DE1518660A1 - Process for the preparation of amino-substituted dioxocyclobutenes - Google Patents

Description

Process for the preparation of amino-substituted dioxocyclobutenes The invention relates to a process for the preparation of amino-substituted dioxocyclobutenes of the general formulas in which R is an aliphatic radical with 2 to 5 carbon atoms and X1, X2, X3 and X4 either hydrogen, a cycloaliphatic, optionally substituted radical with 4 to 6 carbon atoms or an aliphatic, optionally substituted radical with 1 to 15 C- Mean atoms, where X and X2 and / or X3 and X4 can be closed to form a heterocyclic ring. Compounds of this structure have not yet been described.

According to the invention, these compounds are obtained when dieters of dioxocyclobutene of the general formula @t ammonia or primary or optionally substituted aliphatic, cycloaliphatic or heterocyclic amines. In the above formula, R denotes an aliphatic radical with 2 to @ atoms, for example the ethyl, butyl or amyl radical, ... especially the ethyl radical.

Possible primary aliphatic amines are, for example: methylamine, ethylamine, Propylamine and butylamine; as secondary acid amines z. B.

Dimethylamine, diethylamine, dipropylamine and dibutylamine; as substituted aliphatic amines e.g. ethanolamine, diethanolamine, diisopropanolamine or two or polyvalent amines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; as cycloaliphatic amines e.g. cyclobutylamine, cyclohexylamine and dicyclohexylamine ; as heterocyclic amines e.g. B. Morpholint Piperidine and Pyrrolidinrs like other Substitution products such as the pipecoline and α-methylmorpholine.

The reaction is conveniently carried out in a thickening medium, in which both the dioxocyclobutene diets and the amine are wholly or partially soluble are. The use of z. B. diethyl ether, dibtyl ether, tetrahydrofuran, Dioxane, benzene and toluene.

The desired implementation usually takes place very quickly and is already in place when mixing the components at room temperature. q4Le is made by cooking under Reflux completed. The molar @ ratio of the substances to be used depends according to the desired reaction product: Should only one ether group in the cyclobutene are replaced by an amino group, the ratio of amine to dioxocyclobutene diether may be used do not exceed the value 1; if double substitution is desired it conveniently 2, however cause greater amine excesses no further reaction such as a substitution of the oxo groups.

Are the two ether groups of the dialkoxycyolobutendione against two If different amino groups are exchanged, only one ether group becomes at first by an amino group and tarauds the resulting amino-alkoxy-cyclobutenedione reacted with another amine.

Reaction products are generally insoluble in the solvents or sparingly soluble and can be isolated by filtering off. You are in this Condition is sufficiently pure for most purposes and can be obtained by recrystallization further cleaned. If the reaction product is soluble in the solvent, so it is made by evaporation and possibly subsequent fractional distillation won.

Nine number of the compounds obtained have surprisingly herbicidal properties or have pesticidal properties. In addition, the compounds are valuable intermediates, for example in the manufacture of pharmaceuticals.

The high temperature resistance is also particularly surprising the doubly amino-substituted cyclobutenediones, which are used as starting materials on the production of thermally stable polymers. So can z. B. the reaction products with amines containing hydroxyl groups, e.g. B. diethanolamine, for the manufacture of polycondensation products be drawn in. Example 1 Preparation of diamino cyclobutenedione: 25.5 g Diethoxy-cyclobutenedione (0.15 mol) will dissolve 180 ml of ether and as long as ammonia initiated until no further failure falls out. The latter is suctioned off, washed with ether and peton and dried. Yield 98.1% of the Theory.

The substance changes color from 250 ° C and does not melt until 240 oc ..

C4H4N2O2 (112.09) Calc .: 42.86% C 3.60% H 25.00% N Calc .: 42.95% C 3.72% H 23.94% N Example 2 Preparation of bis (butylamino) cyclobutenedione : 0.15 moles of diethoxy-cyclobutenedione are poured into 60 ml of dioxane, with a solution of 0.35 mol of butylamine mixed in 50 ml of dioxane and the reaction mixture 3 1/2 Heated to the boil for hours on the Rtok river. The precipitating product is filtered off, washed and recrystallized from methanol. Melting point: 253 to 255 ° C; yield 97.5% of theory.

C12H20N2O2 (224.3) calc .: 64.23% C 8.98% H 12.49% N found: 64.07 % C 8.96% H 12.45% N Example 3 Preparation of dipyrrolidino-cyclobutenedione: 0.15 mol of diethoxy-cyclobutenedione are poured into 60 ml of dioxane, with a solution of 0.35 mol of pyrrolidine mixed in 50 ml of dioxane and the reaction mixture 1 1/2 Heated to boiling under reflux for hours. The precipitating product is filtered off, washed and recrystallized from acetonitrile. Melting point: 278 to 280 ° C; Yield 97-5% of theory.

121620.3) Ber. s 65.35% C 7.31% H 12.72% N Found: 65 # 37% 0 7932% H 12, 93% N @@ game 4 Production of dipiperidino-cyclobutenedione : 0.15 mol of diethoxy-cyclobutenedione are dissolved in 60 ml of dioxane, with a solution of 0.35 mol of piperidine mixed in 50 ml of dioxane and the reaction mixture a Heated to boiling under reflux for one hour. The precipitating product is filtered off, washed and recrystallized from dioxane. Melting point: 158 to 160 ° C; yield 100% of theory.

@ 14H20N2O2 (248.3) calc. : 67, 69% C 8.11% H 11, 28% N found: 67, 69% C 8, 24% H 11,% N Example 5 Preparation of bis- (cyclohexylamino) -cyclobutenedione : D, 15 moles of diethcyclobutenedione are dissolved in 60 ml of dioxane, with a solution of 0.35 mol of cyclohexylamine mixed in 50 ml of dioxane and the reaction mixture Heated to boiling under reflux for two hours. The precipitated product is filtered off, washed and recrystallized from acetonitrile. Melting point: 314 to 323 ° C; Yield: 99% of theory.

C16H24N2O2 (276.2) Calc .: 69.53% C 8.75% H 10.13% N Found: 69.79 % C 8.66% H 10.07% N Example 6 Preparation of dibutylamino-ethoxy-cyclobutenedione : 0.05 moles of dietoxy cyclobutenedione are dissolved in 20 ml of ether at 20 ° C with a solution of 0.05 mol of dibutylamine in 20 ml of ether mixed and the reaction mixture Heated for 45 minutes to the (. Thereafter, the ether is evaporated and the residue is fractionally distilled. The product passing over at 154 ° C./0.005 torr is collected; nD20: 1.5242; Yield: 80% of theory.

C14H23NO3 (253.3) Calc .: 66.31% C 9.15% H 5, 53% N Found: 66, 42 % C 9122% H 5.52% N Example 7 Production of morpholino-ethoxy-cyclobutenedione : 0.05 mol of diethoxyS clobutendione are dissolved in 20 ml of ether, at 20 ° C with a Solution of 0.05 mol of morpholine mixed in 20 ml of ether. Then the precipitate filtered off and recrystallized from tetrahydrofuran. Melting point: 154 to 157 ° C; Yield: 83% of theory.

C10H13NO4 (211.2) Calc .: 56.85% C 6.20% H 6.63% N Calc .: 56.77% C 6.23% H 6.59% N Example 8 production of di- (β-hydroxy-ethyl) -amino-ethoxy-cyclobutenedione : 0.05 mol of diethoxy-cyclobutenedione are dissolved in 20 ml of ether at 20 ° C with a solution of 0.05 mol diethanolamine in 20 ml ^ Nther mixed, and the reaction mixture Heated to the boil for three hours. Then the ether is evaporated and the residue analyzed. Yield 100% of theory.

C10H15NO5 (229.2) calc .: 52.40% C 6.60% H 6.11% N found: 51.95% C 6.81% H 5.56% N E Example 9 Preparation of morpholino-piperidino-cyclobutenedione : @ orpholino-ethoxy-cyclobutendione is prepared as in Example 7 and the filtered off Crude product used (yield 97%).

0.097 moles of morpholino-ethoxy-cyclobutenedione and 0.1 moles of piperidine are taken up in 80 ml of dioxane and the reaction mixture is boiled for 2 hours heated. After cooling, the precipitate becomes filtered off and off Dioxane recrystallized. Yield: 58% of theory.

C13H18N2O3 (250.2) calc .: 62.35% C 7.19% H 11.19% N found: 62.11 % C 7.25% H 10.69% N

Claims (3)

Claims for the preparation of amino-substituted dioxocyclobutenes of the general formulas in which R is an aliphatic radical with 2 to 5 carbon atoms and X1, X2, X3 and X4 either hydrogen, a cycloaliphatic, optionally substituted radical with 4 to 6 carbon atoms or an aliphatic, optionally substituted radical with 1 to 15 C- Mean atoms, where X1 and X2 and / or X3 and X4 can be closed to form a heterocyclic ring, characterized in that one diether of the dioxocyclobutene of the general formula With ammonia or primary or secondary, optionally substituted aliphatic, cycloaliphatic or heterocyclic; chien amines. 2. Amino-alkoxy-dioxocyclobutenes of the general formula ir R is an aliphatic radical with 2 to 5 carbon atoms and X. and X2 are either hydrogen, a cycloaliphatic, optionally substituted radical with 4 to 6 carbon atoms or an aliphatic, optionally substituted radical with 1 to 15 carbon atoms, where XI and X2 can be closed to form a heterocyclic ring. 3. Diamino-dioxocyclobutenes of the general formula in which X1, X2, X3 and X4 are either hydrogen, a cycloaliphatic, optionally substituted radical having 4 to 6 carbon atoms or an aliphatic, optionally substituted radical having 1 to 15 carbon atoms, where Xi and X2 and / or X3 and X4 can be closed to form a heterocyclic ring.