• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    A process is disclosed for selectively making trans-cyclohexane-1,4-diisocyanate, trans-cyclohexane-1,4-diamine, a trans-cyclohexane-1,4-diurethane, a trans-cyclohexane-1,4-diurea and trans-cyclohexane-1,4-disulphonyl urea by reacting ammonia with a mixture of cis and trans-cyclohexane-1,4-dicarboxylic acid, a lower alkyl ester, a glycol ester, an oligomeric ester or a polyester to make a solid trans-dicarboxylic acid diamide in a first step. The diamide is chlorinated to form cyclohexane-1,4-dicarboxylic acid-bis-N-chloramide. The latter compound is then converted into a (a) trans-cyclohexane-1,4-diamine with an alkali metal hydroxide or alkaline earth metal hydroxide; or into a (b) a trans-cyclohexane-1,4-diurethane by reaction with an alcohol or glycol in a reaction mixture containing an alkali metal hydroxide or alkaline earth metal hydroxide; or into (c) a trans-cyclohexane-1,4-diurea by reaction with a primary or secondary amine in a reaction mixture containing an alkali metal hydroxide or alkaline earth metal hydroxide; or into a (d) trans-cyclohexane-1,4-sulphonyl urea by reaction with a primary sulphonamide in a reaction mixture containing an alkali metal hydroxide and dimethyl formamide and water. The diurea prepared in (c) may be converted into trans-cyclohexane-1,4-diisocyanate with gaseous hydrogen chloride in an inert solvent. The diurethane prepared in (b) and the disulphonyl urea prepared in (d) may be thermally decomposed into trans-cyclohexane-1,4-diisocyanate.
    公开号:SU841579A3
    申请号:SU792734749
    申请日:1979-03-06
    公开日:1981-06-23
    发明作者:Ценгель Ханс；Бергфельд Манфред
    申请人:Акцо Н.В. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a new "method for producing cyclohexane-1,4-diamine, which is a valuable raw material for the synthesis of polyurethanes, polyamides and other poly-5 measures. Important properties of these poly. For example, resistance, shrinkage (compression) resistance and glass transition temperature depend to a decisive extent on the stereoisomeric form of the cyclohexane derivatives used, and these properties are better the higher the proportion of trans isomers in the mixture of isomeric 1,4-derivatives of cyclohexane. fifteen
    Known methods for producing trans-cyclohexane-1,4-diamine, for example by hydrogenation of n-phenylenediamine on nickel or cobalt catalysts, tori in dioxane [1]. 20
    There is also known a method for the isolation of trans-cyclohexane-1., 4-diamine from a mixture with the cis-isomer by fractional crystallization [2].
    Closest to the proposed 25 is a method for producing ^ ran-cyclohexane-1, 4-diamine by hydrogenation of trans-1,4-dinitrocyclohexane in acetic acid in the presence of a platinum catalyst at 25 0 [3]. thirty
    The disadvantages of these methods are the need to use expensive catalysts and high pressure, the difficulty of isolating an individual trans isomer, and the yield of the target product is not high enough (no more than 70%).
    The purpose of the invention is the elimination of these disadvantages and increase the yield of the target product.
    This goal is achieved in that cyclohexane-1,4-dicarboxylic acid or its ester-lower alkyl, glycol, oligomeric or polyester of this acid or a mixture of these compounds is treated with ammonia in polyhydric alcohol at a temperature of 25-200 ° C and at a partial pressure of 0 1-50 atm, solid diamide precipitated is separated, suspended in aqueous mineral acid or in water and chlorinated at 0-40 ° C, the resulting bis-K-chloramide cyclohexane-1,4-dicarboxylic acid is separated, washed with water to chlorine ion removal and processing They are hydrated with alkali or alkaline earth metal hydroxide.
    As the polyhydric alcohols from which the desired oligo or polyesters are obtained, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1 are preferably used 2-propanediol ', 2,3-dimethyl-1,3-propanediol, 2,2, .4-trimethylhexanediol, cyclohexane-1,4-dimethanol and glycerol. The above polyhydric alcohols and mixtures of these alcohols are used as the reaction medium. The alcohol that forms the alcohol component of the cyclohexane-1,4-oligo- or polyester is preferably used.
    The reaction temperature is 25-200 ° C, preferably 50-160 ° C, the partial pressure of ammonia is in the range of 0.1-50 atm.
    Ammonolysis can be carried out in such a way that the oligomeric or polyester is first dissolved or suspended in polyhydric alcohol and then gaseous ammonia is passed into the solution or suspension under reaction conditions with simultaneous stirring. Upon receipt of the diamide in polyhydric alcohol, a significant portion of cyclohexane-1,4-diamide remains dissolved in the reaction mixture. The use of ethylene glycol as a ’reaction medium gives a precipitate of approximately 80% of diamide, which forms almost in quantitative yield. The dissolved diamide remaining in the filtrate of the reaction mixture after separation of the solid diamide is unsuitable for the synthesis of pure trans compounds obtained by the proposed method. The glycol mother liquor can again be used in ammonolysis, i.e. enter into circulation. In this case, the amount of cyclohexane-1,4-dicarboxylic acid diamide increased from the reaction mixture increases to 95% of the theoretical value.
    The resulting cyclohexane-1,4-dicarboxylic acid diamide is then suspended in aqueous mineral acid or in water and chlorinated at 0-40 ° C. to give cyclohexane-1, 4-dicarboxylic acid bis-Y-chloramide.
    As the aqueous mineral acids, it is preferable to use, for example, dilute aqueous hydrochloric acid, sulfuric acid and phosphoric acid. This preferably proceeds from a neutral aqueous suspension of diamide, the hydrogen chloride formed during chlorination as a by-product being dissolved in the reaction mixture and thus the reaction is carried out in a dilute aqueous hydrochloric acid medium.
    Chlorination of diamide proceeds exothermically. It is carried out at temperatures of 0-40 ° C. The use of high temperature borea is disadvantageous. 4 since in this case a significant amount of cyclohexane-1,4-dicarboxylic acid is formed by hydrolysis. Chlorination is preferably carried out at 5-25 ° C, the heat of the reaction is removed by cooling with water.
    Chlorination is carried out both at normal pressure and at elevated, the preferred pressure range is about 1-6 atm.
    Chlorination ends in about 0.25–2 hours. Diamide is almost quantitatively converted to bis-N-chloramide. The suspension obtained after chlorination contains exclusively bis-Y-chloramide cyclohexane-1,4-dicarboxylic acid as a solid; it is separated, for example by filtration or centrifugation. For washing, water with a temperature of 0-15 ° C., preferably ice water, is used. The precipitate is washed until it is completely free of chlorine, washed and dried, for example, at 50 ° C in vacuo. Then cyclohexane-1,4-dicarboxylic acid bis-N-chloramide obtained by ammonolysis of cyclohexane-1, 4-dicarboxylic acid monomeric, oligomeric or polymeric ester in polyhydric alcohol and subsequent chlorination of the resulting cyclohexane-1,4-dicarboxylic diamide acids are further converted to diamine.
    The synthesis of cyclohexane-1,4-diamine is carried out by reacting bis-N-chloramide cyclohexane-1,4-dicarboxylic acid with an alkali or alkaline earth metal hydroxide. Bis-N-chloramide is dissolved or suspended, preferably in aqueous hydroxide, and heated. As the hydroxides use sodium hydroxide and calcium. Hydroxide is used in stoichiometric amounts.
    The conversion of bis-Y-chloramide is carried out, for example, at temperatures of 20-95 ° C (preferably 30-80 ° C). 5-45 wt.% Solutions of bis-1H-chloramide or suspensions of bis-N-chloramide are used. The isolation of diamine from the reaction mixture is carried out by extraction with chloroform, 1,2-dichloroethane or another solvent.
    Example 1. In a 1 liter glass autoclave equipped with a gas inlet tube, stirrer and reflux condenser, 564 g of ethylene glycol (9.1 mol) was placed and 163.7 g (0.82 mol) of cyclohexane-1 dimethyl ether was quickly added. 4-dicarboxylic acid (cis / trans ratio = 9: 1) and then the reaction mixture was saturated with ammonia at room temperature. After that, it is slowly heated, and starting from 80 ° C, the methanol formed is already distilled off. At 100-130 ° С, as well as the simultaneous passage of ammonia, the transesterification is completely completed and the methanol formed in this case is distilled off. At the end of the reaction, one homogeneous solution is formed from the initially available two phases, which is refluxed for 15 minutes and at the same time a weak stream of ammonia is passed through the hot solution.
    After the end of transesterification, the reflux condenser is disconnected and at 110-135 C and an ammonia pressure of 5-9 atm the amidation of the reaction mixture completely ends. In this case, a fine-crystalline white precipitate precipitates, which within 5 hours passes into a dense slurry of crystals. The autoclave is unloaded, the white precipitate is suctioned off from the glycol mother liquor and washed three times with cold water. After drying, ° 115.1 g (82% of theory) of pure cyclohexane-1, 4-dicarboxylic acid diamide (mp 345 350 ° C), 14.0 g (10% of theory) of diam. cyclohexane-1,4-dicarboxylic acid is in the glycol filtrate and another 9.15 g (7% of theory) is found in the washings. The total yield of diamide is 99% of theoretical.
    The mother liquor with cyclohexane-1,4-dicarboxylic acid diamide dissolved in it is reacted with the cis-trans mixture of cyclohexane-1,4-dicarboxylic acid dimethyl ester. The yield of cyclohexane-1, 4-dicarboxylic acid diamide in this case increases to 95-97% of theoretical. about
    Example 2. Analogously to example 1, 163.7 g of cyclohexane-1, 4-dicarboxylic acid dimethyl ester (cis / trans ratio is 1: 1) is mixed with 564 g of ethylene glycol in a 1 L glass autoclave. then heated to 80-110 ° C, introduced into the reaction under catalysis with ammonia and at 110-135 ° C, as well as at an ammonia pressure of 5-9 atm, they completely decompose to cyclohexane-1,4-dicarboxylic acid diamide. After cooling to room temperature, filtering the mother liquor and washing the residue with ice water, 119.2 g (85.5% of theory) of cyclohexane-1,4-dicarboxylic acid diamide are obtained.
    Example 3. Analogously to example 1, 163.7 g of cyclohexane-1,4-dicarboxylic acid dimethyl ester (cis / trans ratio is 1: 9) is transesterified with 564 g of ethylene glycol and then under an ammonia pressure of 5-10 atm at 110 -140 ° C is broken down to cyclohexane-1,4-dicarboxylic acid diamide. After filtration, repeated washing with water at 15 ° C, 129.0 g (92.6% of theory) of cyclohexane-1,4-dicarboxylic acid diamide are obtained from the reaction mixture.
    Example 4. 224 g (1.30 mol)
    Cyclohexane-1,4-dicarboxylic acid (cis / trans ratio 7: 3) and 1000 g of ethylene glycol in the presence of 0.5 wt. £ antimony trioxide, calculated as cyclohexane-1,4-dicarboxylic acid, is heated with stirring for one hour at 190-195 ° C. Then, 600 g of ethylene glycol / water were distilled off over an hour. The oily residue is transferred to an autoclave and (in the manner described in Example 1) an ammonia treatment is carried out. The reaction temperature is 120 ° C, ammonia pressure is 9 atm, the reaction time is 10 hours. After cooling to room temperature, 250 ml of water are added to the reaction suspension containing about 400 g of glycol, then it is filtered off and washed first with 200 ml of water and then with 100 ml of methanol . After drying, 195 g (87.2% of theory) of di cyclohexane-1,4-dicarboxylic acid amide are obtained.
    Example 5. 224 g (1.30 mol,
    Cyclohexane-1,4-dicarboxylic acid, cis / trans ratio 3: 2) and 1500 g (24.2 mol) of ethylene glycol are refluxed in a 2 L glass autoclave with stirring for 45 minutes. Then, 750 g of a mixture of glycol and water are distilled off at atmospheric pressure for 5 hours. After the contents of the autoclave have cooled to 130 ° C, ammonia is passed under atmospheric pressure for
    hours Then the autoclave is cooled, reduce the pressure to normal and the reaction mixture is filtered. Moistened with glycol, the filter residue is washed twice more with 100 ml of methanol or water and then dried in vacuum at 60-80 ° C. The yield of pure cyclohexane-1,4-dicarboxylic acid diamide is 1β7 g (83.6% of theory).
    .Example 6. 172 g (1.01 mol)
    The cyclohexane-1,4-dicarboxylic acid diamide obtained according to Examples 1-4 (filter residue) is dispersed in 2 L of 17% hydrochloric acid at 5 ° C. under vigorous stirring, and then it is passed through this suspension for 30 minutes strong current of chlorine. The temperature should not exceed 10 ° C. After 90 min, chlorination is completed and cyclohexane — 1,4-bis-L-chloramide is separated from the suspension by filtration through a glass filter and washed three times with 100 ml of cold water (5-10. ° С). Out. is 225 g (93% of theory). Bis-I-chloramide cyclohexane-1,4-diconic acid was isolated as pure white crystals, which were dried at 40 ° С.
    Example 7. 17.2 g of cyclohexane-1,4-dicarboxylic acid diamide (0.101 mol) obtained according to Example 5 (filter residue) was suspended in 130 ml of water in a glass | autoclave and then reacted for 15 minutes. pressure of chlorine 5 8 atm temperature 5-15 ° C and vigorous stirring. Then bring the pressure to atmospheric, the precipitate is filtered off and washed with ice water to remove chlorine. 22.0 g (91% of theory) of bis-I-chloro-cyclohexane-1,4-dicarboxylic acid id are obtained.
    Example 8. In a 250 ml three-necked flask, with vigorous stirring, 9.57 g (0.04 mol) of cyclohexane-1, 4-dicarboxylic acid bis-I-chloramide, 4-dicarboxylic acid was dispersed in 70 ml of water and mixed dropwise with solution 10 at 5 ° C 4 g (0.26 mol) of sodium hydroxide (dissolved in 100 ml of water). After the addition of sodium hydroxide solution is complete, a clear solution forms. Remove external cooling and substitute a water bath with a temperature of 35 ° C. After the temperature of the mixture reaches 27 ° C, an exothermic reaction begins, and the temperature of the reaction mixture rises to 66 ° C. After the next 4 minutes, the temperature begins to decline again. Continue to heat for another 45 minutes at 50-75 ° C. Finally a clear, light brown colored solution is formed. It is extracted in the extractor with chloroform for 3.5 hours. After drying over calcium chloride and after removing the solvent, from the chloroform phase
    4.273 g (93.5% of theory) of pure trans-cyclohexane-1,4-diamine (mp. 53-60 °) are irradiated.
    权利要求:
    Claims (3)
    [1]
    The invention relates to a new process for the production of cyclohexane-1,4-diamine, which is a valuable raw material for the synthesis of polyurethanes, polyamides and other polymers. Important properties of these polymers, such as durability, resistance to shrinkage (compression) and glass transition temperature, depend to a decisive extent on the stereoisomeric form of the cyclohexane used (to derivatives, and these properties are better, the higher the fraction of trans-isomers in the mixture of isomeric 1,4-derivatives of cyclohexane. There are known methods for producing trans-cyclohexane-1,4-diamine, for example, by hydrogenating p-phenylenediamine on nickel or cobalt catalysts in dioxane 1. Also known is a method of separating trans-cyclohexane-1., 4-diamine from mixtures with cis-isomer by fractional crystallization 2; Closest to the present invention is a method for preparing ran-cyclohexane-1, 4-diamine by hydrogenating trans-1,4-dinitroxychlohexane in acetic acid in the presence of a platinum catalyst at 25 ° 3, Disadvantages These methods require the use of expensive catalysts and high pressure, the difficulty of isolating the individual trans isomer and the insufficiently high yield of the target product (not more than 70%). The purpose of the invention is to eliminate the indicated disadvantages and increase the yield target product. The goal is achieved by the fact that cyclohexane-1,4g-dicarboxylic acid or its ester-lower alkyl, glycolic, oligomeric or polyester of this acid or a mixture of these compounds is treated with ammonia in a polyhydric alcohol at a temperature of 25-200 s and at a partial pressure of 0, 1-50 atm, precipitated solid diamide is precipitated, suspended in aqueous mineral acid or in water and chlorinated at, the resulting bis-K-chloroamide cslohexane-1,4-dicarboxylic acid is separated, washed with water to remove chlorine ion and process Alkali or alkaline earth metal hydroxide. As polyhydric alcohols, from which the desired oligoyl polyethers are obtained, it is preferable to use ethylene glycol, diethylene glycol, 1-, 3-propandiol, 1,4-butanediol / 1, b-hexanediol, 1,8-octane diol, 1,10-decandiol, 1, 2-propandiol, 2,3-dimethyl-1, 3-propandiol, 2,2, .4-trimethylhexanediol, cyclohexane-1,4-rimethanol and glycerin, as the reaction medium use the above polyols, and the same mixture of these alcohols . Preferably, the alcohol is used which forms the alcohol component of the cyclohexane-1,4-oligo- or polyester complex. The reaction temperature is 25–200 / C, preferably 50–1 ° C, the partial pressure of ammonia is in the range of 0.1–50 atm Ammonolysis can be carried out in such a way that the complex oligo or polyester is first dissolved or suspended in a polyhydric alcohol and then ammonia gas is passed into the solution or suspension under simultaneous mixing conditions. In the preparation of diamide in a multiple atomic alcohol, a significant portion of cyclohexane-1,4-diamide remains dissolved in the reaction mixture. Applying ethylene glycol as a reaction medium gives a precipitate of about 80% diamide, which forms almost quantitatively. Dissolved diamide, which exists in the filtrate of the reaction mixture after separating solid diamide, is unsuitable for synthesis and is obtained by the proposed method of pure trans compounds. Glycolic mother liquor can be used again with ammonium, i.e. enter the circulation. In this case, the amount of BQ of diamide cyclohexane-1,4-dicarboxylic acid that falls out of the reaction mixture is increased to a value of 95% of the theoretical. The obtained diamide cyclohexane-1, 4-dicarbric acid is then suspended in aqueous mineral acid or in water and chlorinated at 0-40 ° to obtain cyclohexane-1, 4-dicarboxylic acid bis-chloroimide. As aqueous mineral acids, it is preferable to use, for example, dilute aqueous hydrochloric acid, sulfuric acid, and phosphonic acid. In this case, it is preferable to emit from a neutral aqueous suspension of diamide, whereby chlorine formed as a by-product as a by-product dissolves hydrogen chloride in the reaction mixture and, thus, the reaction takes place in a dilute aqueous acid hydrochloride. Chlorination of diamide is exothermic. It is carried out at temperatures of 0-40 ° C. The use of high temperatures in Borea is disadvantageous, since in this case a significant amount of cyclohexane-1,4-dicarbanoic acid is formed by hydrolysis. Chlorination is preferably carried out at 5-25 ° C, the heat of the reaction is removed by cooling with water. Chlorination is carried out both at normal pressure and at elevated pressure, the preferred pressure range is about 1-6 atm. Chlorination is complete in about 0.25-2 hours. The diamide is almost quantitatively converted to bis-N-chloramide. The suspension after chlorination contains exclusively bis-y-chloramide cyclohexane-1,4-dicarboxylic acid as a solid; it is separated, for example by filtration or centrifugation. Water with a temperature of 0-15 ° C, preferably ice water, is used for washing. The precipitate is washed until completely free of chlorine, washed and dried, for example at 50 ° C under vacuum. Then bis-N-chloramide cyclohexane-1,4-dicarboxylic acid, obtained by ammonolysis of the monomeric, oligomeric or polymeric ester of cyclohexane-1, 4-dicarboxylic acid in a polyhydric alcohol and the subsequent chlorination of the thus obtained diamide cyclohexane-1,4-dicarboxylic acids are further converted to diamine. The synthesis of cyclohexane-1,4-diamine is carried out by reacting cyclohexane-1,4-dicarboxylic acid bis-N-chloramide with an alkali or alkaline earth metal hydroxide. The vis-N-chloramide is dissolved or suspended, preferably in aqueous hydroxide and heated. Sodium and calcium hydroxides are used as hydroxides. Hydroxide is used in stoichiometric amounts. The conversion of bis-N-chloramide is carried out, for example, at temperatures of 20-95 ° C (preferably 30-80 ° C). 5-45 wt.% - solutions of bis-N-chloramide or suspensions of bis-N-chloramide are used. The isolation of the diamine from the reaction mixture is carried out by extraction with chloroform, 1,2-dichloroethane or another solvent. Example 1 Into a 1 liter glass autoclave equipped with a gas inlet tube, a stirrer and a reflux condenser, 564 g of ethylene glycol (9.1 mol) are placed and 163.7 g (0.82 mol) of cyclohexane dimethyl ether are quickly added. 1,4-dicarboxylic acid (cis / trans ratio of 9: 1) and then the reaction mixture is saturated with ammonia at room temperature :: perurature. Thereafter, it is slowly heated, and starting from 80 ° C the resulting methanol is already distilled off. At 100-130 seconds, as well as simultaneous transmission of ammonia, the ester exchange is completely completed and the methanol that has been broken off is distilled off. At the end of the reaction, a single homogeneous solution is formed from the initially existing two phases, which is refluxed for 15 minutes and a weak stream of ammonia is passed through the hot solution. After the transesterification is completed, the reflux condenser is disconnected, and at 110-135 ° C and an ammonia pressure of 5-9 atm the amidation of the reaction mixture is completely completed. In this case, a fine-crystalline white ossvdoc falls out of the solution, which passes into a dense slurry of crystals within 5 hours. The lavklav is unloaded, the white precipitate is sucked off from the glycol mother liquor and washed three times with cold water. After drying, a temperature of 115.1 g (82% of tepfeT.) Of pure diamide cyclohexane-1, 4-dicarboxylic acid (mp. 345), 14.0 g (10% of theoretical), diami da and cyclohexane-1.4 is obtained. - dicarboxylic acid is found in the glycol filtrate and another 9.15 g (7% of theoretical.) - in the wash water. The overall yield of the diamide is 99% of the theoretical. The mother liquor with dissolved cyclohexane-1, 4-dicarboxylic acid / in it is reacted with a cis-trans mixture of cyclohexane-1,4-dicarboxylic dimethyl ester. The yield of cyclohexane-1, 4-dicarboxylic diamide increases in this case to 95-97% of theoretical, l Example 2. Similarly to the example of 1, 163.7 g of cyclohexane-1, 4-dicarboxylic acid (cis The trans ratio is 1: 1) is mixed with 564 g of ethylene glycol in a 1 L glass autoclave and. then lagged to SO-llO-C, reacted with catalysis, with ammonia and at 110-135 ° C, as well as under an ammonia pressure of 5-9 atm, completely decompose cyclohexane-1,4-dicarboxylic acid to the diamide. After cooling to room temperature, filtration of the mother liquor and washing of the residue with ice water, 119.2 g (85.5% of theoretical) of cyclohexane-1,4-dicarboxylic diamide are obtained. Example 3. Similar to Example 1, 163, 7 g of cyclohexane-1,4-dicarboxylic dimethyl ester (cis / trans ratio is 1: 9) are transesterified with 564 g of ethylene glycol, and then, under an ammonia pressure of 5-10 atm, at 110-140 ° C the cyclohexane is cleaved -1,4-dicarboxylic acid. From the reaction mixture, after filtration, repeated PR01-1LENCHs with water at 15 s, 129.0 g (92.6% of theoretical) of cyclohexane-1,4-dicarboxylic diamide is obtained. Example 4. 224 g (1.30 mol) of Cyclohexane 1,4-dicarboxylic acid (cis / trans ratio of 7: 3) and 1000 g of ethylene glycol in the presence of O, 5 weight. antimony trioxide, based on Hexane-1,4-dicarboxylic acid is heated under stirring for one hour at 190-195 ° C. Then 600 g of ethylene glycol / water mixture is distilled off within 5 hours. The oily residue is transferred to an autoclave and (in the manner described in Example 1) is treated with ammonia. The reaction temperature, ammonia pressure 9 atm, reaction time 10 hours. After cooling to room temperature, 250 ml of water is added to the reaction suspension containing about 400 g of glycol, then filtered and first washed with 200 ml of water and then 100 ml of methanol. After drying, 195 g (87.2% of theoretical.) Of cyclohexane-1,4-dicarboxylic acid amide are obtained. Example 5. 224 g (1.30 mol: Cyclohexane-1,4-dicarboxylic acids cis / tracy ratio 3: 2) and 1500 g (24.2 mol) of ethylene glycol are refluxed in a glass autoclave with a capacity of 2 l with stirring for 45 minutes Then within 5 hours 750 g of glycol-water mixture is distilled off at atmospheric pressure. After the contents of the autoclave are cooled to 130 ° C, aMNwaK is passed under pressure of 6 atm for 3 hours. Then the autoclave is cooled, pressure is reduced to normal and the reaction mixture is filtered. Moistened with glycol filter residue is washed twice more with 100 ml of methanol or water and then dried in vacuum at 60-80 ° C. The yield of pure diamide cyclohexane-1,4-dicarboxylic acid is 1p7 g (83.6% of theoretical). . Example 6. 172 g (1.01 mol) of cyclohexane-1,4-dicarboxylic diamide, prepared according to examples 1-4 (filter residue), is dispersed in 2 l of 17% hydrochloric acid at 5 ° C and vigorous stirring, and then for 30 min a strong chlorine current is passed through this suspension. The temperature should not exceed. After 90 minutes, the chlorination is complete and the cyclohexane-1, 4-bis-M-chloroamide is separated from the suspension by filtration through a glass filter and washed three times with 100 ml of cold water (5-10.c). Out is 225 g (93% of theor.). Bis-M-chloramide cyclohexane-1,4-dicanoic acid is isolated in the form of 6ejttix pure crystals, which are dried at 40 ° C. Example 7. 17.2 g of diamide cyclohexane-1,4-dicarboic acid (0.101 mol) prepared according to example 5 (filter residue), sus, are withdrawn into 130 ml of water in a glass I autoclave and then transformed for 15 min at chlorine pressure 5 8 atm temperature 5-15 ° C and vigorous stirring. The pressure is then brought to atmospheric pressure, the precipitate is filtered and washed with ice water to remove chlorine. 22.0 g (91% of theoretical.) Of bis-M-chloro1 and cyclohexane-1,4-dicarboxylic acid are obtained. Example 8. In a three-necked flask with a capacity of 250 ml, 9.57 (0.04 mol) of cyclohexan-1, 4-dicarboxylic acid bis-M-chloroamide are dispersed in 70 ml of water with vigorous stirring, and mixed with dropwise at 5c a solution of 10.4 g (0.26 mol of sodium hydroxide (dissolved in 100 ml of water). After the addition of caustic soda solution is added, a clear solution is formed. External cooling is removed and the water bath is replaced with a temperature. After the temperature of the mixture reaches 21 ° C, an exothermic reaction begins, the temperature of the reaction mixture being increased After a further 4 minutes, the temperature begins to decrease again. Continue heating for another 45 minutes at 50- 75 C. Finally, a clear, colored in brown color solution is formed. It is extracted in chloroform for 3.5 hours. after drying over calcium chloride and after removal of the solvent, 4.273 g (93.5% of theory) of pure trans-cyclohexane-1,4-diamine is obtained (mp. 53-60 °). Claim 1. Method for producing trans-cyclohexan-1, 4-diamine, characterized in that, in order to increase the yield of the target product, cyclohexan-1, 4-dicarboxylic acid or its lower alkyl ether, glycol ether, oligomeric ether or polyester or the mixture of these compounds is treated with ammonia in a polyhydric alcohol at 25–200 ° C and at a partial pressure of 0.1–50 atm, the solid diamide precipitated is separated, washed with water, suspended in aqueous mineral acid or in water, and chlorinated at yet poluchkhtsiyes bis-M-chlorine Id loop hexane-1,4-dicarboxylic acid from water flushes to remove chlorine ion. and treated with hydrochloric acid or alkaline earth meta la. Sources 1 of the information taken into account in the examination 1. US patent number 2175003., cl. 260-553, publ. 1952.
    [2]
    2. Patent of the USA No. 3657345, cl. 260-553, publ. 1969.
    [3]
    3.A.T.Nielsen. The Isomeric Dinitrocyc1ohexanes. - Org. Chem., 1962, 27, p. 1998 (prototype).
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    US3959377A|1976-05-25|Method for preparing 2-nitro-4-amino-N-phenylaniline
    AT359519B|1980-11-10|METHOD FOR PRODUCING TRANS-CYCLOHEXANE-1,4-DIURETHANE
    SU825505A1|1981-04-30|Method of preparing p-phenylenediamine
    JP3787866B2|2006-06-21|Process for producing binuclear dimethylol compound of p-cresol
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    同族专利:
    公开号 | 公开日
    CA1100522A|1981-05-05|
    BR7800560A|1978-10-03|
    AT355010B|1980-02-11|
    US4203916A|1980-05-20|
    BE864741A|1978-07-03|
    DD132865A5|1978-11-15|
    ATA918177A|1979-07-15|
    US4418211A|1983-11-29|
    NL7802232A|1978-09-13|
    FR2383169A1|1978-10-06|
    FR2383169B1|1982-12-17|
    AU519392B2|1981-12-03|
    IT1104132B|1985-10-14|
    US4457871A|1984-07-03|
    JPS62246547A|1987-10-27|
    DE2710595A1|1978-09-14|
    ES466943A1|1978-10-01|
    US4275223A|1981-06-23|
    US4439370A|1984-03-27|
    JPS6229425B2|1987-06-25|
    US4467114A|1984-08-21|
    JPS53112849A|1978-10-02|
    AU3382678A|1979-09-06|
    JPS638097B2|1988-02-19|
    GB1598666A|1981-09-23|
    DE2710595C3|1980-11-06|
    IT7847615D0|1978-01-12|
    SE7802752L|1978-09-12|
    DE2710595B2|1980-03-13|
    US4486603A|1984-12-04|
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    法律状态:
    优先权:
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    DE2710595A|DE2710595C3|1977-03-11|1977-03-11|Process for the preparation of the trans isomers of cyclohexane-1,4-diamine, diurethanes, -diureas, -disulfonylureas and -diisocyanate|
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