziridine and 100 μl of benzene. In the course of 1 8td. 59.7 g (0.5 mol) of chloroform dropped in.
Die Ausführung der Reaktion erfolgt wir in Seispiel 1 beschrieben. Man ernalt 38.9 g (43 % der Theorie) Tris-2-methylaziridinomethan. Kp0,2 : 40°.The reaction is carried out as described in Example 1. 38.9 g (43% of theory) of tris-2-methylaziridinomethane are obtained. Kp0.2: 40 °.
Beispiel 4 Zu einer Suspension von 72,0 g (1,8 Mol) pulverisiertem Natriumhydroxid in 103,0 g (1,5 lol) 2,2-Dimethylaziridin werden in 45 Min. 52,2 g (0,4 Mol) Chlors form zugetropft. nährend der Zugabe von Chloroform wird die Reaktionstemperatur durch Kühlen im Eisbad auf 20° gehalten, Weiter werfährt man wie in Beispiel 1 beschrieben, Es werden 29,3 g (30 % der Theorie) Tris-2,2-dimethylaziridinmentan erhalten. Kp0,3 = 57,5°Example 4 To a suspension of 72.0 g (1.8 moles) of powdered Sodium hydroxide in 103.0 g (1.5 lol) 2,2-dimethylaziridine becomes 52.2 g (0.4 mol) of chlorine form was added dropwise. during the addition of chloroform, the reaction temperature becomes kept at 20 ° by cooling in an ice bath, the procedure is as described in Example 1, 29.3 g (30% of theory) tris-2,2-dimethylaziridinmentane are obtained. Kp0.3 = 57.5 °
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681795085 DE1795085A1 (en) | 1968-08-07 | 1968-08-07 | Tris-aziridinomethanes and process for their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681795085 DE1795085A1 (en) | 1968-08-07 | 1968-08-07 | Tris-aziridinomethanes and process for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1795085A1 true DE1795085A1 (en) | 1971-12-30 |
Family
ID=5708051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19681795085 Pending DE1795085A1 (en) | 1968-08-07 | 1968-08-07 | Tris-aziridinomethanes and process for their preparation |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1795085A1 (en) |
-
1968
- 1968-08-07 DE DE19681795085 patent/DE1795085A1/en active Pending
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