Abstract:
A process for preparing a bicyclooctanone, in particular 1,5-dialkylbicyclo[3.2.1]octan-8-one, by reacting a bicyclooctanol, in particular dialkylbicyclo[3.2.1]octan-8-ol, with 
     a. a catalyst applied to an active-carbon support and comprising heteropolyoxometallate anions of vanadium, molybdenum and phosphorus, and also a corresponding alkali-metal, alkaline-earth-metal and/or ammonium counter ion, and 
     b. a gaseous, oxygen-containing oxidizing agent.

Description:
The present invention relates to a catalytic process for the selective oxidation of a bicyclooctanol to give a bicyclooctanone using an active-carbon-supported heteropolymetallate anion catalyst. In particular, the invention relates to oxidizing 1,5-dimethylbicyclo[3.2.1]octan-8-ol to the ketone using oxygen, oxygen-containing gases or air. 
     BACKGROUND OF INVENTION 
     Various processes are known for oxidizing secondary alcohols to give ketones. However, these conventional oxidation processes are associated with numerous disadvantages, e.g. 
     the use of relatively expensive oxidizing agents in stoichiometric quantities or even in excess, 
     the separation and disposal of used and unused oxidizing agent, 
     the production of salts, creating disposal costs and making isolation of the product more difficult, 
     high pressures, 
     low selectivity, and 
     lack of complete conversion. 
     Examples of known established processes are the Oppenauer oxidation using Al systems and the H 2 O 2  oxidation using Ti, Mo and V systems, and transfer (de)hydrogenations. 
     The conventional processes are therefore frequently expensive and energy-intensive and burdened by considerable material separation problems in the isolation of the product from a complex reaction mixture. It is often difficult to dispose of oxidizing agents and auxiliary chemicals without harming the environment. 
     An object of the present invention was to provide a process for the selective oxidation of bicyclooctanols to the ketones which avoids the disadvantages of conventional oxidations, has low costs and is environmentally acceptable. 
     An oxidation process has now been found which uses an active-carbon-supported catalyst comprising a heteropolymetallate anion and which, under mild reaction conditions and even at atmospheric pressure, can use inexpensive oxidizing agents, such as oxygen-containing gases and even air, 
     and can achieve high conversions and even complete conversion with high selectivities 
     and without producing salts. 
     SUMMARY OF THE INVENTION 
     The present invention therefore provides a process for preparing a bicyclooctanone, in particular 1,5-dialkylbicyclo[3.2.1]octan-8-one, by reacting a bicyclooctanol, in particular 1,5-dialkylbicyclo[3.2.1]octan-8-ol, with 
     a. a catalyst applied to an active-carbon support and comprising heteropolyoxometallate anions of vanadium, molybdenum and phosphorus, and also a corresponding alkali-metal, alkaline-earth-metal and/or ammonium counter ion, and 
     b. a gaseous, oxygen-containing oxidizing agent. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG.  1 : Pure oxygen, clorobenzene 
     FIG.  2 : Pure oxygen, butyl acetate 
     FIG.  3 : Air, chlorobenzene 
     FIG.  4 : Air, butyl acetate 
     FIG.  5 : Air, chlorobenzene, 3-fold increase in catalyst quantity and starting material quantity 
     FIG.  6 : Scale-up in a 4 liter stirred flask (atmoshpere pressure, chlorobenzene, air) 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Alkyl are preferably, independently of one another, branched or unbranched methyl, ethyl, propyl, butyl, pentyl, hexyl or cyclohexyl radicals. 
     The oxidizing agent used comprises oxygen, oxygen-containing gases or air. 
     The novel oxidation can be carried out in the temperature range from 100 to 300° C., preferably from 120 to 250° C., and in the pressure range from 1 to 30 bar, preferably from 1 to 25 bar, in a variety of solvents or in bulk. In the case of the dimethyl compounds preferred conditions are from 140 to 250° C. and from 1 to 20 bar. The oxidizing agents used may comprise pure or diluted oxygen, in particular air or lean air. A particular embodiment of the present invention uses atmospheric pressure, and the oxygen-containing gas or air is introduced directly, either continuously or batchwise, with atmospheric pressure (or with the pressure drop produced through the reactor) via injection equipment into the liquid reaction mixture. 
     If the conduct of the reaction gives full conversion there is no problem of removing starting materials from the reaction mixture and recirculating the same, and materials separation is therefore enormously simplified. The catalyst can be synthesized from inexpensive precursors by a process which is simple, reproducible and capable of industrial-scale operation. The catalyst can be repeatedly recycled. 
     The reaction may be carried out without solvent, i.e. in bulk, or in a solvent. Suitable solvents are any organic solvent or mixture of these with water in which the catalyst is stable and which is stable to the catalyst. For example, the active component (heteropolyanion) must not become separated from the support to any significant extent, and the solvent (in particular alcohols) must not itself be oxidized under the reaction conditions selected, and the solvent must not react with the alcohol starting material (e.g. acids giving esters) or with reaction products (e.g. anhydrides with water to give acid). Examples of suitable solvents are benzene, alkylated aromatics, in particular toluene, xylenes, chlorinated and fluorinated C 1 -C 10  alkanes and aromatics, dichloroethane, chlorobenzenes, in particular monochloro-benzene, o- or m-dichlorbenzene, benzonitrile, alkanecarboxylic acids, in acetate, liquid alkanes and cycloalkanes, e.g. decane, acetonitrile, benzonitrile, DMF, dimethylacetamide, dimethyl sulfoxide (DMSO), alkylated naphthalenes, alkylated biphenyls, decalin, tetralin, diphenylmethane, silicone oils and mixtures of these with water. Particularly suitable solvents for the dimethyl compound are chlorobenzene, dichlorobenzenes, ethyl acetate or butyl acetate. 
     The catalyst used for the novel process is known from the literature (Fujibayashi, Nakayama, Hamamoto, Sakaguchi, Nishiyama, Ishii, J. Mol. Catal. A 110 (1996) 105-117). This literature is expressly incorporated herein by way of reference. The active component is a NPVMo/C catalyst or an active-carbon-supported ammonium molybdatovanadophosphate. Very generally, the catalyst is composed of a heteropolyoxometallate anion comprising the elements P, V, MO and an alkali metal, alkaline-earth metal and/or ammonium as counter ion, preferably ammonium, on an active-carbon support. 12-Metallophosphates are preferred. 
     1.) The oxidation of activated alcohols with benzylic or allylic protons at low temperatures of &lt;120° C. is now described. 
     Heteropolyanions belong to the class of polyoxometallates and exist in an almost infinite variety. The best known members of the group have Keggin structure typically featuring an atom of the 3rd, 4th or 5th main group (e.g. B, Si, P, As) surrounded tetrahedrally by M 3 O 10  units (M=Mo,W) which, in turn, are linked to one another via oxygen atoms. The general empirical formula is H 3 XM 12 O 40 . In addition to these there are also a wide variety of defect structures and larger aggregates, e.g. Dawson-type heteropolyacids. The tungsten-containing heteropolyacids in particular feature high acid strength, while the molybdenum-containing heteropolyacids also have pronounced redox properties. Molybdenum and tungsten can replace one another and also be replaced by other metals, e.g. Nb or V. This and the choice of the appropriate heteroatom permit the various properties of the heteropolyacids to be controlled as desired. In addition, other modifications to properties can be achieved by substituting metal ions for the protons. Heteropolyphosphoric acids particularly suitable for the present invention are those of molybdenum in which much of the molybdenum has been substituted by vanadium. This substitution lowers the pKa and increases the susceptibility of the heteropolyacid to reduction. At a degree of substitution of up to 3 the synthesis gives particular Keggin-type heteropolyacids. At the degree of substitution prevailing in the present invention, however, no definite compound is obtained, but rather a complicated mixture of positional, substitutional and structural isomers of the molybdatovanadophosphate. 
     A particularly suitable compound for the present invention is an ammonium molybdatovanadophosphate obtained from NaVO 3  and Na 2 MoO 4  by adding H 3 PO 4  and introducing the aqueous solution into NH 4 Cl solution, and isolating and purifying the precipitate. This active component is then applied to the active-carbon support by saturation. Active-carbon supports are known low-cost supports for noble metals and, due to their large internal surface area, are known adsorbents. The internal surface is generally occupied by functional groups which can give the active carbon either acid or basic properties. Some active carbons have a proportion of heteroatoms (O, N, H) which can be more than 10% by weight. Depending on their preparation, active carbons may be microporous or else mesoporous. 
     Active-carbon supports particularly suitable for the present invention are those which have been chemically activated and feature a high proportion of large pores, and the internal surface area of these is therefore markedly less than from 1400 to 1600 m 2 /g. They are typically obtained from water-vapor-activated microporous active carbons. Among the active carbons tested, particularly successful types are those whose BET surface area is in the range from 500 to 1500 m 2 /g, preferably from 1000 to 1400 m  2 /g. The pH of the active-carbon supports may be from 1 to 10, preferably from 2to6. The support may be blended with other (inert) components, binders and additives and be utilized in the form of pellets, beads, tablets, rings, strands, stars or other moldings, or as granules, paste or powder. The diameter or the length and thickness of the molded supports is generally from 1 to 10 mm. However, for the suspension method in the liquid phase no moldings are needed, but powders, pastes or granules may, of course, still be used. 
     Other metals and nonmetals may also be used to promote or dope the catalyst. 
     The NPVMo loading of the catalyst is generally in the range from 1 to 25% by weight, preferably in the range from 3 to 15% by weight. The required loading can be applied in one step or by multiple deposition. 
     To apply the heteropolyanion to the active-carbon support use may be made of the usual processes, such as saturating, impregnating, dipping or spray-impregnating. 
     The novel process features in particular high conversions simultaneously with good selectivity. Specifically, the selectivity of the reaction after 100 hours is ≧90% at a conversion of &gt;90%. 
     The examples below are intended to illustrate the invention. 
     EXAMPLE 1 
     Preparation of the Catalyst 
     1) Preparation of the NPVMo Active Component 14.64 g of sodium metavanadate NaVO 3 .H 2 O are charged to a 250 ml multinecked flask, dissolved in 76 ml of bidistilled water and stirred to give a milky solution. 
     16.4 g of sodium molybdate dihydrate Na 2 MoO 4 .2H 2 O are dissolved in 24 ml of bidistilled water and then added to the NaVO 3  solution, and stirring is continued for 10 min. 
     A solution of 15.2 g of H 3 PO 4  (85%) in 20 ml of bidistilled water is slowly added dropwise via a 50 ml dropping funnel. A yellow coloration immediately appears and changes to dark red toward the end of the dropwise addition. 
     Stirring is continued for 1 h at 95° C. and the mixture is allowed to stand overnight. 
     The contents of the flask are stirred into 300 ml of a saturated ammonium chloride solution, giving a brown precipitate. This precipitate is filtered off through a glass suction filter and then purified twice using 0.25 molar H 2 SO 4  (50 ml). The precipitate is dried overnight in a drying cabinet. 
     2.) Applying the NPVMO Active Component to an Active-Carbon Support 
     The active-carbon support used in the examples has a BET specific surface area of 1300 m 2 /g and a pH of 4. 12 g of the abovementioned active composition are mixed with 400 ml of distilled water and stirred for 2 h at room temperature. This solution is then filtered to give a clear red solution. 108 g of active carbon are added to this red solution and the mixture is stirred for 4 h at room temperature, then filtered via a suction filter. The black powder is dried in a drying cabinet. 
     EXAMPLE 2 
     Laboratory Autoclave Experiment (Experiment 20) 
     0.38 g=2.5 mmol of 1,5-dimethylbicyclo[3.2.1]octan-8-ol starting material in 10 ml of chlorobenzene solvent are charged with 250 mg of catalyst to a 100 ml Roth laboratory autoclave with magnetic stirrer (giving 90 ml of gas space) and once the reaction temperature of 150° C. has been achieved synthetic air is applied under pressure at 15 bar. During the course of the reaction the pressure in the autoclave falls due to consumption of the air. The duration of the reaction is 15 h. No further air is introduced, i.e. the amount of oxygen is limited. With air at 15 bar (=3 bar of O 2 ) and 150° C. the amount of oxygen charged is about 7.7 mmol, i.e. there is an approximately 3-fold molar excess of oxygen. An HP 5890 GC with Supelco 2-5358 capillary column (105 m×0.53 mm, 3 mm film, isothermal 145° C.) was used for analysis. The analysis was only qualitative, i.e. the conversion and yields given below have been calculated from the integrated peak areas without correction/quantitative calibration. 
     The results of the catalyst tests are given in Table 1. 
     EXAMPLES EXPERIMENTS 14 to 88 
     Further Laboratory Autoclave Experiments 
     The autoclave experiments are carried out in a Roth 100 ml autoclave or in a Berkhoff 200 ml autoclave with Teflon lining. Both reactors have a magnetic stirrer. 
     The experimental procedure is the same as that in Example 2 except that reaction conditions, concentrations, solvents and process details were different in each case, and these can be found in Table 1 together with the results obtained (yield, conversion and selectivity in GC area %). 
     If the reaction temperature is lowered below 150° C. the reaction rate falls dramatically. 
     Higher reaction temperatures in the range from 180 to 220° C. allow the reaction rate to rise markedly and therefore the duration of the reaction to be reduced without sacrificing selectivity. These higher-temperature experiments are listed again in Table 5. 
     The experiments with varying starting material quantities and catalyst quantity are summarized again in Tables 3 and 4. 
     Selectivity can be further improved by varying the process to maintain a local shortage of oxygen at the active center of the catalyst. The pressure here can be reduced to &lt;10 bar. 
     Continuous or else discontinuous afterfeed of oxygen at low pressures or even at atmospheric pressure has proven advantageous. 
     EXAMPLES 89 TO 83 
     Laboratory Reflux Apparatus Version at Atmospheric Pressure 
     The experiments at atmospheric pressure were carried out in a reflux apparatus composed of multinecked flask with magnetic stirrer, gas feed pipe, internal thermometer and rapid-cooling unit with continuous oxygen/air feed under atmospheric pressure. The gas feed was controlled via an MFC with a gas flow of 2.5 l/h. The solvent volume was 50 ml. 
     The results of the catalyst tests are found in FIGS. 1-5. 
     Pure Oxygen as Oxidizing Agent 
     FIGS. 1 and 2 show the progress of the oxidation in chlorobenzene or butyl acetate as solvent. It can be seen that in chlorobenzene complete conversion is achieved in 70 h, while selectivity is about 90%. The only significant GC byproduct (RT=31.3 in chlorobenzene) does not appear until 30 h have passed and then increases continuously to about 2%. The concentration of this byproduct as a function of time suggests two versions of the process for industrial use, specifically high selectivity with partial conversion or full conversion, avoiding removal of starting material from the reaction mixture. 
     In butyl acetate only 50 h are required for full conversion to be reached. The byproduct is already present at the start of the reaction and increases approximately linearly to about 6% as the reaction progresses. Since further byproduct continues to be formed at 100% conversion it may be concluded that this is produced by a follow-on reaction from product already formed (presumably further oxidation of the ketone with ring-opening of the bicyclic system). There is also a conclusion for the industrial conduct of the reaction: that the reaction must be terminated at the correct juncture (shortly after reaching full conversion) to avoid unnecessary selectivity losses. 
     Air Oxidation 
     FIG. 3 shows the progress of air oxidation at atmospheric pressure (gas flow 2.5 l/h of air) in chlorobenzene. 
     After 70 h conversion is 100% and selectivity is greater than &gt;95%. FIG. 4 shows the progress of air oxidation at atmospheric pressure (gas flow 2.5 l/h of air) in butyl acetate. After 80 h conversion is 100% and selectivity is greater than &gt;90%. 
     Selectivity can therefore be increased by using air instead of pure O 2 . 
     FIG. 5 shows the progress of air oxidation at atmospheric pressure (gas flow 2.5 l/h of air) in chlorobenzene with a 3-fold increase in catalyst quantity and starting material quantity. Full conversion is achieved after 55 h at a selectivity of &gt;95%. The starting material quantity and alcohol quantity may therefor then be increased without difficulty by a factor of two or three. Higher concentrations are desirable since they simplify the subsequent treatment of the materials (Experiment 90). 
     EXAMPLE 84 
     Pilot Plant Experiments in a 1 l Autoclave (Scale-Up Experiments) 
     Two experiments (each with different starting material/catalyst concentrations) were carried out in a 1 liter autoclave in a high-pressure pilot plant. In each case the initial charge was 400 g of chlorobenzene and use was made of 
     for Experiment 77: 14 g of cat+15.2 g of alcohol 
     for Experiment 78: 28 g of cat+30.4 g of alcohol (doubled cat/alcohol quantity) 
     at 150° C. and with lean air (10% O 2 ) at 2.5 bar with a gas flow of 50 l/h and with mechanical stirring at 600 rpm. The product was not isolated, but the reaction mixture was simply analyzed by GC. 
     The results obtained are even better than in the laboratory autoclave experiments. Experiment 77 (using standard concentrations of cat/alcohol) gives full conversion with 91% selectivity (based on GC area %) after only 24 h, whereas the laboratory apparatus operated at atmospheric pressure had required 70 h, i.e. the duration of the reaction can be further dramatically reduced by optimizing mixing (gas flow, stirrer rotation rate). 
     A simultaneous two-fold increase in catalyst concentration and alcohol concentration gives a further reduction in the duration of the reaction to 15 h, without loss of selectivity. 
     Tables 2 and 3 again show results from Experiments 77 and 78. 
     EXAMPLE 85 
     Scale-Up Experiment in a 4 Liter Stirred Flask 
     FIG. 6 shows the progress of the air oxidation in a mechanically stirred reflux apparatus with a 4 liter flask, operated at atmospheric pressure (Experiment 100, 1 kg of chlorobenzene, 70 g of catalyst, 76 g of alcohol, 150° C., gas flow 7.5 l/h of synthetic air). 100% conversion and &gt;95% selectivity are achieved after 50 h. 
     Table 1: Laboratory Autoclave Experiments 
     Results of Catalytic Oxidation of 1,5-dimethylbicyclo[3.2.1]octan-8-ol to the Ketone. 
     Yields and Selectivities in GC Area % 
     BRIEF DESCRIPTION OF DRAWINGS 
     FIGS.  1 - 5 : Laboratory Reflux Apparatus Version at Atmospheric Pressure 
     Results From Catalytic Oxidation of 1,5-dimethylbicyclo[3.2.1]octan-8-ol to the Ketone 
     Yields and Selectivities in GC Area % 
     FIG.  1 : Pure oxygen, chlorobenzene 
     FIG.  2 : Pure oxygen, butyl acetate 
     FIG.  3 : Air, chlorobenzene 
     FIG.  4 : Air, butyl acetate 
     FIG.  5 : Air, chlorobenzene, 3-fold increase in catalyst quantity and starting material quantity 
     FIG.  6 : Scale-up in a 4 liter stirred flask (atmospheric pressure, chlorobenzene, air) (Experiment 100) 
     Results of the Catalytic Oxidation of 1,5-dimethylbicyclo[3.2.1]octan-8-ol to the Ketone 
     Tables 2 and 3: Pilot Plant Experiments With Lean Air in a 1 l Autoclave 
     Results From Catalytic Oxidation of 1,5-dimethylbicyclo[3.2.1]octan-8-ol to the Ketone 
     Table 2: Experiment 77 
     Table 3: Experiment 88 
     
       
         
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 Exp. 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 No. 
                 Reactor 
                 Solvent 
                 Temperature 
                 Pressure 
                 Time 
                 GC area % 
                 Conversion 
                 Selectivity 
                 Remarks 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 Roth 
                 Chlorobenzene 
                 220° C. 
                 30 
                 4 
                 83.6 
                 100 
                 83.6 
                 250 mg cat./385 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 2 
                 Roth 
                 Chlorobenzene 
                 220° C. 
                 15 
                 15 
                 90 
                 100 
                 90 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 3 
                 Roth 
                 Chlorobenzene 
                 150° C. 
                 15 
                 15 
                 95 
                 100 
                 95 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 4 
                 Roth 
                 Acetic acid 
                 150° C. 
                 15 
                 15 
                 51 
                 100 
                 51 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 5 
                 Roth 
                 Toluene 
                 150° C. 
                 15 
                 15 
                 41 
                 84 
                 48.8 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 6 
                 Roth 
                 Methanol 
                 150° C. 
                 15 
                 15 
                 18 
                 19 
                 94.7 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 7 
                 Roth 
                 Ethanol 
                 150° C. 
                 15 
                 15 
                 5 
                 5 
                 100 
                 250 mg/cat./360 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 8 
                 Roth 
                 Ethyl acetate 
                 150° C. 
                 15 
                 15 
                 57 
                 60 
                 95 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 9 
                 Roth 
                 n-Decane 
                 150° C. 
                 15 
                 15 
                 10 
                 45 
                 22.2 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 10 
                 Roth 
                 DMF 
                 150° C. 
                 15 
                 15 
                 11 
                 80 
                 13.8 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 11 
                 Roth 
                 Benzonitrile 
                 150° C. 
                 15 
                 15 
                 15 
                 100 
                 15 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 12 
                 Roth 
                 Dichloroethane 
                 150° C. 
                 15 
                 15 
                 8 
                 18 
                 44.4 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml solv. 
               
               
                 13 
                 Roth 
                 Acetic acid 
                 150° C. 
                 15 
                 15 
                 28 
                 85 
                 32.9 
                 250 mg cat./380 mg alco./ 
               
               
                   
                   
                 10% water 
                   
                   
                   
                   
                   
                   
                 10 ml solv. &amp; 1 ml water. 
               
               
                 14 
                   
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 0% 
                 0% 
                 0% 
                 Exp. with only catalyst, 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 no alcohol 
               
               
                 15 
                   
                 Chlorobenzene 
                 100° C. 
                 15 bar 
                 15 h 
                 4.86% 
                 13.35% 
                 36.40% 
                 Berghof autoclave, 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. = colorless 
               
               
                 16 
                   
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 71.64% 
                 81.80% 
                 87.60% 
                 Berfhof autoclave, 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. = yellowish 
               
               
                 17 
                   
                 Chlorobenzene 
                 125° C. 
                 0 bar 
                 5 h 
                 from 3.21% 
                 from 8.32% 
                 from 38.58% 
                 Glass app at atm. pres., in 1 
               
               
                   
                   
                   
                 150° C. 
                   
                 39 h 
                 to 66.67% 
                 to 69.94% 
                 to 95.32% 
                 terminated due to flask failure 
               
               
                 18 
                   
                 Chlorobenzene 
                 160° C. 
                 15 bar 
                 10 h 
                 75.00% 
                 87.59% 
                 85.60% 
                 Berghof autoclave, 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. = yellowish 
               
               
                 19 
                   
                 Chlorobenzene 
                 160° C. 
                 10 bar 
                 15 h 
                 76.39% 
                 84.48% 
                 90.40% 
                 Small autoclave, 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. = yellowish 
               
               
                 20 
                   
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 79.06% 
                 90.00% 
                 87.80% 
                 Small autoclave as described 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 in Example 2 with only 10 ml 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of solv. 
               
               
                 21 
                   
                 Chlorobenzene 
                 160° C. 
                 15 bar 
                 10 h 
                 70.62% 
                 93.58% 
                 75.50% 
                 Berghof autoclave/doubled 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 quantity of cat. &amp; octanol 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 with 20 ml of solv. 
               
               
                 22 
                   
                 Chlorobenzene 
                 160° C. 
                 5/10/15 
                 3/6/9 h 
                 69.01% 
                 76.05% 
                 90.74% 
                 Berghof autoclave, 
               
               
                   
                   
                   
                   
                 bar 
                 h 
                   
                   
                   
                 as Exp. 17 
               
               
                 23 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 85.83% 
                 97.52% 
                 88.00% 
                 Small autoclave/but with 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 more cat. 375 mg of cat./380 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 mg of alcohol/10 ml of solv. 
               
               
                 24 
                   
                 Chlorobenzene 
                 160° C. 
                 10 bar 
                 5 h/ 
                 61.22%/ 
                 69.09%/ 
                 88.61% 
                 Berghof/doubled amount of 
               
               
                   
                   
                   
                   
                   
                 10 h 
                 71.30% 
                 96.99% 
                 73.51% 
                 cat. &amp; alco. sample after 5 h/ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat./then further 5 h 
               
               
                 25 
                   
                 Chlorobenzene 
                 140° C. 
                 15 bar 
                 15 h 
                 76.09% 
                 85.82% 
                 88.66% 
                 Small autoclave/as Exp. 20 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 temp. 10° C. lower 
               
               
                 26 
                   
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 83.84% 
                 92.04% 
                 91.09% 
                 Small autoclave/but with 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 more cat. 375 mg of cat./380 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 mg of alco./10 ml of solv. 
               
               
                 27 
                   
                 Chlorobenzene 
                 160° C. 
                 7 bar 
                 15 h 
                 73.23% 
                 92.73% 
                 78.97% 
                 Berghof/doubled amount of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat. &amp; alco. As Exp. 23 but 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 15 h 
               
               
                 28 
                   
                 Chlorobenzene 
                 150° C. 
                 6 bar 
                 15 h 
                 80.00% 
                 86.28% 
                 92.72% 
                 Small autoclave/but with 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 more cat. 375 mg of cat./380 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 mg of alco./10 ml of solv. 
               
               
                 29 
                   
                 Chlorobenzene 
                 140/150/160 
                 8 bar 
                 5 h/10 h 
                 70.07% 
                 81.47% 
                 86.00% 
                 Berghof/doubled amount of 
               
               
                   
                   
                   
                   
                 3 bar 
                 15 h 
                   
                   
                   
                 cat. &amp; alco. Temperature 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 gradient 
               
               
                 30 
                   
                 Chlorobenzene 
                 160° C. 
                 5 bar 
                 15 h 
                 68.79% 
                 82.67% 
                 83.21% 
                 Berghof/as Exp. 27 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 but lower pressure 
               
               
                 31 
                   
                 Chlorobenzene 
                 150° C. 
                 6 bar 
                 20 h 
                 84.56% 
                 92.22% 
                 91.69% 
                 Small autoclave/as Exp. 28 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 but 5 h longer 
               
               
                 32 
                   
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 80.60% 
                 88.10% 
                 91.49% 
                 Small autoclave/but with 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 more cat. As Exp.26 but with 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 new cat. charge 
               
               
                 33 
                   
                 Chlorobenzene 
                 150° C. 
                 atm. 
                 78 h 
                 92.70% 
                 98.59% 
                 94.03% 
                 As 16 but with doubled 
               
               
                   
                   
                   
                   
                 pres. 
                   
                   
                   
                   
                 amount of cat., &amp; alco., with 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 50 ml of chlorobenzene 
               
               
                 34 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar/ 
                 5 h/10 h 
                 82.80% 
                 89.89% 
                 92.11% 
                 Small autoclave/but with more 
               
               
                   
                   
                   
                   
                 7 bar 
                 15 h 
                   
                   
                   
                 cat. pressure gradient 
               
               
                   
                   
                   
                   
                 4 bar 
               
               
                 35 
                   
                 Chlorobenzene 
                 150° C. 
                 5 bar 
                 15 h 
                 20.80% 
                 26.89% 
                 77.35% 
                 Büchi autoclave/Lab. 209/ 
               
               
                   
                   
                   
                   
                 post 
                   
                   
                   
                   
                 1250 mg cat./1900 mg alco./ 
               
               
                   
                   
                   
                   
                 regul. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 50 ml of chlorobenzene 
               
               
                 36 
                   
                 Toluene 
                 150° C. 
                 10 bar 
                 15 h 
                 52.90% 
                 64.31% 
                 82.26% 
                 Berghof/20 ml of toluene/250 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 mg of cat. 380 mg of alcohol/ 
               
               
                 37 
                   
                 Toluene 
                 150° C. 
                 5 bar 
                 15 h 
                 48.43% 
                 57.51% 
                 84.21% 
                 Berghof/Autoclave// 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat. &amp; 380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco. &amp; 20 ml of t 
               
               
                 38 
                   
                 Toluene 
                 150° C. 
                 10 bar 
                 15 h 
                 59.64% 
                 69.34% 
                 86.01% 
                 Roth autoclave//250 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat. &amp; 380 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml of t 
               
               
                 39 
                   
                 Ethyl acetate 
                 150° C. 
                 10 bar 
                 15 h 
                 84.10% 
                 92.55% 
                 90.87% 
                 Berghof/Autoclave// 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat. &amp; 380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco. &amp; 20 ml of ea 
               
               
                 40 
                   
                 Ethyl acetate 
                 150° C. 
                 8 bar 
                 15 h 
                 57.14% 
                 62.19% 
                 91.88% 
                 Roth autoclave//as Exp. 26 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 375 mg of cat. &amp; 380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco. &amp; 10 ml ea 
               
               
                 41 
                   
                 Ethyl acetate 
                 150° C. 
                 5 bar 
                 15 h 
                 56.33% 
                 62.90% 
                 89.55% 
                 Berghof/Autoclave// 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat. &amp; 380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco. &amp; 20 ml of ea 
               
               
                 42 
                   
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 81.82% 
                 88.45% 
                 92.50% 
                 Roth autoclave as Exp. 22 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat. test batch 2 &amp; 3 
               
               
                 43 
                   
                 Ethyl acetate 
                 150° C. 
                 15 bar 
                 15 h 
                 69.05% 
                 76.98% 
                 89.70% 
                 Roth autoclave // as Exp. 40 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 375 mg of cat. &amp; 380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco. &amp; 10 ml of ea 
               
               
                 44 
                   
                 Chlorobenzene 
                 160° C. 
                 8 bar 
                 15 h 
                 75.08% 
                 94.02% 
                 79.86% 
                 Berghof/Autoclave//as 30 bar 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 increased 500 mg of cat. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 760 mg of alco. &amp; 20 ml of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 chlorobenzene 
               
               
                 45 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 12.78% 
                 19.21% 
                 66.53% 
                 Büchi autoclave/repeat of 35 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 1.25 g of cat./1.9 g of alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 50 ml of chlorobenzene 
               
               
                 46 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 66.02% 
                 77.64% 
                 85.03% 
                 Berghof/Autoclave//conc. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 increase 500 mg of cat. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 760 mg of alco. &amp; 20 ml of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 ch 
               
               
                 47 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 48.81% 
                 55.76% 
                 87.54% 
                 Roth autoclave//conc. increase 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 500 mg of cat. &amp; 760 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco. &amp; 10 ml of ch 
               
               
                 48 
                   
                 Butyl Acetate 
                 150° C. 
                 atm. 
                 71.5 h 
                 91.94% 
                 100% 
                 91.94% 
                 Glass app. 
               
               
                   
                   
                   
                   
                 pres. 
                   
                   
                   
                   
                 1250 mg of cat./1900 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./50 ml of ba 
               
               
                 49 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 51.51 
                 59.08 
                 87.19 
                 Roth autoc. Exp. with used 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat. from Exp. 33/250 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat./380 mg of alco. 
               
               
                 50 
                   
                 Butyl acetate 
                 150° C. 
                 10 bar 
                 15 h 
                 79.29 
                 91.7 
                 86.47 
                 Berghof/Autoclave//butyl 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 acetate solv. 250 mg of cat./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 380 mg of alco./20 ml of solv. 
               
               
                 51 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 75.93 
                 84.55 
                 89.8 
                 Roth autoc. Exp. with used 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat. 375 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./10 ml of ch 
               
               
                 52 
                   
                 Butyl acetate 
                 160° C. 
                 8 bar 
                 15 h 
                 71.33 
                 79.9 
                 89.27 
                 Berghof/Autoclave//as 44/low 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 bar 500 mg of cat. &amp; 760 mg. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of alco. &amp; 20 ml of ba 
               
               
                 53 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 68.73 
                 77.83 
                 88.31 
                 Berghof/Autoclave//250 mg 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of cat./380 mg of alco./20 ml 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of solv. 
               
               
                 54 
                   
                 Acetic acid 100% 
                 150° C. 
                 10 bar 
                 15 h 
                 39.15 
                 98.98 
                 39.55 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./10 ml of solv. 
               
               
                 55 
                   
                 Acetic acid 100% 
                 150° C. 
                 15 bar 
                 15 h 
                 43.1 
                 99.33 
                 43.39 
                 Roth Autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./10 ml of solv. 
               
               
                 56 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 45.36 
                 48.83 
                 92.89 
                 Büchi Autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of solv. 
               
               
                 57 
                   
                 Acetic anhydride 
                 150° C. 
                 10 bar 
                 15 h 
                 16.43 
                 100 
                 16.43 
                 Berghof Autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 375 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of solv. 
               
               
                 58 
                   
                 Acetic anhydride 
                 150° C. 
                 15 bar 
                 15 h 
                 11.33 
                 100 
                 11.33 
                 Berghof Autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 375 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of solv. 
               
               
                 59 
                   
                 Acetic anhydride 
                 150° C. 
                 10 bar 
                 15 h 
                 10.03 
                 100 
                 10.03 
                 Roth Autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./10 ml of solv. 
               
               
                 60 
                   
                 Acetic anhydride 
                 150° C. 
                 8 bar 
                 15 h 
                 15.79 
                 100 
                 15.79 
                 Berghof Autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 375 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of solv. 
               
               
                 61 
                   
                 Chlorobenzene 
                 150° C. 
                 0 bar 
                 79 
                 94.4 
                 100 
                 94.4 
                 Glass app., synth. air 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 1250 mg of cat./1900 mg 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of alco./50 ml of solv. 
               
               
                 62 
                   
                 Acetic anhydride 
                 150° C. 
                 15 bar 
                 15 h 
                 9.82 
                 100 
                 9.82 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./10 ml of solv. 
               
               
                 63 
                   
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 35.16 
                 100 
                 35.16 
                 Roth autoc. as Exp. 26 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 1st cat. test Batch IV. 
               
               
                 64 
                   
                 Ethylene glycol 
                 150° C. 
                 10 bar 
                 15 h 
                   
                   
                   
                 Berghof autoclave 
               
               
                   
                   
                 experiments 
                   
                   
                   
                   
                   
                   
                 150 mg of et. glycol/250 mg 
               
               
                   
                   
                 Chlorobenzene 
                   
                   
                   
                   
                   
                   
                 of cat./10 ml of solv. 
               
               
                 65 
                   
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 84.03 
                 98.33 
                 85.46 
                 Roth autoc. as Exp. 26 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 150 mg of et. clycol/250 mg 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of cat./10 ml of solv. 
               
               
                 66 
                   
                 Ethylene glycol 
                 150° C. 
                 10 bar 
                 15 h 
                   
                   
                   
                 Repeat of Exp. 26 
               
               
                   
                   
                 experiments 
               
               
                   
                   
                 Chlorobenzene 
               
               
                 67 
                   
                 Ethylene glycol 
                 150° C. 
                 10 bar 
                 15 h 
                   
                   
                   
                 Roth autoclave 
               
               
                   
                   
                 experiments 
                   
                   
                   
                   
                   
                   
                 150 mg of et. glycol/250 
               
               
                   
                   
                 Chlorobenzene 
                   
                   
                   
                   
                   
                   
                 mg of cat./20 ml of solv. 
               
               
                 68 
                   
                 Ethylene glycol 
                 160° C. 
                 10 bar 
                 15 h 
                   
                   
                   
                 Berghof autoclave 
               
               
                   
                   
                 experiments 
                   
                   
                   
                   
                   
                   
                 150 mg of et. glycol/250 mg 
               
               
                   
                   
                 Chlorobenzene 
                   
                   
                   
                   
                   
                   
                 of cat./20 ml of solv. 
               
               
                 69 
                   
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 88.27 
                 97.89 
                 90.17 
                 Roth autoc. as Exp. 26 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 3rd cat. test Batch IV. 
               
               
                 70 
                   
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 72.75 
                 89.11 
                 81.64 
                 Berghof autclave/Conc. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 increase 500 mg of cat./760 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 mg of alco./20 ml of solv. 
               
               
                 71 
                   
                 Butyl acetate 
                 150° C. 
                 0 bar 
                 85 h 
                 89.96 
                 100 
                 89.96 
                 Glass app., synth. air 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 1250 mg of cat./1900 mg 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of alco./50 ml of ba 
               
               
                 72 
                   
                 Chlorobenzene 
                 150° C. 
                 3 × 8 
                 3 × 5 h 
                 76.14 
                 90.28 
                 84.54 
                 Berghof autoclave/conc. 
               
               
                   
                   
                   
                   
                 bar 
                   
                   
                   
                   
                 increase 300 mg of cat./760 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 mg of alco./10 ml of solv. 
               
               
                 73 
                   
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 47.65 
                 54.2 
                 87.91 
                 Roth autoclave/conc. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 increase 300 mg of cat./760 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 mg of alco./10 ml of solv. 
               
               
                 74 
                   
                 o-Xylene 
                 150° C. 
                 10 bar 
                 15 h 
                 69.92 
                 74.66 
                 93.65 
                 Roth autoclave//375 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat./380 mg of alco./10 ml of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. 
               
               
                 75 
                   
                 o-Xylene 
                 150° C. 
                 8 bar 
                 15 h 
                 44.70 
                 73.62 
                 60.71 
                 Roth autoclave//375 mg 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of cat./380 mg of alco./10 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 ml of solv. 
               
               
                 76 
                   
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 1 × 10 h 
                 54.45 
                 60.65 
                 89.78 
                 Berghof autoclave//as Exp. 72 
               
               
                   
                   
                   
                   
                   
                 1 × 5 h 
                 74.96 
                 87.33 
                 85.84 
                 500 mg of cat./760 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of solv. 
               
               
                 77 
                   
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 24 h 
                 90.97 
                 100 
                 90.97 
                 1 Ltr. autoclave in pilot plant 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 400 g of solv/14 g of cat./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 15.2 g of alco. 
               
               
                 78 
                   
                 Chlorobenzene 
                 150° C. 
                 8 
                 15 h 
                 48.35 
                 54.54 
                 88.65 
                 Roth autoclave//500 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat./760 mg of alco./10 ml 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of solv. 
               
               
                 79 
                   
                 Chlorobenzene 
                 150° C. 
                 15 
                 15 h 
                 68.40 
                 86.65 
                 78.94 
                 Berghof autoclave//3× conc. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 750 mg of cat./1.14 g of alco./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 80 
                   
                 No solvent 
                 150° C. 
                 10 
                 15 h 
                 8.61 
                 17.88 
                 48.15 
                 Roth autoclave//375 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cat./5 g of alco. 
               
               
                 81 
                   
                 Chlorobenzene 
                 150° C. 
                 0 
                 69 h 
                 94.5 
                 100 
                 94.5 
                 Glass app//2.5 g of cat./ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 3.8 g of alco./50 ml of solv. 
               
               
                 82 
                   
                 Chlorobenzene 
                 220° C. 
                 25 
                 2 h 
                 92.15 
                 100 
                 92.15 
                 Roth autoclave//250 mg 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of cat./385 mg of alco./10 ml 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 of solv. 
               
               
                 83 
                   
                 Chlorobenzene 
                 150° C. 
                 15 
                 15 h 
                 73.17 
                 83.18 
                 87.97 
                 Roth autoclave//as Exp. 78 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 doubled conc. 
               
               
                 84 
                   
                 Chlorobenzene 
                 150° C. 
                 15 
                 15 h 
                 64.89 
                 94.91 
                 68.37 
                 Berghof autoclave//as Exp. 79 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 but more cat. 1 g of cat./1.14 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 g of alco./20 ml of solv. 
               
               
                 85 
                   
                 No solvent 
                 150° C. 
                 15 
                 15 h 
                 11.58 
                 20.02 
                 57.84 
                 Roth autoclave//as Exp. 80 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 at higher pressure//5 g of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./385 mg of cat. 
               
               
                 86 
                   
                 Decalin 
                 150° C. 
                 15 
                 15 h 
                 57.18 
                 81.15 
                 70.46 
                 Berghof autoclave//new solv. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of decalin 
               
               
                 87 
                   
                 Chlorobenzene 
                 220° C. 
                 20 
                 2 h 
                 87.44 
                 94.74 
                 92.29 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 as Exp. 82 
               
               
                 88 
                   
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 15 h 
                 91.77 
                 100 
                 91.77 
                 1 Ltr. autoclave in pilot plant 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 as Exp. 77 but doubled conc. 
               
               
                 89 
                   
                 Diphenylmethane 
                 150° C. 
                 15 
                 15 h 
                 17.64 
                 97.3 
                 18.13 
                 Berghof autoclave/new solv. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 g of solv. 
               
               
                 90 
                   
                 Chlorobenzene 
                 150° C. 
                 0 
                 55 h 
                 96.93 
                 100 
                 96.93 
                 Glass app.//3.75 g of cat./5.7 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 g of alco./50 ml of solv. 
               
               
                 91 
                   
                 Chlorobenzene 
                 220° C. 
                 15 
                 2 h 
                 70.76 
                 70.76 
                 100 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                 4 h 
                 79.59 
                 83.46 
                 95.36 
                 250 mg/380 mg/10 ml of solv. 
               
               
                 92 
                   
                 Chlorobenzene 
                 150° C. 
                 8 
                 15 
                 57.7 
                 96.82 
                 58.94 
                 Berghof autoclave/ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 500 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of solv. 
               
               
                 93 
                   
                 Chlorobenzene 
                 150° C. 
                 15 
                 15 
                 62.26 
                 97.89 
                 63.6 
                 Berghof autoclave/ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 750 mg of cat./760 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./20 ml of solv. 
               
               
                 94 
                   
                 Chlorobenzene 
                 200° C. 
                 25 
                 2 h 
                 86.02 
                 92.32 
                 93.17 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/10 ml of solv. 
               
               
                 95 
                   
                 Chlorobenzene 
                 150° C. 
                 10 
                 15 
                 10.24 
                 12.95 
                 79.09 
                 Berghof autoclave/new 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 support 750 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 HAAL0001/ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 380 mg of alco./20 ml of a 
               
               
                 96 
                   
                 Chlorobenzene 
                 200° C. 
                 20 
                 2 h 
                 89.44 
                 96 
                 93.17 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/ 10 ml of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. 
               
               
                 97 
                   
                 Chlorobenzene 
                 180° C. 
                 25 
                 2 h 
                 81.67 
                 87.4 
                 93.44 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/10 ml of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. 
               
               
                 98 
                   
                 Chlorobenzene 
                 150° C. 
                 10 
                 15 
                 14.61 
                 14.61 
                 100 
                 Berghof autoclave/new 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 support 1500 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 HAAL0001/ 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 380 mg of alco./20 ml of s 
               
               
                 99 
                   
                 1,2-Dichlorobenzene 
                 150° C. 
                 8 
                 15 
                 84.07 
                 90.17 
                 93.24 
                 Roth autoclave//new solv. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 375 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./10 ml of a 
               
               
                 100 
                   
                 Chlorobenzene 
                 150° C. 
                 0 
                   
                   
                   
                   
                 4 Ltr. glass app.//1000 g of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv.: 70 g of cat.//76 g of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alcohol 
               
               
                 101 
                   
                 1,3-Dichlorobenzene 
                 150° C. 
                 10 
                 15 
                 78.46 
                 83.56 
                 93.9 
                 Berghof autoclave/new solv. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/20 ml of solv. 
               
               
                 102 
                   
                 1,3-Dichlorobenzene 
                 150° C. 
                 15 
                 15 
                 76.24 
                 85.2 
                 89.48 
                 Berghof autoclave/101 higher 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 pr. 250 mg/380 mg/20 ml of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solv. 
               
               
                 103 
                   
                 1,2-Dichlorobenzene 
                 180° C. 
                 8 
                 4 
                 31.11 
                 35.72 
                 87.09 
                 Roth autoclave//higher temp. 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 375 mg of cat./380 mg of 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 alco./10 ml of s 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 This experiment was carried out in a 1 ltr. autoclave 
               
               
                 400 g of solvent/14 g of catalyst/15.2 g of the alcohol 
               
             
          
           
               
                 Solvent 
                 Temperature 
                 Pressure 
                 Time 
                 GC area % 
                 Conversion 
                 Selectivity 
                 Byproduct 
               
               
                   
               
               
                 Chlorobenzene 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Chlorobenzene 
                   
                   
                 0 h 
               
               
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 3.5 h 
                 34.64 
                 40.12 
                 86.34 
                 0.36 
               
               
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 11 h 
                 70.79 
                 77.98 
                 90.78 
                 2.90 
               
               
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 18 h 
                 87.25 
                 94.2 
                 92.62 
                 4.02 
               
               
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 24 h 
                 90.97 
                 100 
                 90.97 
                 6.50 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 This experiment was carried out in a 1 ltr. autoclave 
               
               
                 400 g of solvent/28 g of catalyst/30.4 g of the alcohol 
               
               
                 (Doubled quantity of starting materials) 
               
             
          
           
               
                 Solvent 
                 Temperature 
                 Pressure 
                 Time 
                 GC area % 
                 Conversion 
                 Selectivity 
                 Byproduct 
               
               
                   
               
               
                 Chlorobenzene 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Chlorobenzene 
                   
                   
                 0 h 
               
               
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 7.5 h 
                 67.48 
                 72.12 
                 93.57 
                 3.085 
               
               
                 Chlorobenzene 
                 150° C. 
                 2.5 bar 
                 15 h 
                 91.77 
                 100 
                 91.77 
                 6.53  
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Concentration Experiments 
               
             
          
           
               
                   
                 Reactor 
                 Solv. 
               
             
          
           
               
                   
                 Berghof = 200 ml 
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Roth = 100 ml 
                 Temp. 
                 Pressure 
                 Time 
                 Prod. % 
                 Conversion 
                 Selectivity 
                 Remarks 
               
               
                   
                   
               
             
          
           
               
                 46 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 66.02 
                 77.64 
                 85.03 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 47 
                 Roth 
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 48.81 
                 55.76 
                 87.54 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml of solv. 
               
               
                 52 
                 Berghof 
                 butyl acetate 
                 160° C. 
                 8 bar 
                 15 h 
                 71.33 
                 79.9 
                 89.27 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 70 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 72.75 
                 89.11 
                 81.64 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 72 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 3 × 8 bar 
                 3 × 5 h 
                 76.14 
                 90.28 
                 84.54 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 73 
                 Roth 
                 Chlorobenzene 
                 150° C. 
                 10 bar 
                 15 h 
                 47.65 
                 54.2 
                 87.91 
                 300 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml of solv. 
               
               
                 76 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 1 × 10 h 
                 54.45 
                 60.65 
                 89.76 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                 1 × 5 h 
                 74.96 
                 87.33 
                 85.84 
                 20 ml of solv. 
               
               
                 78 
                 Roth 
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 48.35 
                 54.54 
                 88.65 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml of solv. 
               
               
                 79 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 68.4 
                 86.65 
                 78.94 
                 750 mg of cat./1140 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 83 
                 Roth 
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 73.17 
                 83.18 
                 87.97 
                 500 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 10 ml of solv. 
               
               
                 84 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 64.89 
                 94.91 
                 68.37 
                 1000 mg of cat./1140 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 92 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 8 bar 
                 15 h 
                 57.70 
                 96.82 
                 58.94 
                 500 mg of cat./380 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 20 ml of solv. 
               
               
                 93 
                 Berghof 
                 Chlorobenzene 
                 150° C. 
                 15 bar 
                 15 h 
                 62.26 
                 97.89 
                 63.6 
                 750 mg of cat./760 mg of alco. &amp; 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 ml of solv. 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Experiments at High Temperature 
               
             
          
           
               
                 No. 
                 Solvent 
                 Temp. 
                 Pressure 
                 Time 
                 % Product 
                 % Conversion 
                 % Select. 
                 Comment 
               
               
                   
               
               
                 82 
                 Chlorobenzene 
                 220° C. 
                 25 
                 2 h 
                 92.15 
                 100 
                 92.15 
                 Roth autoclave//250 mg of cat./385 mg 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 of alco./10 ml of solv. 
               
               
                 87 
                 Chlorobenzene 
                 220° C. 
                 20 
                 2 h 
                 87.44 
                 94.74 
                 92.29 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 as Exp. 6.72 
               
               
                 91 
                 Chlorobenzene 
                 220° C. 
                 15 
                 2 h 
                 70.76 
                 100 
                 100 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/10 ml of solv. 
               
               
                 94 
                 Chlorobenzene 
                 220° C. 
                 25 
                 2 h 
                 86.02 
                 92.32 
                 93.17 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/10 ml of solv. 
               
               
                 96 
                 Chlorobenzene 
                 220° C. 
                 20 
                 2 h 
                 89.44 
                 96 
                 93.17 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/10 ml of solv. 
               
               
                 99 
                 Chlorobenzene 
                 180° C. 
                 25 
                 2 h 
                 81.67 
                 87.4 
                 93.44 
                 Roth autoclave 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 250 mg/380 mg/10 ml of solv.