DEP0046188DA - Process for the production of ether alcohols - Google Patents
Process for the production of ether alcoholsInfo
- Publication number
- DEP0046188DA DEP0046188DA DEP0046188DA DE P0046188D A DEP0046188D A DE P0046188DA DE P0046188D A DEP0046188D A DE P0046188DA
- Authority
- DE
- Germany
- Prior art keywords
- ether alcohols
- production
- copper
- condensation
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 5
- -1 ether alcohols Chemical class 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims 2
- 238000004519 manufacturing process Methods 0.000 title description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- LYWWXPVUSWJFCZ-UHFFFAOYSA-N 1-ethoxybut-1-en-3-yne Chemical group CCOC=CC#C LYWWXPVUSWJFCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- NPKGQBIUYHHPOT-UHFFFAOYSA-N [Cu+2].[C-]#[C-] Chemical class [Cu+2].[C-]#[C-] NPKGQBIUYHHPOT-UHFFFAOYSA-N 0.000 description 2
- 150000000475 acetylene derivatives Chemical class 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GFSQUFUIPGFIHV-UHFFFAOYSA-N copper;ethynylbenzene Chemical compound [Cu].C#CC1=CC=CC=C1 GFSQUFUIPGFIHV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Phenylacetylene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VXJUUVKQTUQXIB-UHFFFAOYSA-N [Ag+2].[C-]#[C-] Chemical class [Ag+2].[C-]#[C-] VXJUUVKQTUQXIB-UHFFFAOYSA-N 0.000 description 1
- LAWJMNDTDHTXCL-UHFFFAOYSA-N [Ag+].[Ag+].[Ag+].[Ag+].[C-]#[C-].[C-]#[C-] Chemical compound [Ag+].[Ag+].[Ag+].[Ag+].[C-]#[C-].[C-]#[C-] LAWJMNDTDHTXCL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229940027985 antiseptics and disinfectants Silver compounds Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229940100890 silver compounds Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
Es ist bekannt, dass Verbindungen der Acetylenreihe, die am 3-fach gebundenen Kohlenstoffatom noch ein freies Wasserstoffatom besitzen, sich mit Carbonylverbindungen kondensieren lassen. Derartige Kondensationen können mittels der Grignard-Verbindungen der Acetylene ausgeführt werden. Man kann ferner die Kondensation der Acetylene selbst mit den Carbonylverbindungen mit Hilfe von Alkalimetallen oder Alkalihydroxyden oder auch von Kupferacetyliden durchführen.It is known that compounds of the acetylene series which still have a free hydrogen atom on the triple bonded carbon atom can be condensed with carbonyl compounds. Such condensations can be carried out by means of the Grignard compounds of the acetylenes. You can also carry out the condensation of the acetylenes themselves with the carbonyl compounds with the aid of alkali metals or alkali hydroxides or copper acetylides.
Es wurde nun gefunden, dass man Ätheralkohole erhalten kann, wenn man Alkoxyvinylacetylene mit Formaldehyd oder dessen Polymeren, wie Paraformaldehyd, in Gegenwart von Schwermetallacetyliden kondensiert und die erhaltenen Kondensationsprodukte gegebenenfalls hydriert. Die Alkoxyvinylacetylene kann man beispielsweise durch Umsetzen von Diacetylen mit Alkoholen nach dem Verfahren des DRP 601 822 erhalten. Als Schwermetallacetylide kommen nicht nur das Kupfer- oder Silberacetylid in Frage, auch das Kupfer- oder Silberdiacetylid sowie die Kupfer- oder Silberverbindungen der Alkoxyvinyl-acetyline kommen in Betracht. Als besonders geeignet hat sich das Kupferacetylid des Phenylacetylens erwiesen. Die Kondensation wird zweckmässig in Gegenwart von organischen Lösungs- oder Verdünnungsmitteln durchgeführt, wofür auch ein Überschuss an Alkoxyvinylacetylen in Betracht kommen kann. Die Kondensation erfolgt zweckmässig bei erhöhter Temperatur. Das bei der Kondensation entstehende Alkoxy-(5)-pentin-(2)-en-(4)-ol-(1) kann durch Destillation, zweckmässig im Vakuum, oder durch Wasserdampfdestillation isoliert werden. Beabsichtigt man die Herstellung des daraus durch Hydrierung entstehenden Alkoxy-(5)-n-pentanol-(1), so kann man auf eine Isolierung verzichten und das anfallende Reaktionsgemisch nach Abtrennung des verwendeten Schwermetallacetylides durch Filtrieren der Hydrierung in Gegenwart von Katalysatoren unterwerfen.It has now been found that ether alcohols can be obtained if alkoxyvinylacetylenes are condensed with formaldehyde or its polymers, such as paraformaldehyde, in the presence of heavy metal acetylides and the condensation products obtained are optionally hydrogenated. The alkoxyvinylacetylenes can be obtained, for example, by reacting diacetylenes with alcohols by the method of DRP 601 822. Not only copper or silver acetylides come into consideration as heavy metal acetylides, but also copper or silver diacetylide and the copper or silver compounds of alkoxyvinyl acetylines. The copper acetylide of phenylacetylene has proven to be particularly suitable. The condensation is expediently carried out in the presence of organic solvents or diluents, for which an excess of alkoxyvinylacetylene can also be considered. The condensation is expediently carried out at an elevated temperature. The alkoxy- (5) -pentyne- (2) -en- (4) -ol- (1) formed during the condensation can be isolated by distillation, advantageously in vacuo, or by steam distillation. If one intends to prepare the alkoxy- (5) -n-pentanol- (1) formed therefrom by hydrogenation, isolation can be dispensed with and the resulting reaction mixture can be subjected to hydrogenation in the presence of catalysts after the heavy metal acetylide used has been separated off by filtration.
Die erhaltenen ungesättigten Ätheralkohole sind wichtige Zwischenprodukte zur Durchführung von Synthesen, während die daraus durch Hydrieren erhaltenen gesättigten Ätheralkohole als Lösungsmittel, Esterkomponenten, ferner als Regler bei der Superpolyamidherstellung und als Zwischenprodukt bei der Herstellung von Äthercarbon- bzw. Dicarbonsäuren verwendet werden können.The unsaturated ether alcohols obtained are important intermediate products for carrying out syntheses, while the saturated ether alcohols obtained therefrom by hydrogenation can be used as solvents, ester components, as regulators in the production of super polyamides and as an intermediate in the production of ether carbon or dicarboxylic acids.
Beispiel.Example.
200 Gewichtsteile Äthoxyvinylacetylen und 30 Gewichtsteile Paraformaldehyd werden in Gegenwart von 10 Gewichtsteilen Phenylacetylenkupfer unter Rühren 2 Stunden lang auf 90° gehalten. Man destilliert das im Überschuss angewandte Äthoxyvinylacetylen ab und erhält beim Kp.(sub)2mm : 95-100° Äthoxy-(5)-pentin-(2)-en-(4)-ol-(1). Hydriert man das erhaltene Gemisch nach dem Abfiltrieren des Phenylacetylenkupfers in Gegenwart von Raney-Nickel unter einem Druck von 200 Atm bei einer allmählich von 20 auf 200° steigenden Reaktionstemperatur, so erhält man nach dem Aufarbeiten durch Destillation Äthoxy-(5)-n-pentanol-(1) vom Kp.(sub)1mm : 70° neben Äthylbutyläther, der aus dem im Überschuss angewandten Äthoxyvinylacetylen entstanden ist.200 parts by weight of ethoxyvinylacetylene and 30 parts by weight of paraformaldehyde are kept at 90 ° for 2 hours with stirring in the presence of 10 parts by weight of phenylacetylene copper. The ethoxyvinylacetylene used in excess is distilled off and obtained at b.p. (sub) 2mm: 95-100 ° ethoxy- (5) -pentine- (2) -en- (4) -ol- (1). If the mixture obtained is hydrogenated after filtering off the phenylacetylene copper in the presence of Raney nickel under a pressure of 200 atm and a reaction temperature gradually rising from 20 to 200 °, then after working up by distillation, ethoxy- (5) -n-pentanol is obtained - (1) from Kp. (Sub) 1mm: 70 ° in addition to ethyl butyl ether, which arose from the ethoxyvinylacetylene used in excess.
Claims (1)
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