DE1014991B - Process for the production of cycloaliphatic 1,2-diamines - Google Patents

Description

GERMAN

The invention relates to a new process for the preparation of cycloaliphatic 1, 2-diamines, which represent, for example, valuable starting materials for pharmaceuticals, pesticides and textile auxiliaries.

It has surprisingly been found that cycloaliphatic 1,2-diamines with six to eight ring members can be used in the ring bearing the amino groups according to the general formula

NH,

XH-NH ₉

wherein R one the group, CH - CH, ^to one

Cycloalkylene, bicycloalkylene or benzocycloalkenylene radical supplementing, divalent hydrocarbon radical with 1,4-, 1,5- or 1,6-valences means, from the ao easily accessible a-halocycloalkanones of the general formula

XO

II

XH shark

where Hal is chlorine or bromine and R is the same divalent hydrocarbon radical as in formula I, can be prepared in a three-stage reaction sequence that can be carried out with good yields by a halogen ketone of the general formula II is heated with urea in the presence of a hydrogen halide acceptor, the resulting imidazolone from one of the two tautomeric formulas

Method of manufacture
of cycloaliphatic 1,2-diamines

Applicant:
JR Geigy AG, Basel (Switzerland)

Representative: Dr. F. Zumstein
and Dipl.-Chem, Dr. rer. nat. E. Assmann,
Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority:
Switzerland from June 16, 1955

Dr. Charles Simon, Basel (Switzerland),
has been named as the inventor

Q - N. K CH- NH '" III ) co λ \ : NH : —NH III '

XO

by means of catalytically activated hydrogen to an imidazolidone of the general formula

r;

XH-NH,

"CH-NH"

IV

hydrogenated and this preferably in mineral acid solution to a 1,2-diaminocycloalkane, bicycloalkane or benzocycloalkane of the general formula I hydrolyzed.

As a hydrogen halide acceptor in the first stage, for example, an excess of urea of Serve at least half the molar amount. It is expedient to use about 2 moles or in this case more urea to 1 mol of haloketone and follows the course of the reaction on the basis of the evolution of carbon dioxide. The reaction between halocycloalkanone and urea usually sets in between 50 and 150 ° and goes under Heat development in front of you, so that mostly the use of an organic solvent and diluent is necessary to control the course of the reaction.

Suitable diluents have been diethylene glycol ethers, such as. B. the diethylene glycol diethyl ether, proven.

As starting materials of the general formula II come

z. B. ^ - chlorocyclohexanone, 2-bromocyclohexanone, 3-chloro-methylcyclohexanone- (2), 4-chloro-1-methyl-cyclohexanone - (3), 3 - chlorine -1 - methylcyclohexanone - (4), 2 - chlorine- and 2-bromocycloheptanone, 2-bromocyclooctanone and also fused halogenocycloalkanones, e.g. B. lXhlordekahydronaphthalin-2-one, 3-chlorodecahydronaphthalen-2-one, 1-chloro- and l-bromotetrahydronaphthalen-2-one, are possible.

Suitable catalysts for the hydrogenation of the poly

methylenimidazolones of the general formula III are

z. B. nickel catalysts, such as Raney nickel or nickel on kieselguhr, also noble metal catalysts, z. B. platinum catalysts.

The solvents used in the hydrogenation are, for. B. alcohols such as ethanol or propanol into consideration. The Hydrogen is advantageously left under pressure at temperature

709 660/428

Claims (1)

temperatures of 100 to 180 ° act until the theoretical amount is absorbed. The hydrolysis of the imidazolidones to the desired end products can be carried out by means of mineral acid, e.g. B. 60% sulfuric acid or 70% phosphoric acid, can be carried out with good yield. In contrast to the products from other processes, the cycloaliphatic 1,2-diamines obtainable according to the invention can be quantitatively converted into uniform crystalline-liquid product which is readily soluble in water and which strongly attracts carbonic acid. Example 2 Using 73 parts of 2-chlorocycloheptanone (boiling point 14 = 96 to 98 °) and 66 parts of urea in 110 parts of diethylene glycol diethyl ether, cycloheptimidazol-2-one (4,5-cyclopentamethyleneimidazol-2-one; M.p. that the two amino groups are in the cis position to one another, while they are in the trans position to one another in the main products of other industrial processes By-products which were difficult to isolate and which were obtained in small amounts were accessible (len urea) with a melting point of 253 ° (from methanol) can be hydrogenated. 31 parts of this imidazolidone and 60 parts of 650% sulfuric acid are stirred for about 15 hours at an internal temperature of 135 to 145 °. After this time, the evolution of carbon dioxide has practically ended. The solution is cooled, diluted with 40 parts of water and made alkaline with concentrated sodium hydroxide solution, whereupon implementation 20 separates the 1,2-diaminocycloheptane as an oil. It is "" extracted with ether, the extract is dried with sodium sulfate, evaporated and the residue is distilled over sodium hydroxide. The 1,2-diaminocycloheptane (bp 23 = 106 to 107 °) boils and is obtained from the cycloheptimidazolidane in a yield of about 80%. explain the new procedure in more detail. Parts mean parts by weight; these relate to parts by volume as g to cm3. EXAMPLE 1 Example 3 32 parts of 1-chlorodecahydronaphthalen-2-one (m.p. 108,200 parts by volume of diethylene glycol diethyl ether heated to an internal temperature of 135 to 140 °. Carbon dioxide escapes and a white reaction product begins to crystallize out after a short time. After 4 to 5 hours the evolution of carbon dioxide has ended It is cooled to room temperature and the pasty contents are filtered, the filter residue is mixed with hot water, filtered again, washed with water and then dried. A mixture of 66 parts of urea and 100 parts by volume of diethylene glycol diethyl ether is heated to 140 ° until the urea has melted Then, with vigorous stirring, 66 parts of freshly distilled 2-chlorocyclohexanone 30 to 110 °, prepared by chlorinating decahydro, are added dropwise over the course of 20 to 30 minutes, the temperature being reduced despite removal of the naphthalen-2-one) with 23 parts of urea in a heater up to 150 ° and at the same time carbon dioxide s t soft. One soon notices a progressive precipitation of white crystals in the liquid. After the end of the dropwise addition, the mixture is stirred for about x / 2 hours at 35 140 ° until the elimination of carbon dioxide has ceased. The mixture is then allowed to cool, the pulpy reaction mixture is stirred into 200 parts of water and filtered off with suction. The filter material is washed with water and then dried. The crude 4,5-Cycloheximid- 40 net obtained in this way. This gives 27 parts of octahydronaphthimidazol-2-one azol-2-one (4, S-cyclotetramethyleneimidazol ^ -one) is in the form of a yellowish powder. Recrystallization from ethanol gives it white; its decomposition point is then around 256 to 260 °. The imidazolone thus obtained is suspended in 200 parts of absolute ethanol, mixed with 10 parts of Raney nickel and hydrogenated at 130 to 150 ° under 120 atmospheric pressure. The octahydronaphthimidazolidone with a melting point of 159 to 160 ° (from ethyl acetate) 145 ° hydrogen under 120 to 125 atmospheric pressure can be isolated from the resulting solution in a yield of over 90%. Act by boiling the imidazolidone obtained in this way until the hydrogen was absorbed, which corresponds to the amount of 1,2-diamino required theoretically with 60% sulfuric acid. Thereupon, the cadecahydronaphthalene is filtered off as a colorless, strongly basic liquid lyser, the solvent is evaporated off and the residue is distilled in vacuo. The 4,5-cycloheximidazolidone (N, N'-cyclohexyleneurea) goes over at 55 Kp.14 = 218 to 220 ° (melting point 149 to 150 °). For hydrolysis, 14 parts of 4,5-cycloheximidazolidone are heated with 30 parts of 60% sulfuric acid while stirring. At 95 ° carbon dioxide slowly begins to develop, which becomes lively at 105 °. This temperature is maintained for about 1 hour until the evolution of carbon dioxide ceases and the reaction mixture is a clear R.I solution. After cooling, the CH NH solution is carefully made alkaline with concentrated sodium hydroxide solution with external cooling (e.g. suspended with 80 parts of 31.5% strength 6g in about 200 parts by volume of absolute alcohol at boiling temperature, then cooled and filtered off. If desired, this pre-purified product can are recrystallized from absolute ethanol, whereupon it melts with decomposition at 290 ° to 300 ° C. For hydrogenation, 28 parts of 4,5-cyclohexmidazol-2-one are suspended in 200 parts by volume of absolute ethanol, 10 parts of Raney nickel are added and left at 135 to A good yield of 0i02 = 87 °. 1. Process for the preparation of cycloaliphatic 1,2-diamines of the general formula , CH-NH ₂ Lye) and the precipitated base extracted with ether. The ether extract is evaporated and distilled over 3 to 4 parts of sodium hydroxide. The obtained in a yield of 75 to 80%, sterically uniform 1,2-Diaminoc3 ^r clohexan (Kp. _U = 70 to 73 °) is a colorless, wherein R is the group .CH - CH. to a divalent hydrocarbon radical supplementing a cycloalkylene, bicycloalkylene or benzocycloalkenylene radical with 1,4-, 1,5- or permanent valences means, characterized in that a haloketone of the general formula XO T? I TT R j II XH- shark heated with urea in the presence of a hydrogen halide acceptor, the resulting imidazolone of one of the two general formulas CN _n ) co <ll NH CH-NH ⁷ T -NH III III ' CO by means of catalytically activated hydrogen to an imidazolidone of the general formula XH-NH, ; co hydrogenated and this preferably hydrolyzed in mineral acid solution. ^. Method according to claim 1, characterized in that that as hydrogen halide acceptor urea in an excess of at least the half the molar amount used. © 709 660/428 8.57