DE1091103B - Process for the preparation of compounds containing one or two nitrogen-containing radicals and one carbon-carbon triple bond - Google Patents

Description

Process for the preparation of compounds containing one or two nitrogen-containing radicals and one carbon-carbon triple bond It has been found that one or two nitrogen-containing radicals and one carbon-carbon triple bond-containing compounds of the general formula wherein - is an amino group disubstituted by aliphatic, cycloaliphatic or aromatic hydrocarbon radicals optionally bearing hydroxyl groups or in which R1 and R2 together with the nitrogen atom are members of a heterocyclic ring, R3, R4 and R5 are hydrogen atoms or identical or different alkyl, cycloalkyl, aralkyl or Aryl groups are or R8 and R4 or R4 and Rs together are two to six methylene groups connected to one another and Z is a hydrogen atom or the remainder is obtained when using enamines of the general formula derived from aliphatic, araliphatic or cycloaliphatic carbonyl compounds wherein have the above meaning, acetylene in the presence of metals of the I. or II. Subgroup of the Periodic Table can act.

Suitable enamines are, for. B. the conversion products at the by Mannich and Davidsen in Ber. d.

German. Chem. Gesellschaft, 69, pp. 2106-2112 (1936) Method by the action of secondary aliphatic, cycloaliphatic or aromatic Amines, e.g. B. of diethylamine, dibutylamine, ethylbutylamine, diethanolamine, dicyclohexylamine, Methylaniline, propylaniline or of cyclic secondary amines such as pyrrolidine, Piperidine, morpholine or piperazine, to aliphatic, araliphatic or cycloaliphatic saturated carbonyl compounds, e.g. B. on acetaldehyde, propionaldehyde, butyraldehyde, Isobutyraldehyde, enanthaldehyde, phenylacetaldehyde, hydrozimaldehyde, phenylacetone, Cyclopentanone, cyclohexanone, cycloheptanone or cyclooctanone can be obtained.

Suitable enamines are e.g. B. l-dimethylaminobutene- (1), 1-diethylamino-butene (1), 1-pyrrolidinobutene- (1), 1-piperidino-butene (1), 1-morpholino-2-methylpropen- (1), 2-methyl-6piperidino-butene (3), 1-morpholino-cyclopentene- (1), 1-pyrrolidino-cyclopentene- (1), 1-dimethylamino-cyclohexene (1), 1-methylbutylamino-cyclohexene (t), l-piperidino-cyclohexene (t), l-morpholinocyclohexen- (l), l-pyrrolidino-cyclohepten- (l), l-diethylamino-cycloocten- (1), 1-pyrrolidino-cycloocten- (1).

The reaction can be carried out either at normal or elevated temperature, z. B. at temperatures up to about 200 "C, under atmospheric or elevated pressure, z. B. pressures from 1 to 50 at. To implement it, it is advisable to proceed as follows: that the enamine with the catalyst is poured into a reaction vessel, if necessary a solvent or diluent is added and acetylene is introduced into the mixture or after Forcing acetylene into the reaction vessel up to one allows higher acetylene pressure to act. The acetylene does not have to be pure rather, it can, which is particularly advantageous when working under higher pressures can be by inert gases, e.g. B. with nitrogen, methane and noble gases, diluted will. Solvents or diluents can be present during the reaction. as such are z. B. hydrocarbons such as benzene, toluene, xylene, ligroin, also open or cyclic ethers, such as diethyl ether, tetrahydrofuran, dioxane and Alcohols such as methyl, ethyl, propyl or butyl alcohol, cyclohexanol or esters, z. B. methyl acetate, ethyl acetate or dimethyl adipate, as well as N-methylpyrrolidone, dimethylformamide and dimethyl urethane.

The catalysts are compounds of the metals of the I. or II. Subgroup of the periodic system into consideration. Particularly suitable are, for. B. the salts of these metals with inorganic or organic acids, such as fatty acids or benzoic acid, as well as the acetylene compounds known from these metals. Suitable catalysts are, for. B. copper or silver acetylide, copper (I) - or Copper (II) chloride, auric chloride, silver acetate, copper acetate, copper benzoate, silver benzoate, Zinc chloride, zinc cyanide, zinc acetate, zinc stearate, zinc benzoate, cadmium chloride, cadmium acetate, Cadmium naphthenate and mercuric acetate.

The reaction of the acetylene with the enamine component, for example with 2-methyl-4-piperidino-butene (3), proceeds according to the equation: where compound 1 can react with further enamine, e.g. B. with 2-MethylWpiperidino-butene (3), to form the 2,9-dimethyl-4,7-diperidino-decyne- (5) of the formula Both reactions generally take place side by side, but the reaction of one molecule of acetylene with one molecule of enamine is much more rapid.

It is therefore in your hand, by choosing suitable implementation conditions, in particular the temperature, the acetylene concentration, d. b. the acetylene pressure, and the exposure time as well as the amount and type of solvent both the compounds with acetylene group still carrying hydrogen or the compounds to obtain, in which both hydrogen atoms of acetylene are substituted. For the preparation of the latter compound, it is generally particularly expedient at higher temperatures, e.g. B. those between about 60 and 200 ° C and lower acetylene concentrations to work while the formation of the still substitutable hydrogen on one of the carbon-carbon triple bonds containing carbon atoms bonded Compounds in general achieved by expediently low working temperatures chooses and uses the acetylene in high concentration. This can e.g. B. by the Working under increased acetylene partial pressure or by using solvents, in which acetylene is particularly soluble, z. B. of N-methylpyrrolidone, Dimethyl urethane and tetrahydrofuran can be achieved. The most favorable conditions, under which essentially only one or the other connection is obtained, are different for the individual enamines and can easily be determined by preliminary experiments determine.

From the reaction mixture can be obtained according to the invention, one or two nitrogen-containing radicals and one carbon-carbon triple bond containing, mostly new compounds in a simple manner according to conventional ones Easily separate methods, e.g. B. by distillation or crystallization The invention available compounds have fungicidal properties, in particular show the acetylenediamines obtained by reacting acetylene on both sides in the Control of powdery mildew excellent effect.

From the German patent 724 756 it is known that amines or amides which contain a propene group are obtained by clicking on one on an α-carbon atom hydroxylated amine or amide acetylene in the presence of heavy metals of I. or II. Group of the Periodic Table can act. Such a condensation reaction, when intermolecular water escapes, however, there is no indication of how and under which conditions are attached to a C = C double bond of enamines acetylene can. One already has aldimines of the general formula R- = C H -wherein R and R ' Are alkyl groups (see US Pat. No. 2,665,311), or carbonyl compounds Ethinylated with acetylene. It dealt with the raw materials previously used however, it is always about compounds that exist between a non-carbon atom and a Carbon atoms contain a double bond and are therefore strongly polarized. It was unexpected that the far less polar enamines, in which the double bond is between 2 carbon atoms, are capable of a reaction with acetylene.

The parts given in the examples are parts by weight.

Example 1 A mixture of 50 Parts of l-diethylamino-butene (1), 50 parts of ethyl acetate and 2 parts of cuprous chloride at room temperature with a mixture of nitrogen and acetylene in a ratio of 1: 1.5 treated under 25 at pressure. The acetylene consumed will be through from time to time Repressing added. When about the calculated amount of acetylene is consumed, will the pressure vessel is released and the reaction mixture is filtered and distilled. Man receives 49 parts 3-Diethylaminohexyne- (1) from Kr.19 = 65 to 66 "C. The yield corresponds to 820% of theory.

Example 2 As described in Example 1, a mixture of 90 Parts of l-piperidino-butene (l), 60 parts of ethyl acetate and 2 parts of copper acetate Treated room temperature with acetylene until about the equivalent of piperidinobutene Amount of acetylene is added. The reaction mixture is filtered and distilled. 97 parts of 3-piperidinohexyne- (1) with a boiling point 2.2 = 69 to 71 ° C. are obtained. The yield is 91 01o of theory.

Example 3 In a pressure vessel with a stirrer a mixture of 760 parts of 2-methyl-4-piperidino-butene (3) 800 parts of ethyl acetate and 30 parts Cuprous chloride at 25 "C with a C2 H2: N2 mixture as in Example 1 under one Treated pressure of 25 at. The acetylene consumed in the reaction is through half-hourly re-pressing to a pressure of 25 at was added. Once in essence there is no more acetylene uptake, the pressure vessel is released. The raw conversion mixture is distilled with steam until no more organic matter passes over. from In the distillate, the organic layer is separated from the aqueous layer by phase separation Shift off. The non-aqueous layer is distilled, after a forerun, which mainly contains the ethyl acetate, 803 parts of 2-methyl-4-piperidono-hexyne- (5) vom Kr. ,, = 98 to 99 "C.

The yield is 900% of theory.

Example 4 In a pressure vessel fitted with a shaker is connected, a mixture of 60 parts of 2-methyl-4-piperidino-butene (3), 40 parts of tetrahydrofuran and 2 parts of cuprous chloride at 60 "C with acetylene, as in Example 1 described, implemented. Distillation of the reaction mixture gives 36 parts of 2-methyl-4-piperidino-hexyne- (5) and a fraction with a boiling point of 150 to 180 ° C of 14 parts. The latter solidifies to crystals of F. = 50 to 53 "C. It exists from 2,9-dimethyl-4,7-di-piperidino-decyne- (5).

Example 5 In a pressure vessel fitted with a shaker is connected, a mixture of 60 parts of 2-methyl-4-piperidino-butene (3), 40 parts of toluene and 5 parts of tin stearate at 160 "C with a mixture of acetylene and nitrogen in a ratio of 1: 1.5 at a pressure of 25 atm. Of the Pressure is maintained by injecting the gas mixture every half hour. As soon as the uptake of acetylene has essentially ended, the pressure vessel is left cool and relax him. The reaction mixture is distilled.

After removing the solvent, a b.p. 0.8 = 170 bis 1800C 40 parts of 2,9-dimethyl-4,7-dipiperidino-decyne- (5). The yield is 61 ovo the theory.

Example 6 In a solution of 100 parts of 2-methyl-4-piperidinobutene- (3) in 200 parts of ethyl acetate, in which 3 parts of cuproacetylide are suspended, becomes 20 Introduced for hours at 40 "C acetylene in an hourly amount of 5 to 6 parts. Then the mixture is filtered. The filtrate is washed several times with dilute hydrochloric acid shaken out.

The extracts are made strongly alkaline with 15% sodium hydroxide solution Reaction added and the deposited organic bases in 250 parts of ether or Tetrahydro furan added. The organic solution is dried with potash and fractionally distilled. 40 parts of 2-methyl-4-piperidino-hexyne- (5) are obtained and 21 parts of 2,9-dimethyl-4,7-di-piperidino-decyne- (5).

Example 7 2000 parts of 1-pyrrolidino-cyclohexene (1), 1600 parts of ethyl acetate, 40 parts of cuprous chloride are placed in a pressure vessel with a stirrer is provided, at 600 C with an acetylene-nitrogen mixture in the ratio 1.5 : 1 treated at 25 at, the pressure being increased by injecting the gas mixture every half hour is maintained. As soon as the acetylene uptake has essentially ended, let the vessel cool down and relax it. From the implementation mixture that becomes The solvent is distilled off under a weak vacuum. The residue is steamed distilled. There are 2080 parts of 1-pyrrolidino-1-äthinyl-cyclohexane of F. = 63 to 65 "C. The yield is 8701, of theory.

Example 8 As described in the previous example, 50 parts 1-pyrrolidino-cyclohexene (1), 40 parts of ethyl acetate and 2 parts of silver acetate at 60 "C. and 25 at with acetylene diluted with nitrogen (C2 H2: N2 = 1.5: 1) treated. After cooling and releasing the pressure in the reaction vessel, the contents of the vessel become filtered and the filtrate is distilled. Between 75 and 95 "C / 1.5 mm Hg, 48 parts go 1 -pyrrolidino-1-ethinyl-cyclohexane, which soon crystallize. The yield is 8701o of theory.

If you work in the same way under the same conditions, however, if the 2 parts of silver acetate are replaced by 2 parts of mercuric acetate, this is obtained 38 parts of 1-pyrrolidino-1-ethinyl-cyclohexane.

Example 9 50 parts of 1-piperidino-cyclohexene (1), 40 parts of ethyl acetate and 2 parts of cuprous chloride are, as described in Example 7, reacted with acetylene. 49 parts of 1-piperidino-1-ethinyl-cyclohexane are obtained. The connection is melting after recrystallization from aqueous acetone at 89 to 91 ° C. The yield is 930 / o of theory.

Example 10 50 parts of l-morpholino-cyclohexene (l), 40 parts of ethyl acetate, 2 parts of cuprous chloride are reacted with acetylene at 70 ° C., as described in Example 7. The mixture is filtered and the solvent is removed from the filtrate in vacuo. There remain 58 parts of crude crystalline residue of 1 - morpholino - 1 - äthinyl- cyclohexane back.

The compound melts after recrystallization from aqueous acetone at 96 to 980 C.

Example 11 A mixture of acetylene is left in a pressure vessel and nitrogen (ratio 1.5: 1) to the 50 parts of 1-pyrrolidino-cyclopenten- (1), 40 parts of ethyl acetate and 2 parts of cuprous chloride prepared mixture at 60 "C and 25 at act. The pressure is increased every half hour by forcing in the gas mixture regulated.

As soon as the acetylene uptake is much slower even after re-pressing takes place than at the beginning of the exposure, the vessel is allowed to cool and relaxed. That filtered mixture is distilled in vacuo. 40 parts of I-pyrrolidino- i-ethinyl-cyclopentane, which pass at 68 to 78 "C at 1 mm Hg pressure the After recrystallization from acetone-water, the compound melts at 57 to 59 ° C.

Example 12 100 parts of 1-pyrrolidino-cyclohexene and 5 parts of zinc stearate are in a shaking autoclave at 1600C with an acetylene-nitrogen mixture treated in a ratio of 1.5: 1 at 25 atm until no more acetylene uptake takes place. The crystallized reaction mixture is dissolved in dilute mineral acid and the base was deposited from the filtered solution by alkali.

After drying, 85 parts of 1,2-bis [pyrrolidino-cyclohexyl] ether of the formula are obtained The yield is 780% of theory. The compound melts after recrystallization from petroleum ether or acetone at 110 to 111 "C.

If 5 parts of zinc stearate are used as catalyst 5 instead of the 5 parts Parts cadmium acetate and otherwise works in the same under the same conditions Way, the 1,2-bis [pyrrolidino-cyclohexyl] ethine is obtained in one yield from 7501, the theory.

Example 13 120 parts of 1-morpholino-cyclohexene and 5 parts of zinc stearate are in a shaking pressure vessel at 165 "C with an acetylene-nitrogen mixture treated in a ratio of 1.5: 1 at 25 atm until no more exposure occurs. That crystallized The reaction mixture is recrystallized from ethyl acetate. 72 parts are obtained 1,2-Bis- [pyrrolidino-cyclohexyl] -ethine with a melting point of 175 to 176 "C.

Example 14 50 parts of l-piperidino-cyclohexene (l), 40 parts of toluene, 4 parts of zinc stearate are, as described in Example 12, at 1600C with a C2H2: N2 mixture treated and worked up as in Example 12 under a pressure of 25 atm.

There are 30 parts of 1, 2-bis- {piperidino-cydohexyl] ethine from F. = 146 to 148 "C obtained.

Example 15 100 parts of 1-pyrrolidino-cyclopentene- (1) and 5 parts of zinc stearate are, as described in Example 12, treated with acetylene at 160 "C and worked up. 90 parts of 1,2-bis [pyrrolidino-cyclopentyl] -ethine are obtained, that is 820in the theory. After recrystallization from ligroin, the base melts at 86.degree.

Claims (1)

PATENT CLAIM: Process for the preparation of compounds of the general formula containing one or two nitrogen-containing radicals and a carbon-carbon triple bond wherein is an amino group disubstituted by aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, optionally bearing hydroxyl groups, or in which Ri and R2 together with the nitrogen atom are members of a heterocyclic ring, R3, R4 and R5 are hydrogen atoms or identical or different alkyl, cycloalkyl, aralkyl or aryl groups are or R3 and R4 or R4 and R5 together are two to six methylene groups connected to one another and Z is a hydrogen atom or the remainder is characterized in that enamines of the general formula derived from aliphatic, araliphatic or cycloaliphatic carbonyl compounds are used wherein Have the above meaning, acetylene in the presence of compounds of the metals of the I. or II. Subgroup of the Periodic Table can act. Documents considered: German Patent No. 724 759; U.S. Patent No. 2,665,311.