Sustainable process for the manufacture of 1,1,4,4-tetramethoxy-2-butene
12516009 ยท 2026-01-06
Assignee
Inventors
Cpc classification
C07C41/58
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention is directed to a process for the manufacture of 1,1,4,4-tetramethoxy-2-butene from 2,5-dimethoxy-2,5-dihydrofuran with methanol in the presence of an acidic ion exchanger as catalyst, whereby the molar ratio of 2,5-dimethoxy-2,5-dihydrofuran to methanol is 1:45. The present invention is further directed to a process of separating 1,1,4,4-tetramethoxy-2-butene, methanol and 2,5-dimethoxy-2,5-dihydrofuran from each other and H2O whereby a basic compound, preferably a basic metal salt or a basic ion exchanger, is present. Both processes can be carried out on an industrial scale, batch-wise or in continuous mode and are sustainable since the selectivity and the space-time-yields are high and less waste compared to known processes is produced. Further objects of the present invention are the use of a basic compound in the distillation of a mixture comprising H2O, 1,1,4,4-tetramethoxy-2-butene and 2,5-dimethoxy-2,5-dihydrofuran, as well as the use of an acidic ion exchanger as catalyst in a reaction of 2,5-dimethoxy-2,5-dihydrofuran with methanol to 1,1,4,4-tetramethoxy-2-butene, whereby the molar ratio of 2,5-dimethoxy-2,5-dihydrofuran to methanol is 1:45.
Claims
1. A process for manufacturing 1,1,4,4-tetramethoxy-2-butene comprising the following steps: a) providing 2,5-dimethoxy-2,5-dihydrofuran (DMDF optionally comprising 1,1,4,4-tetramethoxy-2-butene; b) reacting the DMDF optionally comprising 1,1,4,4-tetramethoxy-2-butene provided in step a) with methanol in a molar ratio of the DMDF to methanol being 1:45, in the presence of an acidic ion exchanger as catalyst and optionally in the presence of water, with a mixture comprising water and 1,1,4,4-tetramethoxy-2-butene until at most 79% of DMDF has been reacted to 1,1,4,4-tetramethoxy-2-butene to obtain a reaction mixture comprising water, methanol, 1,1,4,4-tetramethoxy-2-butene and DMDF; c) bringing the reaction mixture comprising water, methanol, 1,1,4,4-tetramethoxy-2-butene and DMDF into contact with a basic compound; c) distilling the reaction mixture comprising water, methanol, 1,1,4,4-tetramethoxy-2-butene and DMDF in the presence of the basic compound to thereby separate these compounds from each other and obtain 1,1,4,4-tetramethoxy-2-butene, methanol and un-reacted DMDF, wherein step c) is practiced by adding the basic compound to the reaction mixture obtained in step b) or before or during the distillation of step d), and wherein the process is conducted in the absence of any acetalization agent except for the presence of the methanol.
2. The process according to claim 1, which further comprises recycling the un-reacted DMDF obtained in step d) back into either step a) or step b), respectively.
3. The process according to claim 1, wherein the catalyst used in step b) is an acidic ion exchanger having a concentration of acid sites of at least 2.5 eq/kg, and/or wherein the catalyst used in step b) is an acidic ion exchanger containing sulfonic acid groups and having a concentration of acid sites of at least 2.5 eq/kg.
4. The process according to claim 3, wherein the acidic ion exchanger has a particle size distribution 400 m and a water retention capacity <60%.
5. The process according to claim 3, wherein the acidic ion exchanger has a particle size distribution <400 m and a water retention capacity >60%.
6. The process according to claim 1, wherein the reaction in step b) is carried out at a temperature in a range from 0 to 50 C. and/or at atmospheric pressure.
7. The process according to claim 1, wherein the reaction of step b) is carried out until at most 75% of the DMDF has been reacted to 1,1,4,4-tetramethoxy-2-butene.
8. The process according to claim 1, wherein the molar ratio of the DMDF to methanol in step b) is in a range from 1:45 to 1:100.
9. The process according to claim 1, wherein the process is conducted in the absence of trialkyl orthoformate.
10. The process according to claim 1, wherein when the reaction of step b) is stopped, water is present in a range from 0 to 100 mol % in relation to the amount of DMDF.
11. A process of separating 1,1,4,4-tetramethoxy-2-butene, methanol and 2,5-dimethoxy-2,5-dihydrofuran (DMDF) from a mixture comprising water, methanol, 1,1,4,4-tetramethoxy-2-butene and DMDF, the process comprising the following steps: i) providing a reaction mixture comprising water, methanol, 1,1,4,4-tetramethoxy-2-butene, and DMDF; ii) bringing the reaction mixture into contact with a basic compound; and iii) distilling the reaction mixture comprising water, methanol, 1,1,4,4-tetramethoxy-2-butene and DMDF in the presence of a basic compound to separate methanol, 1,1,4,4-tetramethoxy-2-butene and DMDF from each other, wherein step ii) is practiced either by providing the reaction mixture of step i) with the basic compound or adding the basic compound to the reaction mixture before or during the distillation according to step iii), and wherein the reaction mixture contains no acetalization agent other than the methanol, and wherein the basic compound is a basic metal salt, a basic ion exchanger or a mixture thereof and is present in an amount in a range from 0.03 to 0.3 weight-%, based on the total weight of the reaction mixture.
12. The process according to claim 11, which further comprises recycling the basic compound which is separated from the methanol, 1,1,4,4-tetramethoxy-2-butene and DMDF.
13. The process according to claim 12, wherein the basic ion exchanger is a strong anion exchange resin containing hydroxy groups or the corresponding salts.
14. The process according to claim 12, wherein the basic metal salt is an alkali, alkaline earth and/or ammonium salt soluble in methanol.
15. The process according to claim 11, wherein step iii) is performed at a temperature in a range from 20 to 180 C. and/or at a pressure in a range from 0.1 to 1013 mbar.
16. The process according to claim 11, wherein the process is carried out continuously.
17. The process according to claim 1, wherein the process is carried out continuously.
Description
BRIEF DESCRIPTION OF THE DRAWING
(1)
DETAILED DESCRIPTION OF THE INVENTION
(2) These needs are fulfilled by the present invention, which is directed to a process (PROCESS 1) for the manufacture of 1,1,4,4-tetramethoxy-2-butene (=C.sub.4-diacetal) comprising the following steps: a) providing 2,5-dimethoxy-2,5-dihydrofuran, which optionally contains 1,1,4,4-tetramethoxy-2-butene; b) reacting said 2,5-dimethoxy-2,5-dihydrofuran, whereby optionally 1,1,4,4-tetramethoxy-2-butene is present, provided in step a) with methanol, in the presence of an acidic ion exchanger as catalyst, whereby optionally water is present, to a mixture comprising H.sub.2O and 1,1,4,4-tetramethoxy-2-butene until at most 79% of 2,5-dimethoxy-2,5-dihydrofuran have been reacted to 1,1,4,4-tetramethoxy-2-butene, whereby the molar ratio of 2,5-dimethoxy-2,5-dihydrofuran to methanol is 1:45; c) optionally adding a basic compound to the mixture comprising H.sub.2O, methanol, 1,1,4,4-tetramethoxy-2-butene and 2,5-dimethoxy-2,5-dihydrofuran; d) distilling said mixture comprising H.sub.2O, methanol, 1,1,4,4-tetramethoxy butene, 2,5-dimethoxy-2,5-dihydrofuran in the presence of said basic compound to separate these compounds from each other, whereby 1,1,4,4-tetramethoxy-2-butene, methanol and un-reacted 2,5-dimethoxy-2,5-dihydrofuran are obtained; whereby either a basic compound is added to the mixture in step c) or a basic compound is present during the distillation of step d).
(3) In a preferred embodiment of PROCESS 1 un-reacted 2,5-dimethoxy-2,5-dihydrofuran obtained in step d) is recycled back into step a) or b), respectively, thus adding to the sustainability of the process.
(4) The single steps are disclosed in more detail below.
(5) Step a)
(6) Preferably the amount of C.sub.4-diacetal is <1 mol-%, more preferably <0.5 mol %, most preferably <0.1 mol-%, related to the amount of DMDF.
(7) Step b)
(8) Preferably the reaction is carried out in continuous mode in reactors as known to the person skilled in the art. Especially preferred are fixed-bed or tube reactors or tube bundle reactors.
(9) The reaction is preferably performed at a temperature in the range of from 0 to 50 C., more preferably at a temperature in the range of from 10 to 30 C., most preferably at a temperature in the range of from 15 to 25 C., and/or preferably at atmospheric pressure.
(10) Catalyst
(11) In a preferred embodiment the catalyst used in step b) is an acidic ion exchanger having a concentration of acid sites of at least 2.5 eq/kg, preferably at least 3.0 eq/kg, more preferably at least 4.0 eq/kg, most preferably 5.0 eq/kg. If an acidic ion exchanger is used which has a lower concentration of acid sites than 2.5 eq/kg, the selectivity and the turn-over are still high, but the reaction time is longer (see example 1F compared to the examples 1A-1E).
(12) In a more preferred embodiment the catalyst is an acidic ion exchanger containing sulfonic acid groups and having a concentration of acid sites of at least 2.5 eq/kg, preferably at least 3.0 eq/kg, more preferably at least 4.0 eq/kg, most preferably 5.0 eq/kg.
(13) Surprisingly it has been found that the use of acidic ion exchangers with the preferences as given above that have a certain particle size distribution and a certain water retention capacity results in an even higher selectivity towards the product, i.e. the C.sub.4-diacetal.
(14) Such preferred catalysts are either acidic ion exchangers having a particle size distribution 400 m and a water retention capacity <60%, preferably a water retention capacity in the range of from 40 to 60%, more preferably a water retention capacity in the range of from 50 to 60%, or acidic ion exchangers having a particle size distribution <400 m and a water retention capacity >60%, preferably a water retention capacity in the range of from 60 to 80%, more preferably a water retention capacity in the range of from 60 to 75%.
(15) The acidic ion exchangers showed a high activity over a long period of time. Nevertheless, if their activity is decreasing, they may be re-activated by washing with a polar organic solvent, preferably by washing with methanol, or by washing with a protic organic solvent or by washing with a protic inorganic solvent such as an acid.
(16) The person skilled in the art will choose the amount of the catalyst, i.e. the bed volume, according to the amount of the reaction mixture.
(17) Any acidic ion exchanger with one or more of the preferred characteristics as given above can successfully be employed in the process of the present invention.
(18) The most preferred acidic ion exchangers have all preferred characteristics as given above.
(19) Amount of Methanol
(20) The molar ratio of 2,5-dimethoxy-2,5-dihydrofuran to methanol in step b) is preferably in the range of from 1:45 to 1:100, more preferably in the range of from 1:50 to 1:90, even more preferably in the range of from 1:60 to 1:80, most preferably in the range of from 1:70 to 1:80.
(21) Conversion Rate
(22) Preferably the reaction is carried out until at most 75% of DMDF have been reacted to C.sub.4-diacetal, more preferably until 20 to 72% of DMDF have been reacted to C.sub.4-diacetal, even more preferably until 35 to 70% of DMDF/40 to 65% of DMDF/45 to 60% of DMDF, respectively, have been reacted to C.sub.4-diacetal, most preferably until 50 to 60% of DMDF have been reacted to C.sub.4-diacetal.
(23) Absence of an Acetalization Agent Except Methanol
(24) In a preferred embodiment of the present process no acetalization agent except methanol is present. Especially excluded is the use of trialkyl orthoformate as used in the processes of EP 581 097 and WO 2006/108664, since the use of trialkyl orthoformate leads to the formation of methyl formate which adds to the waste produced in the process. Since no acetalization agent except methanol is present in the process of the present invention, the amount of waste is minimized.
(25) Since H.sub.2O is formed during the reaction which facilitates the return reaction to the starting materials, as well as the reaction to the by-product DMB, the amount of H.sub.2O is preferably below a certain level to still guarantee a sufficient turn-over. It has been found that the amount of water when stopping the reaction of step b) is preferably in the range of from 0 to 100 mol %, more preferably in the range of from 20 to 80 mol %, most preferably in the range of from 30 to 65 mol %, related to the amount of 2,5-dimethoxy-2,5-dihydrofuran.
(26) The combination of steps c) and d) is also an invention. Thus, the present invention is also directed to a process (PROCESS 2) of separating 1,1,4,4-tetramethoxy butene (=C.sub.4-diacetal), methanol and 2,5-dimethoxy-2,5-dihydrofuran (=DMDF) from a mixture comprising H.sub.2O, methanol, 1,1,4,4-tetramethoxy-2-butene and 2,5-dimethoxy-2,5-dihydrofuran comprising the following steps: i) providing a mixture comprising H.sub.2O, methanol, C.sub.4-diacetal, DMDF and optionally a basic compound; ii) optionally adding a basic compound to said mixture; iii) distilling said mixture comprising H.sub.2O, methanol, C.sub.4-diacetal and DMDF in the presence of said basic compound to separate methanol, C.sub.4-diacetal and DMDF from each other;
whereby either a basic compound is already present in the mixture provided in step i) or a basic compound is added in step ii).
Step c and d)/Step i) and ii), Respectively
(27) The starting mixture comprises preferably <70 mol-% of DMDF, more preferably DMDF in an amount in the range of from 20 to 70 mol-%, even more preferably DMDF in an amount in the range of from 30 to 60 mol-%, most preferably DMDF in an amount in the range of from 40 to 50 mol-%, based on the total amount of C4-diacetal and DMDF.
(28) The amount of C.sub.4-diacetal in the starting mixture is preferably >30 mol-%, more preferably it is in the range of from 30 to 80 mol-%, even more preferably it is in the range of from 40 to 70 mol-%, most preferably it is in the range of from 50 to 60 mol-%, based on the total amount of C.sub.4-diacetal and DMDF.
(29) The amount of water in the starting mixture is preferably >30 mol-%, more preferably it is in the range of from 30 to 80 mol-%, even more preferably it is in the range of from 40 to 70 mol-%, most preferably it is in the range of from 50 to 60 mol-%, based on the total amount of C.sub.4-diacetal, H.sub.2O and DMDF.
(30) Preferably the basic compound is a heterogenous basic compound, more preferably it is a basic metal salt or a basic ion exchanger or a mixture thereof, most preferably the basic compound is a basic ion exchanger. Advantageously the basic compound can be recycled.
(31) In general any basic salt being soluble in methanol is suitable. Such salts are e.g. alkali, alkaline earth and ammonium salts soluble in methanol. Preferred examples of such salts are potassium carbonate, sodium carbonate and diammonium hydrogen phosphate, whereby potassium and sodium carbonate are preferred. Also mixtures of these salts, especially of these preferred salts, may be used.
(32) Basic ion exchangers encompass strong anion exchange resins containing hydroxy groups or the corresponding salts.
(33) The amount of said basic compound is preferably in the range of from 0.01 to 1 weight-%, more preferably in the range of from 0.02 to 0.75 weight-%, even more preferably in the range of from 0.03 to 0.5 weight-%, most preferably in the range of from 0.03 to 0.3 weight-%, based on the total weight of the reaction mixture comprising methanol, H.sub.2O, C.sub.4-diacetal and DMDF.
(34) A higher amount of basic compound may be used, but leads to more waste making the process less sustainable.
(35) The presence of the basic compound prevents the loss of desired product (=C.sub.4-diacetal) and un-reacted starting material (=DMDF) during distillation of the mixture. By the presence of the basic compound the loss of both compounds, C.sub.4-diacetal and DMDF, could be reduced to an amount of less than 7 mol-%, preferably to an amount of less than 5 mol-%.
(36) Step iii
(37) Step iii) is preferably performed at a temperature in the range of from 20 to 180 C., more preferably at a temperature in the range of from 30 to 150 C., most preferably at a temperature in the range of from 40 to 110 C., and/or preferably at a pressure in the range of from 0.1 to 1013 mbar, more preferably at a pressure in the range of from 0.5 to 500 mbar, most preferably at a pressure in the range of from 1 to 100 mbar.
(38) The present invention encompasses any combination of one or more preferred embodiments as mentioned above of the PROCESSES 1 and 2.
(39) Further embodiments of the present invention are the use of a basic compound as defined above in the distillation of a mixture comprising H.sub.2O, 1,1,4,4-tetramethoxy-2-butene and 2,5-dimethoxy-2,5-dihydrofuran, and the use of an acidic ion exchanger as catalyst in a reaction of 2,5-dimethoxy-2,5-dihydrofuran with methanol to 1,1,4,4-tetramethoxy-2-butene, whereby the molar ratio of 2,5-dimethoxy-2,5-dihydrofuran to methanol is 1:45.
(40) The invention is now further illustrated in the following non-limiting examples.
EXAMPLES
(41) The following acidic ion exchangers are tested:
(42) Acidic Ion Exchanger
(43) Amberlyst 15WET (commercially available from Dupont Water SolutionsDDP Specialty Products Germany GmbH Et Co. KG, Neu-Isenburg, Germany): macroporous; particle size distribution: 400-1200 m; water retention capacity: 52-57%; concentration of acid sites: 5 equivalents per kg of ion exchanger; Amberlyst 46 (commercially available from Dupont Water SolutionsDDP Specialty Products Germany GmbH Et Co. KG, Neu-Isenburg, Germany): macroporous; particle size distribution: 400-1200 m; water retention capacity: 26-36%; concentration of acid sites: 1 equivalents per kg of ion exchanger; Dowex88H (commercially available from Dupont Water SolutionsDDP Specialty Products Germany GmbH Et Co. KG, Neu-Isenburg, Germany): macroporous; particle size distribution: 300-1200 m; water retention capacity: 42-48%; concentration of acid sites: 5 equivalents per kg of ion exchanger; Dowex50WX4 50-100 mesh (commercially available from Dupont Water SolutionsDDP Specialty Products Germany GmbH Et Co. KG, Neu-Isenburg, Germany): gel; particle size distribution: 200-400 m; water retention capacity: 64-72%; concentration of acid sites: 5 equivalents per kg of ion exchanger; Dowex50WX4 16-25 mesh (commercially available from Dupont Water SolutionsDDP Specialty Products Germany GmbH Et Co. KG, Neu-Isenburg, Germany): gel; particle size distribution: 400-1200 m; water retention capacity: 64-72%; concentration of acid sites: 5 equivalents per kg of ion exchanger; Dowex50WX4 200-400 mesh (commercially available from Dupont Water SolutionsDDP Specialty Products Germany GmbH Et Co. KG, Neu-Isenburg, Germany): gel; particle size distribution: 37-74 m; water retention capacity: 64-72%; concentration of acid sites: 5 equivalents per kg of ion exchanger.
Basic Ion Exchanger
(44) Amberlyst A26 (commercially available from Dupont Water SolutionsDDP Specialty Products Germany GmbH Et Co. KG, Neu-Isenburg, Germany): particle size distribution: 560-700 m; water retention capacity: 66-75%; surface area: 30 m.sup.2/g (Nitrogen BET); pore diameter: 290 .
Examples 1A-H: Acid-Catalyzed Conversion of DMDF to C.SUB.4.-Diacetal
(45) The reactor is filled with 50 mm glass wool, then an acidic ion exchanger (=catalyst) according to Table 1-3 is added. Then methanol is pumped through the catalyst bed until the solvent is colorless. A solution of DMDF (408 mmol) in methanol (1250 ml, 31.2 mol) is prepared and pumped through the catalyst bed at different temperatures (11-21 C.) and flowrates (1-24 mL/min). Samples are taken after a flow of three bed volumes under constant conditions. The starting solution as well as the samples are analyzed with gas chromatography.
(46) TABLE-US-00001 TABLE 1 various acidic ion exchangers tested under similar conditions Bed time Temperature Conversion Selectivity Yield PMB Example Catalyst [min] [ C.] [%] [%] [%] [%] 1A Dowex88H 17 21 53 93 49 0.0 1B Amberlyst 18 21 52 98 51 0.0 15WET 1C Dowex 50WX4 16 21 46 93 42 0.0 200-400 mesh 1D Dowex 50WX4 8 21 47 94 44 0.0 50-100 mesh 1E Dowex 50WX4 8 21 42 91 38 0.0 16-25 mesh 1F Amberlyst 46 38 21 46 94 44 0.0
(47) TABLE-US-00002 TABLE 2 Amberlyst 15WET tested under various catalyst bed retention times Bed Conver- time Temperature sion Selectivity Yield PMB Example [min] [ C.] [%] [%] [%] [%] 1G 9 21 39.4 98.7 39 0.0 1B 18 21 52.3 97.9 51 0.0
(48) TABLE-US-00003 TABLE 3 Amberlyst 15WET tested under various reaction temperatures Bed Conver- time Temperature sion Selectivity Yield PMB Example [min] [ C.] [%] [%] [%] [%] 1H 18 11 28.0 99.9 28 0.0 1B 18 21 52.3 97.9 51 0.0
Examples 2A-E: Acid-Catalyzed Conversion of DMDF to C.SUB.4.-Diacetal
(49) The reactor is filled with 50 mm glass wool and the acidic ion exchanger Amberlyst 15WET (=catalyst) is added. Then methanol is pumped through the catalyst bed until the solvent is colorless. A solution of DMDF (408 mmol) in methanol (1250 ml, 31.2 mol) is prepared and pumped through the catalyst bed at 21 C. and a flowrate of 4 mL/min. Samples are taken after certain periods. The starting solution as well as the samples are analyzed with gas chromatography. As shown in Table 4 below the catalyst showed a constant high selectivity even after more than 70 hours.
(50) TABLE-US-00004 TABLE 4 Amberlyst 15WET: long-term stability at constant reaction conditions Experiment time Conversion Selectivity Yield PMB Example [hours] [%] [%] [%] [%] 2A 1.5 54.5 97.2 53 0.0 2B 8.0 54.5 98.5 54 0.0 2C 29.2 56.1 95.2 53 0.0 2D 50.6 52.9 98.8 52 0.0 2E 71.0 52.8 97.8 52 0.0
Examples 3A-E: Acid-Catalyzed Conversion of a Mixture of DMDF and C.SUB.4.-Diacetal to C.SUB.4.-Diacetal
(51) The reactor is filled with 50 mm glass wool and the acidic ion exchanger Amberlyst 15WET (=catalyst) is added. Then methanol is pumped through the catalyst bed until the solvent is colorless. A solution of DMDF (408 mmol) and various amounts of C.sub.4-Diacetal (0-142.8 mmol) in methanol (1250 ml, 31.2 mol) is prepared and pumped through the catalyst bed of Amberlyst 15WET at 20 C. and various flowrates (2-14 mL/min). Samples are taken after certain periods. The starting solution as well as the samples are analyzed with gas chromatography. The results are shown in Table 5.
(52) TABLE-US-00005 TABLE 5 Amberlyst 15WET-catalyzed conversion of a mixture of DMDF and C.sub.4-diacetal to C.sub.4-diacetal C.sub.4- Bed Conver- diacetal time sion Selectivity Yield PMB Example [mmol] [min] [%] [%] [%] [%] 3A 0 18 54 98 53 0.0 3B 40.8 18 57 95 54 0.0 3C 61.2 18 58 97 56 0.0 3D 102.0 12 57 94 54 0.0 3E 142.8 12 61 95 58 0.0
(53) The selectivity is still high in the presence of C.sub.4-diacetal.
Examples 4A-B: Acid-Catalyzed Conversion of a Mixture of DMDF, C.SUB.4.-Diacetal and H.SUB.2.O to C.SUB.4.-Diacetal
(54) The reactor is filled with 50 mm glass wool and the acidic ion exchanger Amberlyst 15WET (=catalyst) is added. Then methanol is pumped through the catalyst bed until the solvent is colorless. A solution of DMDF (408 mmol), C.sub.4-Diacetal (142.8 mmol) and H.sub.2O (0 or 1224 mmol) in methanol (1250 ml, 31.2 mol) is prepared and pumped through the catalyst bed of Amberlyst 15WET at 22 C. with a residence time of 18 minutes. Samples are taken after certain periods. The starting solution as well as the samples are analyzed with gas chromatography. The results are shown in Table 6.
(55) TABLE-US-00006 TABLE 6 C.sub.4- Conver- Yield C.sub.4- diacetal H.sub.2O sion Selectivity diacetal PMB Example [mmol] [mmol] [%] [%] [%] [%] 4A 142.8 0 66.0 93.0 61 0.0 4B 142.8 1224 27.3 91.7 25 0.0
(56) If water is present in an amount of 3 times of the amount of DMDF, the conversion of DMDF to C.sub.4-diacetal decreases.
Examples 5A-D: Stability Tests of DMDF and C4-Diacetal in the Presence of Water During Distillation
(57) A 2000 mL round bottom flask was filled with DMDF (245 mmol), C.sub.4-Diacetal (245 mmol) and H.sub.2O (0 or 1000 mmol) in methanol (1000 ml, 25 mol) and an additional basic compound was added according to Table 7. The reaction mixture was evaporated at 70 C./700 mbar to a certain amount. The evaporated solution and starting solution are analyzed with gas chromatography. The results are shown in Table 7.
(58) TABLE-US-00007 TABLE 7 Basic C.sub.4- Mass of solution compound diacetal DMDF Example [g] [g] [mmol] [mmol] 5A 887 none 249 245 5A(ev) 175 none 245 242 5B 863 including 18 g of H.sub.2O none 249 245 (=1000 mmol = 1 mol) 5B(ev) 167 none 150 215 5C 881 including 18 g of H.sub.2O 0.5 K.sub.2CO.sub.3 246 244 (=1000 mmol = 1 mol) 5C(ev) 253 0.5 K.sub.2CO.sub.3 244 245 5D 883 including 18 g of H.sub.2O 2.0 g 245 244 (=1000 mmol = 1 mol) Amberlyst A26 5D(ev) 157 2.0 g 237 244 Amberlyst A26
(59) 5A-5D are the starting solutions.
(60) ev means that the corresponding sample had been evaporated until the amount as given in Table 7 remained.
(61) Sample 5A (887 g) e.g. contained originally 249 mmol of C.sub.4-diacetal and 245 mmol of DMDF; the rest being methanol. When the solvent had been evaporated (=sample 5A(ev)), 245 mmol of C.sub.4-diacetal (98.4% of original amount) and 242 mmol of DMDF (98.8% of original amount) could be retrieved.
(62) When, however, water had been present in the starting solution and no basic compound (see examples 5B and 5B(ev), respectively), then only 150 mmol of C.sub.4-diacetal (60.3% of original amount) and 215 mmol of DMDF (87.8% of original amount) could be retrieved; thus leading to a substantial loss of the desired product (=C.sub.4-diacetal) and the non-reacted starting material (=DMDF).
(63) This loss could be prevented by the presence of the basic compoundsee examples 5C/5C(ev) and 5D/5D(ev), respectively:
(64) In the presence of 0.5 g of K.sub.2CO.sub.3 in the starting solution 5C, after evaporation 244 mmol of C.sub.4-diacetal (99.2% of original amount) and 245 mmol of DMDF (100.4% of the original amount*) could be retrieved. * In the presence of the basic compound, the by-product DMB is reacted to DMDF so that more DMDF is retrieved than originally present.
(65) In the presence of 2.0 g of the basic ion exchanger Amberlyst A26 in the starting solution 5D, after evaporation 237 mmol of C.sub.4-diacetal (96.7% of original amount) and 244 mmol of DMDF (100% of original amount) could be retrieved.