DE2441348C2 - Process for the preparation of oximino-cycloalkenene (l) substituted in the l-position - Google Patents

Description

15th

in which Ri and R2 are the same or different and each is an alkyl radical having 1 to 8 carbon atoms or both together with the neighboring one Nitrogen atom Members of a 5- or 6-membered heterocyclic ring consisting of the morpholino,

20 piperidino, pyrrolidino, piperazino, imidazolidino, pyrrolino (i42 ') or imidazo group, and R _{3 is} an alkylene radical having 2 to 10 carbon atoms, by reaction of cycloalkenes with nitrosating agents, characterized in that one cycloalkenes the general formula

Ri

H-C

wherein Ri, R ₂ and R3 have the above meaning, reacts with 1 to 2 ^ 5 moles of nitrogen monoxide and 0.25 to 1 mole of oxygen per mole of starting material II in organic solvents which are inert under the reaction conditions

The invention relates to the subject matter of the claim.

It is known that l-morpholino-6-oximino-cyclohexen- (l) by reacting 1-morpholino-cyclohexene (l) with nitrosyl chloride in the presence of Triethylamine produces To isolate the end product from the reaction mixture, you need more than 12 hours work-up time (Tetrahedron Letters, Volume 4, pages 203-206, 1964). At the same connection and the 1-piperidino compound is obtained when instead of nitrosyl chloride and the base ethyl nitrite or isoamyl nitrite and as a catalyst BF3 etherate or anhydrous AICI3 used. The reaction mixture must be used to separate the end product to be kept in the refrigerator for a week. In the case of the! -Pyrrolidino compound, the production

+ 2NO + 1 / 2O ₂

treatment only in the absence of solvents and at a temperature of the cooling bath of -45 ° C (Journal für Prakt Chemie, Volume 311, pages 162-164 (1969)). A corresponding synthesis with other alkyl nitrites such as butyl nitrite is described in Japanese laid-open specification 9 531/67, with a reaction time 10 hours at room temperature is recommended.

All of these processes require expensive nitrosating agents and a long reaction or work-up time and are just related on an industrial scale unsatisfactory for a simple and economical way of working.

The reaction is carried out in the case of using l-morpholino-cyclohexene-il) by the following Formulas reproduced:

+ ENT ₂

The nitrous acid formed settles in a subsequent reaction with further 1-morpholino-cyclohexene (1), generally in a molar ratio of 1: 1, to nitrosated secondary products.

Compared to the known method, the method according to the invention provides on a simpler and more economical way in the l-position substituted oximino-cycloalkenes (l) in partly better yield and purity as well as in better space-time yield. Catalysts are not required. The speed of reaction is higher and the work-up of the reaction mixture is sometimes shorter and simpler.

Special measures for cooling the reaction mixture and correspondingly longer work-up at very low temperatures are not necessary. All of these beneficial results are in terms of the state surprising to the technology, since it is known to use nitrous oxide as a nitrosating agent as a result, side reactions occur that pseudonitroles are subsequently formed from the oximes initially formed or nitro acids are formed (Houben-Weyl, Methods of Organic Chemistry, Volume 10/4, page 22). In addition, Houben-Weyl shows that the exact dosage of gaseous nitrous oxide, like it

always forms in the gas mixture of NO and oxygen according to the method according to the invention, causes difficulties; the simple invention Therefore, the way of working could not be expected.

Preferred starting materials II and correspondingly preferred end materials I are those whose formulas Ri and R2 are identical or different and each have an alkyl radical having 1 to 8 carbon atoms or both together with the adjacent nitrogen atom are members of a 5- or 6-membered heterocyclic ring, which is next to the nitrogen atom may contain another nitrogen atom or an oxygen atom, and R ₃ denotes an alkyl radical having 2 to 10 carbon atoms. B. alkyl groups or alkoxy groups each having 1 to 4 carbon atoms may be substituted.

For example, the following cycloalkenes are suitable as starting materials II: l-MorpholinocycIopenten- (l), -hexen- (lX -hepten-fl), -octen- (l), -ηοηεη- (ΐχ -decen- (l), -dodecen- (l); analogous 1-piperidino, I-pyrrolidino, 1-piperazino, 1-dimethylamine, 1-diethylamino, 1-N-methyl-N-ethylamino-, 1-imidazolidine) -, 1-pyrrolino- (d2 ') -, 1-imidazolo-, 1-di-n-propylamino-, 1-diisobutylamino-, 1-dihexylamino- , 1-di-tert-butylamino, 1-Di-n-butylamino compounds.

The starting material II is 1 to 2.5, preferably 1 to 1.2 mol of nitrogen monoxide and 0.25 to 1, preferably 0.25 to 0.3 mol of oxygen per mol of starting material II reacted. Instead of oxygen Oxygen-containing gas mixtures, preferably air, can also be used. The nitric oxide-to-oxygen ratio is usually like this chosen so that it corresponds to the composition of nitrous oxide. A small excess of nitrogen monoxide is found to be beneficial. Also be with substances entrained with nitric oxide which form nitric oxide under the reaction conditions, z. B. nitrogen trioxide or nitrogen dioxide, as the corresponding amount of nitrogen monoxide and oxygen calculated. A ratio of 4 to 4.8 moles of nitric oxide to 1 mole of oxygen is preferred

The reaction is generally carried out batchwise or continuously at a temperature from -20 to +100 ⁰ C, preferably from -10 to +40 ⁰ C, without pressure or under pressure. B. in question: aromatic hydrocarbons, for example toluene, ethylbenzene, o-, m-, p-xylene, isopropylbenzene, methylnaphthalene; Halogenated hydrocarbons, especially chlorinated hydrocarbons, e.g. B. amyl chloride, cyclohexyl chloride, dichloropropane, methylene chloride, dichlorobutane, isopropyl bromide, n-propyl bromide, butyl bromide, chloroform, ethyl iodide, propyl iodide, chloronaphthalene, dichloronaphthalene, carbon tetrachloride, tetrachloroethylene, dachloroethane, trachloroethane, trichluorobenzene, pentifloroethane, trichloroethane, pentifloroethane, trichloroethane, trachloroethane, trichloroethane, n-propyl bromide, n-propyl bromide, 1,2-dichloroethane, 1,1-dichloroethane, n-propyl chloride, 1,2-cis-dichloroethylene, n-butyl chloride, sec-, tert- and iso-butyl chloride, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, o-, p- and m-dichlorobenzene, o-, pm-dibromobenzene, o-, m-, p-chlorotoluene, 1,2,4-trichlorobenzene, 1,10-dibromodecane, 1,4-dibromobutane; Alkanols and cycloalkanols such as ethanol, n-butanol, isobutanol, tert-butanol, cyclohexanol, propanol, methanol; Ether, e.g. B. ethyl propyl ether, methyl tert-butyl ether, n-butyl ethyl ether, di-n-butyl ether, di-iso-amyl ether, diisopropyl ether, anisole, phenetol, cyclohexyl methyl ether, Diethyl ether, tetrahydrofuran, thioanisole, ßß'-Oi chlorodiethyl ether; aliphatic or cycloaliphatic hydrocarbons, e.g. B. heptane, pinane, nonane, o-, m-, p-cymene, gasoline fractions within the boiling point range of 70 to 190 ⁰ C, cyclohexane, methylcyclohexane, petroleum ether, decalin, pentane, hexane, ligroin, 2Ä4-trimethylpentane, 2 £ 3-trimethylpentane, 2,3,3-trimethylpentane, octane and mixtures thereof. The solvent is expediently used in an amount of from 200 to 10,000% by weight, preferably from 200 to 1000% by weight, based on starting material II.

The reaction can be carried out as follows: It is expedient to first displace the air in the By means of an inert gas such as nitrogen and then passing nitric oxide and oxygen into the apparatus Gas space above the reaction mixture that the gases only shortly before the reaction with the im Mix the solvent and the dissolved cycloalkene II. The reactor is advantageously equipped with a pressure relief valve closed; it is expedient to work under a slight excess pressure, e.g. B. 1 to 3 at after initiation of the gases, preferably for 1 to 3 hours, the reaction mixture is advantageously for another 0.5 to 1 hour held at the reaction temperature. The end product is then in the usual way, for. B. by filtration, optionally after precipitation, for example with water, and optionally recrystallization, separated off

The compounds which can be prepared by the process of the invention are valuable starting materials for Manufacture of dyes and pesticides. By implementing the end products I with z. B. Hydroxylammonium chloride gives the corresponding 1,2-dioximinocycloalkanes. These are means for binding metal ions, especially heavy metal cations such as cobalt, copper and especially nickel, and corresponding indicators and Precipitants of corresponding metals. They are strong complexing agents for magnesium, calcium, aluminum, Barium and for heavy metal ions, including z. B. nickel, cobalt, copper, chromium-III, cerium and especially for iron-III ions. They can be used as a masking agent for nickel and iron in aqueous solutions and Suspensions where the iron would otherwise interfere, e.g. in the paper and textile industries, use. In the hydrolysis of the end products I with weak acids, the heterocyclic or replace aliphatic amino radical with hydroxyl groups, e.g. B. by the method described in German patent application P 24 41349- O. Z. 30 767. so From l-morpholino-6-oximino-cyclohexene (l) 2-oximinocyclohexanone is formed.

When the end products I are reacted with nitrosyl halides, 2,6-dioximino-cycloalkanones are formed. So 2,6-dioximino-cyclohexanone is obtained in quantitative yield from l-piperidino-6-oximino-cyclohexene (l) and nitrosyl chloride (Japanese laid-open specification 13 653/1972). Such cycloalkanones can be used as starting compounds for the production of amino acids, e.g. B. of lysine (US 29 99 875). Regarding the For use, reference is made to the publications cited in relation to the prior art.

The parts listed in the following examples are parts by weight. The parts by weight restrained to parts by volume like kilograms to liters.

example 1

In a stirred vessel filled with nitrogen with two separate gas inlet pipes, 33.4 parts

freshly distilled l-morpholino-cyclohexene-O), dissolved in 120 parts by volume of distilled η-hexane, submitted within one hour 4.9 parts by volume Nitric oxide and 1.1 parts by volume of oxygen simultaneously at 20 ° C in the gas space above the solution The apparatus is closed by an overpressure valve. After the gases have been introduced, this will be The mixture was subsequently stirred at 20 ° C. for one hour. After adding 125 parts of water, the mixture is stirred Suspension for 30 minutes at room temperature and sucks off the precipitate. One receives after drying 17.9 parts of l-morpholino-B-oximino-cyclohexene-O) (42% of theory, based on nitrogen monoxide used); Mp 176-177 ° C (ethanol).

Example2

30.6 parts of 1-diethylamino-cydohexene-O), dissolved in 100 parts by volume of cyclohexane, are, as described in Example 1, ^{reacted with 4.8 parts by volume of nitrogen monoxide and 1.1 parts by volume of oxygen at 20 °} C. within one hour the mixture is then mixed with 150 parts of water and stirred for a further 30 minutes. The separated organic phase is washed with water and distilled. 14.6 parts of 1-diethylamino-6-oximino-cyclohexene-O) (37% of theory, based on) are obtained nitric oxide used); M.p. 85 ° C (ethanol).

Example 3

33 parts of l-piperidino-cyclohexene (l), dissolved in tO0 Parts by volume of η-hexane are mixed with 4.9 parts by volume of nitrogen monoxide in the same way as in Example 1 within one hour and 5.7 parts by volume of air at 20 ° C. According to the one described in Example 1 Working up gives 12.7 parts of i-piperidino-6-oximino-cyclohexene (l) (30% of theory, based on nitrogen monoxide used); M.p. 170-171 ° C (ethanol).

Example 4

50 parts of l-morpholino-cyclododecen-il), dissolved in 120 Parts by volume of η-hexane are initially charged. About this solution are analogous to Example 1 within one hour 4.8 parts by volume of nitrogen monoxide and 1.1 parts by volume of oxygen are passed after the gases have been passed in the resulting precipitate is suctioned off. 15.9 parts of l-Morplbolino - ^ - oximino-cyclododecene ^ l) (26.5% of theory, based on nitrogen monoxide used); M.p. 146-148 ° C (ethanol).

Claims (1)

Claim: Process for the production of in l-position substituted oximino-cycloalkenes-fl) the general formula H-C C = N-OH (D 10