DE2055165A1 - Epsilon-caprolactam and c-alkylated epsi- - lon-caprolactams production - Google Patents

Abstract

2-Caprolactam (and C-alkylated derivs. starting from corr. alkylated cpds.) is obtained from 3, 3-pentamthylene-oxaziriline (cyclohexane iso-oxime) in an org. solvent (hydrocarbons, ethers) at 20-160 degrees C, pref. 40-120 degrees C, in presence of a cpd. of V, B, Mo, Ga, Sa, Eu, Tm, Yt, Lu or La, pref. an org. complex V (acetylacetonate etc.). After removal of the catalyst fresh iso-oxime, prepared by treatment of cyclohexane with NH3 and hypochlorite is added to or formed in the reaction mixture, epsilon-caprolactam being simultaneously removed into the aq. phase.

Description

Process for the preparation of # -caprolactam and C-alkylated # -caprolactams The invention relates to a process for the preparation of # -caprolactam and C-alkylated ones # -Caprolactams.

It is known to produce ε-caprolactam on the basis of phenol. The phenol is first hydrogenated to cyclohexanol and this to cyclohexanone dehydrated.

Another process starts from cyclohexane, which leads directly to cyclohexanone is oxidized. The cyclohexanone then becomes the cyclohexanone oxime with hydroxylamine implemented. The last stage consists of a Beckmatin rearrangement of the resulting material Cyclohexanone oxime using concentrated sulfuric acid to # -caprolactam.

The industrial production of s-caprolactam from phenol or cyclohexanone are the most widely used procedures after which one is the predominant today Part of the world production of # -caprolactam wins.

Processes for the production of # -caprolactam are also known, in which a cyclohexanone oxime produced in another way is rearranged. bo it is known to produce the cyclohexanone oxime by nitration of cyclohexane, which is produced by Hydrogenation of benzene was obtained, and subsequent reduction of the resulting Nitrocyclohexane, for example with sulfur dioxide or hydroxylamine, to manufacture. Nitrocyclohexane can also continue to work with ethylene and Raney cobalt too Cyclohexanone oxime are implemented.

Furthermore, cyclohexanone oxime can be produced by photonitrosation of cyclohexane with nitrosyl chloride, by oxidation of toluene to benzoic acid and then Hydrogenation, nitrosation and carboxylation as well as by oxidation of cyclohexanone and ammonia can be obtained with hydrogen peroxide.

It is also known to produce cyclobexanone oxime through catalytic rearrangement to implement # -caprolactam. The processes mostly work at temperatures 360 ° C in the gas phase. As catalysts are boron oxide on aluminum @@, phosphoric acid on diatomaceous earth or kieselguhr or phosphoric acid, boric acid, alkali bisulfite Aluminum oxide, activated carbon, diatomaceous earth, kieselguhr, tin dioxide or titanium dioxide described.

Most of these procedures are basically also suitable for Production of C-alkylated # caprolactams.

It has also been suggested a solution of 3,3-pentamethyllenoxaziridine (Cyclohexanonisoxim) in a suitable organic solvent within a very short time Time to temperatures of 250 to 350 ° C heat, taking £ -caprolactam is obtained in good yields.

Furthermore, it has also already been proposed that # -caprolactam in the way to win that you get cyclohexanone isoxime from a suitable solvent extracted with highly concentrated sulfuric acid and the sulfuric acid solution a Subjects to Beckmann rearrangement at temperatures of 80 to 150 ° C.

The thermal conversion of 3,3-pentamethyleneoxaziridine (cyclohexanone isoxime) for 6-caprolactam requires heating of the feedstock to high temperatures in a very short time, which requires special equipment on an industrial scale power. There is also the risk of the product becoming resinous.

The Beckmann rearrangement of the from a solution by means of sulfuric acid extracted isoxime takes place at lower temperatures, but occurs here the problem of the utilization of the inevitably arising during the implementation Ammonium sulfate.

The purpose of the invention is to remedy the deficiencies in the manufacturing process Avoid i-caprolactam from 3,3-pentamthylenoxaziridine (cyclohexanone isoxime) and this new synthesis on the production of C-alkylated # caprolactams to expand.

The task was therefore to find a method with which it succeeds in both # -caprolactam and C-alkylated # -caprolactams in an economical way Way from the corresponding isoximes under gentle conditions and with avoidance the formation of difficult-to-use by-products in good yields.

This object is achieved by a method for catalytic production of ε-caprolactam and C-alkylated ε-caprolactams according to the invention thereby that one 3,3-pentamethyleneoxaziridine (cyclohexanone isoxime) or its in the cyclohexane ring alkylated derivatives in a suitable organic solvent in the presence its catalyst, the compounds of vanadium, boron, molybdenum, gadolipium, Samariums, Europiums, Thuliums, Ytterbiums, Lutetiums and Lanthans, individually or in the mixture, contains, at temperatures from 20 to 160 ° C., preferably 40 to 120 0C, zar Unsetzang brings and the resulting lactam in a known manner isolated from the reaction mixture.

Such catalysts are particularly suitable for the implementation, which contain oxides, salts or organic complexes of the listed elements. Preferred one uses catalysts that contain organic complex compounds of vanadium.

Practically all organic solvents can be used as solvents into consideration that no reaction with the isoxime under the operational conditions enter, such as benzene, toluene, xylene, gasoline or ether; not suitable are e.g. B. those with hydroxyl or amino groups.

It is particularly advantageous to use isoximes that are obtained by reacting the corresponding ketones with ammonia and a hypochlorite according to X registration P 19 61 474.5 were created. If the I # oximes obtained by this process are used, the ε-caprolactam and the C-alkylated ε-caprolactams can be obtained in a particularly economical manner by extracting the caprolactam in one process step and at the same time preparing new feedstock in the reaction mixture.

This is done in such a way that the reaction mixture obtained in the lactam production after separation of the catalyst is repeated for isoxime production according to P 19 61 474.5 of the ZDi registration is used, the isoxime solution thus produced is used again for the production of caprolactam, the caprolactam is extracted at the same time through the aqueous phase used for production of isoxime and it is isolated therefrom in a manner known per se.

The catalysts used in the process according to the invention can be reused, if necessary after regeneration. As far as it is these are compounds that are insoluble in organic solvents, you can after the transfer is complete.

mechanically separated and easily reused any number of times will. If the catalysts are soluble in the solvent, they must after completion separated from the rearrangement and regenerated before re-use.

The method has the advantage that at relatively low temperatures can be carried out in the liquid phase, so that no solvent evaporates needs to be, which results in a significant energy saving. The procedure continues to provide an extremely pure product in high yield, in particular occurs no inevitable formation of ammonium sulphate.

The isoxime used as the starting material is not particularly necessary to be cleaned, as the reaction conditions are very specific for the isoxime are so that ettl. Impurities contained therein remain unchanged and the Do not disturb the process.

Example 1 In a 5-1 flask fitted with a reflux condenser a solution of 104 g (0.92 mol) of 3.3-pentamethyleneox #ziridine (cyclohexanone isoxime) in 4.5 l of benzene, the excess cgclohexanone from the production of the isoxime contained, introduced and heated to boiling.

A solution of 2.44 g (1 mmol per 100 mmol of isoxime) vanadyl-bis was added (acetylacetonate) (VO (C5H7O2) 2) in 100 ml of benzene and heated the Solution 5 min. To the boil. After the flocculated catalyst had been filtered off, it was distilled one first the benzene at normal pressure, then the cyclohexanone at 20 Torr.

There remain 103 g (0.91 mol) of ε-caprolactam (99% of theory) as almost colorless crystal mass back. The # -caprolactam content was determined by formol titration more than 99% determined. Vacuum distillation at 139 ° C / 12 torr gave a colorless product-from melting point 68 to 69 ° C.

Example 2 In a 5-1 flask fitted with a reflux condenser a solution of 104 g (0.92 mol) of 3.3-pentamethylene ## - aziridine (cyclohexanone isoxime) Brought in 4.5 l of gasoline from the boiling range 120 to 140 ° C and at 100 oO below Stirring with a solution of 4.25 g (1.2 mmol per 100 mmol of isoxine) vanadyl bis (benzoylacotonate) (VO (C10H9O2) 2) in 100 ml of toluene are added. The solution thus obtained was stirred for a further 5 minutes; and heated to 100 0a. After filtering off the flocculated The catalyst was obtained by working up the filtrate by distillation as in the example 101 g (0.895 mol) ε-caprolactam, corresponding to a yield of 97% d. Th.

Example 3 Into a 3-1 flask fitted with a reflux condenser was a solution of 48.5 g (0.43 mol) of 3,3-pentamethyleneoxiaziridine (cyclohexanone isoxime) Brought in 2.4 1 toluene and at 105 ° C with stirring with a solution of 1.12 g (0.7 mmol per 100 mmol of isoxime) bis (8-hydroxychinolinato) dioxovanadine (V) acid (VOOH (C9H6NO) 2) in 30 ml of cyclohexanone. The solution thus obtained was still Stirred for 10 minutes and heated to 1050 in the process. By working up analogously to the example 1 were 47.5 g (0.42 mol) # -caprolactam, corresponding to a yield of 98% d. Th., Received.

Example 4 In a 1 liter flask fitted with a reflux condenser was a solution of t4.6 g (0.129 mol) of 3.3-pentamethyleneox-aziridine (cyclohexanone isoxime) in 820 ml of xylene, the cyclohexanone still in excess from the production of the isooxime contained, introduced and at 140 ° C with stirring with a solution of 0.685 g (2 Sol per 100 mmoles Isoxime) vanadyl bis (acetylacetonate) in 30 ml Xylene added. The solution obtained in this way was still 5 min.

stirred and heated to 140 ° C. in the process. One obtained by working up analogously to Example 1 12.1 g (0.107 mol) of t, -caprolactam, corresponding to a yield of 83% d. Th ..

Example 5 In a flask fitted with a reflux condenser, a Solution of 12.7 g (0.112 mol) 3.3-pentamethylene oxpaziridine (cyclohexanone isoxime) in 760 ml of diethyl ether.

brought and at 30 ° C with stirring with a solution of 0.595 g (2 mZol per 100 mmol isoxime) vanadyl bis (acetylacetonate) in 20 ml cyclohexanone offset. The resulting solution was further heated to 30 ° C and stirred, until a sample taken no longer has the ability to oxidize to a solution of Potassium iodide in glacial acetic acid showed. Working up analogously to Example 1 gave 11.2 g (0.099 mol) of # -caprolactam, corresponding to a yield of 88% of theory. Th ..

Example 6 Into a 2-1 flask fitted with a reflux condenser was a solution of 30.2 g (0.238 mol) of 4-methyl-cyclohexanepiro-3-oxaziridine (4-methylcyclohexanone isoxime) introduced into 1700 ml of toluene and at 100 O with stirring with a Solution of 0.946 g (1.5 mmol per 100 mmol of isoxime) vanadyl bis (acetylacetonate) in 40 ml of toluene are added. The solution obtained in this way was still 5 min.

stirred and heated to 100 ° C. Analogous to the work-up Example 1 went in the vacuum distillation (116 ° C / 1.5 Torr) 28.7 g (0.226 mol) γ-methyl - # - caprolactan from melting point 45 to 46 0C above, corresponding to a Yield of 95% of theory Th ..

Example 7 Into a 1 liter flask fitted with a reflux condenser was a solution of 19.6 g (0.139 mol) of 4-ethyl-cyclohexane-spiro-3-oxaziridine (4-ethylcyclohexanone isoxime) introduced into 800 ml of toluene and heated to boiling. A solution of 0.625 was added g (1.7 mmol per 100 mmol of isoxime) vanadyl bis (acetylacetonate) in 30 ml of toluene and heated the solution thus obtained to boiling for 10 minutes. Analogous to processing Example 1 gave 18.5 g (0.131 Mol) γ-ethyl- # -caprolactam from melting point 56 to 57 ° C above, accordingly a yield of 94% of theory. Th ..

Example 8 In a reflux condenser, 1-1 flask was added a solution of 22.0 g (0.130 mol) of 4-tert-butyl-cyclohexane spiro-3'-oxaziridine (4-tert-butylcyclohexanone isoxime) introduced into 780 ml of toluene and rntt at a temperature of 110 ° C with stirring a solution of 0.55 g (1.6 mmol per 100 mmol isoxime) vanadyl bis (acetylacetonate) added in 25 ml of toluene. The solution obtained in this way was stirred for 10 min heated to 110 0C. When working up the solution according to Example 1 went to the Vacuum distillation at 140 to 141 ° C / 1 Torr 20 g (0.118 mol) γ γ-tert-butyl & -caprolactam with a melting point of 156 ° C. above, corresponding to a yield of 91% d. Th ..

Example 9 In a 5 liter flask fitted with a reflux condenser 10 grams of vanadium pentoxide and a solution of 115 grams (0.905 moles) of 4-methylcyclohexane spiro-3'-oxaziridine (4-methylcyclohexanone isoxime) in 4.2 l of toluene. While stirring was on Heated to reflux until a sample taken no longer showed any oxidative capacity. The organic phase was then decanted from the vanadium pentoxide, and the work-up As in Example 1, vacuum distillation (116 ° C / 1.5 Torr) gave 54 g (0.425 Mol) y-methyl- # -caprolactam from melting point 45 to 46 ° C, corresponding to one Yield of 47% of theory Th .. The vanadium pentoxide left behind during decanting can be used to relocate the next batch.

Example 10 Into a 3-liter flask fitted with a reflux condenser were 10 g vanadyl sulfate. 3 H20 and a solution of 47.1 g (0.417 Mole) 3.3-Peatamethyleneoxaziridine (cyclohexanone isoxime) was introduced into 2540 ml of toluene. The solution was refluxed with stirring until a sample was removed Showed more oxidative power. The organic phase was then removed from the vanadyl sulfab. 3 H20 decanted. Working up the solution as in Example 1 gave 24 g (0.213 Mol) -caprolactam, corresponding to a yield of 51% of theory. Th .. That while decanting Remaining vanadyl sulfate. 3 H20 can be used for rearrangement of the next batch will.

Example 11 In a 5-1 flask fitted with a reflux condenser, 10 g catalyst (composition: 15.7 ffi V205, 20.8 ffi B203 and 63.5% Ti02) and a solution of 113 g (1 mol) of 3,3-pentamethyleneoxaziridine (cyclohexanone isoxime) in 4.38 1 xylene, which contained from the production of isoxime according to cyclohexanone, brought in. While stirring, the solution was heated to 120 ° C until a The sample taken showed no ability to oxidize. The organic phase was decanted. When working up as in Example 1, 65.6 g (0.58 mol) of 6-caprolactam, corresponding to a yield of 58% of theory. Th., Received. The one left behind when decanting Catalyst can be used to rearrange the next batch.

.Examples 12 to 16 When using the catalysts listed below (10 g in each case) under the conditions of Example 11 were those given after it Yields of # -caprolactam achieved: Composition of the catalyst mol g% of theory

25.4% WO3; 40.0% V2O5; 0.54 61.0 54 2.6% P2O5; 32.0% SiO2 25.9 % WO3; 40.8% V2O5; 0.50 56.5 50 1.3% B2O3; 32.0% SiO2 37.8% WO3; 17.9% V2O5; 0.47 53.1 47 12.3% P2O5; 32.0% SiO2 55.5% WO3; 26.3% V2O5; 0.55 62.1 55 18.2 % P2O5 91.7% α-Al2O3; 0.42 47.5 42 5.5% V2O5; 2.8% MoO3 Example 17 In In a 3-liter flask fitted with a reflux condenser, 5 g of boron trioxide and a solution were added of 65 g (0.575 mol) of 3,3-pentamethyleneoxaziridine (cyclohexanone isoxime) in 2.5 l of toluene brought in. While stirring, the solution was refluxed until one The sample taken no longer showed any oxidative capacity. The organic phase was then decanted from the boron trioxide. The work-up of the solution according to Example 1 resulted 41 g (0.362 mol) # -caprolactam, corresponding to a yield of 63% d. Th. The catalyst left behind during decanting can be used for rearrangement the next batch can be used.

Examples 18 to 19 Using the compounds listed below of the boron (5 g each) were under the conditions of Example 17 the following given yields of ε-caprolactam achieved: H3BO3 0.328 mol 37 g 57% of theory. Th, B-iso (0C5H11,) 3 0.27 "30.6 g 47% of theory

Example 20 In a 1 liter flask fitted with a reflux condenser, 1 g of gadolinium oxide and a solution of 14; 3 g (0.126 mol) of 3,3-pentamethyleneoxaziridine (Cyclohexanone isoxime) introduced into. 700 ml of toluene. With stirring, the solution became Heated to the boil until a sample taken no longer has any oxidative capacity showed. The organic phase was then decanted from the gadolinium oxide. The work-up the solution according to Example 1 gave 8.74 g (0.077 mol) of i-caprolactam accordingly a yield of 61% of theory.

The catalyst left behind during decanting can lead to rearrangement the next batch can be used.

Examples 21 to 26 Using the following oxides (in each case 1 g) under the conditions of Example 20, the yields indicated behind it of # -caprolactam, catalyst achieves mol g% of theory

Samarium oxide 0.069 7.86 55 europium oxide 0.052 5.86 41 thulium oxide 0.052 5.86 41 Ttterbium Oxide 0.064 7.30 51 Lutetium Oxide 0.058 6.58 46 Lanthanum Oxide 0.059 6.73 47 Example 27 In a 1-liter flask equipped with a reflux condenser 16.1 g (0.143 mol) of 3,3-pentamethyleneoxaziridine (cyclohexanone isoxime) in 730 ml of toluene, which still contained cyclohexanone from the preparation of the isoxime, and 0.42 g (1 mmol per 100 nalol isoxime) molybdenum bis (acetylacetonate) (Mo (C5H7O2) 2) introduced. the Solution was heated to boiling and stirred at this temperature until a sample taken no longer showed any oxidative capacity.

The organic Ptiase was worked up analogously to the example 1 5.5 g (0.049 mol) # -caprolactam, corresponding to a yield of 34% of theory. Th ..

Example 28 In a 1 liter flask fitted with a reflux condenser 15.2 g (0.134 mol) of 3,3-pentamethyleneoxyziridine (cyclohexanone isoxime) in 750 ml of toluene and 0.53 g (1.5 moles per 1b0 mmoles of isoxime) molybdenum hexacarbonyl (Mo (CO) 6) was introduced. The solution was heated to the boil and stirred at this temperature for so long until a sample taken no longer showed any oxidative capacity. One obtained ourch Working up the organic phase analogously to Example 1 5.6 g (0.05 mol) ε-caprolactam, corresponding to a yield of 37% of theory.

Example 29 In a separating funnel of 6 liters capacity 500 ml (474 g) cyclohexanone, 54 ml (600 mmol) of a 11.2 @ aqueous ammonia solution, 400 ml of water and 2.4 l of toluene were introduced and shaken. One added 580 mmol of a 0.7 molar neutral sodium hypochlorite solution (43.2 g) and shaken half a minute vigorously. Then the organic phase was separated (2.87 l) away. It contained 57.0 g (504: nmol) of 3,3-pentamethyleneoxaziridine (cyclohexanone isoxime), corresponding to a yield of 87% of theory. Th., Based on the sodium hypochlorite solution used. From this solution, which can be briefly desiccated with anhydrous sodium sulfate shaken, were 2.6 1, the 51.6 g (0.456 moles) 3,3-pentamethylene oxaziridine (Cyclohexpnonisoxime) in a 3-1 flask equipped with a reflux condenser introduced and heated to the boil. A solution of 1.27 g (1.05 mmol per 100 mmol of isoxime) vanadyl bis (acetylacetonate) in 50 ml of toluene and stirred the Solution 5 minutes, during which it was heated to the boil. The solution was then allowed to cool and filtered off from the flocculated catalyst. The filtrate, in addition to toluene and Cyclohexanone from -Caprolactam contained, 49.5 g of cyclohexanone were added, about the cyclohexanone consumed in the production of 3.3-pentamethyleneoxaziridine to replace, and was used to manufacture 3.3-pentamethyleneoxaziridine accordingly of the above regulation is used. The yield of 3,3-pentamethyleneoxaziridine was 87% d. Th .. That in the org. Phase existing £ -caprolactam went into the aqueous phase over, from which it is obtained by extraction with methylene chloride and distillation at 139 ° C / 12 torr. The yield was 50.5 g (0.447 mol) # -caprolactam, corresponding to a yield of 98% of theory. Th ..

Claims (6)

Patent claims: Process for the catalytic production of ε-caprolactam and of ε-caprolactams alkylated on carbon, characterized in that 3j3-pentamethyleneoxaziridine (Cyc'lohexanonisoxim) or its derivatives in the cyclohexane ring, alkylated in a suitable one organic solvent in the presence of a catalyst, the compounds of the Vanadins, Bors, Molybdenums, Gadolinimus, Samariums, Europiums, Thuliums, Ytterbiums, Contains lutetiums and lanthanum, individually or as a mixture, at temperatures of 20 to 160 00, preferably 40 to 120 ° C, brings to the reaction and the resulting Lactam isolated from the reaction mixture in a manner known per se. 2. The method according to claim 1, characterized in that the implementation is carried out in the presence of catalysts, the oxides salts or organic Contain complexes of the elements mentioned. 3. The method according to claim 1, characterized in that the implementation is carried out in the presence of catalysts, the organic complex compounds of vanadium included. 4. The method according to claim 1 to 3, characterized in that as Solvent benzene, toluene, xylene, gasoline or ether can be used. 5. The method according to claim 1 to 4, characterized in that the isoximes used by reacting the corresponding ketones with ammonia and a hypochlorite according to the -BBR notation P 19 6 474.5 getting produced. 6. The method according to claim 5, characterized in that the reaction mixture obtained in the lactam production after separation of the catalyst is repeated for isoxime production after P 19 61 474.5 Registration begins, the isoxime solution thus produced is used again for Caprolactamherstelluag and the caprolactam is extracted at the same time through the aqueous phase used for isoxime production and isolated therefrom.