DE1907117C3 - Process for the preparation of oxetanyl esters - Google Patents
Process for the preparation of oxetanyl estersInfo
- Publication number
- DE1907117C3 DE1907117C3 DE19691907117 DE1907117A DE1907117C3 DE 1907117 C3 DE1907117 C3 DE 1907117C3 DE 19691907117 DE19691907117 DE 19691907117 DE 1907117 A DE1907117 A DE 1907117A DE 1907117 C3 DE1907117 C3 DE 1907117C3
- Authority
- DE
- Germany
- Prior art keywords
- oxetanyl
- esters
- preparation
- oxetane
- methyl
- 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
- 238000000034 method Methods 0.000 title claims description 5
- 125000003566 oxetanyl group Chemical group 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000003054 catalyst Substances 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 2
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N Thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- BJYGGFGTOTUNJA-UHFFFAOYSA-N (3-butyloxetan-3-yl)methanol Chemical compound CCCCC1(CO)COC1 BJYGGFGTOTUNJA-UHFFFAOYSA-N 0.000 description 1
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-Methyl-1-butanol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 1
- GMLDCZYTIPCVMO-UHFFFAOYSA-N 2-methylidenebutanal Chemical compound CCC(=C)C=O GMLDCZYTIPCVMO-UHFFFAOYSA-N 0.000 description 1
- DUQGFIKXKISULR-UHFFFAOYSA-N 3-methyloxetane-3-carbaldehyde Chemical compound O=CC1(C)COC1 DUQGFIKXKISULR-UHFFFAOYSA-N 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N Copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 241000054817 Lycaena dione Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZYGBIYVHFAUMJL-UHFFFAOYSA-N [Zn+2].[O-][Cr]([O-])=O Chemical compound [Zn+2].[O-][Cr]([O-])=O ZYGBIYVHFAUMJL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 cadmium chromite silver Chemical compound 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
CH2 CH2 CH2 CH2
O OCH 2 CH 2 CH 2 CH 2
OO
in der R einen niederen Alkylrest mit 1 bis 6 C-Atomen bedeutet, dadurch gekennzeichnet, daß man ein entsprechendes 3-Alkyl-3-hydroxymethyl-oxetan in flüssiger Phase auf Temperaturen zwischen 190° und 270°C in Gegenwart eines Dehydrierungskatalysators erhitztin which R is a lower alkyl radical with 1 to 6 carbon atoms, characterized in that that you have a corresponding 3-alkyl-3-hydroxymethyl-oxetane heated in the liquid phase to temperatures between 190 ° and 270 ° C in the presence of a dehydrogenation catalyst
Die Erfindung betrifft ein Verfahren zur Herstellung von Oxetanyl-Estern durch Erhitzen eines entsprechenden 3-Alkyl-3-hydroxymethyl-oxetans in flüssiger Phase in Gegenwart eines Dehydrierungskatalysators.The invention relates to a method of manufacture of oxetanyl esters by heating a corresponding 3-alkyl-3-hydroxymethyl oxetane in the liquid phase in the presence of a dehydrogenation catalyst.
Aus der US-PS 29 23 645 ist bekannt daß die Dehydrierung von 3-Methyl-3-hydroxymethyl-oxetan und analoger Verbindungen in der Gasphase zum 3-Methyl-3-formyl-oxetan führtFrom US-PS 29 23 645 it is known that the dehydrogenation of 3-methyl-3-hydroxymethyl-oxetane and analogous compounds lead to 3-methyl-3-formyl-oxetane in the gas phase
Überraschenderweise wurde nun gefunden, daß man Oxetanyl-Ester der allgemeinen FormelSurprisingly, it has now been found that oxetanyl esters of the general formula
R C-O-CH2 RR CO-CH 2 R
C CC C
CH2 CH2 CH2 CH2
O OCH 2 CH 2 CH 2 CH 2
OO
erhält, in der R einen niederen Alkylrest mit 1 bis 6 C-Atomen bedeutet, wenn man ein entsprechendes 3-Alkyl-3-hydroxymethyl-oxetan in flüssiger Phase auf Temperaturen zwischen 190° und 270° C in Gegenwart eines Dehydrierungskatalysators erhitzt.obtained, in which R is a lower alkyl radical with 1 to 6 carbon atoms, if you have a corresponding 3-Alkyl-3-hydroxymethyl-oxetane in the liquid phase at temperatures between 190 ° and 270 ° C in the presence a dehydrogenation catalyst heated.
Dieser andersartige Verlauf der Dehydrierung in flüssiger Phase war nicht verauszusehen.This different course of the dehydrogenation in the liquid phase was not foreseeable.
Für das Verfahren geeignete 3-Alkyl-3-hydroxymethyloxetane, die z. B. durch Abspaltung von Kohlendioxid aus den entsprechenden cyclischen Carbonaten erhalten werden können, sind z. B. 3-Methyl-3-hydroxymethyloxetan, 3-Äthyl-3-hydroxymethyloxetan, 3-Butyl-3-hydroxymethyloxetan (Houben — Weyl »Methoden der org. Chemie« 4. Auflage, Bd. 6/3, S. 494 ff, Georg Thieme-Verlag, Stuttgart 1965, und französische Patentschrift 11 22 903). Als Dehydrieru ngskatalysatoren können verwendet werden z.B. Kupferchromit, Zinkchromit, Cadmiumchromit Silberkontakte, bevorzugt jedoch Kupfer/Chrom/Barium enthaltende Katalysatoren, deren Herstellungsvorschrift im Houben — W e y 1 »Methoden der org. Chemie«, Bd, 4/2,3-alkyl-3-hydroxymethyloxetanes suitable for the process, e.g. B. by splitting off carbon dioxide can be obtained from the corresponding cyclic carbonates are, for. B. 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-butyl-3-hydroxymethyloxetane (Houben - Weyl "Methods of Org. Chemistry" 4th edition, Vol. 6/3, p. 494 ff, Georg Thieme-Verlag, Stuttgart 1965, and French Patent 11 22 903). As dehydrogenation catalysts can be used e.g. copper chromite, Zinc chromite, cadmium chromite silver contacts, preferred however, copper / chromium / barium containing catalysts, their manufacturing instructions in Houben - We y 1 »Methods of the org. Chemistry «, Vol. 4/2,
ίο 182, Georg Thieme-Verlag, Stuttgart, 1952, angegeben istίο 182, Georg Thieme-Verlag, Stuttgart, 1952, indicated is
Die Verfahrensprodukte stellen Zwischenprodukte der anderen beispielsweise nach üblichen Verfahren, z.B. durch Verseifen, durch Umsetzung der durchThe process products represent intermediate products of the others, for example by customary processes, e.g. by saponification, by implementing the
is Verseifung erhaltenen Carbonsäure mit Thionylchlorid oder durch Umsetzung der auf diese Weise erhaltenen Säurehalogenide mit Alkoholen, Phenolen, Ammoniak oder Aminen die verschiedensten Oxetanderivate hergestellt werden können.is saponification obtained carboxylic acid with thionyl chloride or by reacting the acid halides obtained in this way with alcohols, phenols, ammonia or amines a wide variety of oxetane derivatives can be prepared.
Der Oxetanring läßt sich in vielfältiger Weise zu Umsätzen, z. B. zur Polyaddition oder zur Hydrolyse oder zur Reaktion mit Säuren oder Alkoholen, heranziehen.The oxetane ring can be converted into a variety of ways, for. B. for polyaddition or hydrolysis or to react with acids or alcohols.
3500 g 3-Äthyl-3-hydroxymethyl-oxetan werden mit 140 g eines Cu/Cr/Ba enthaltenden Katalysators, dessen Herstellung in Houben — Weyl, Methoden der org. Chemie, Band 4/2, Seite 182, beschrieben ist, 4 Stunden auf 220° C erhitzt Während dieser Zeit wird eine rege Wasserstoffentwicklung beobachtet; gleichzeitig destillieren 67Og eines Gemisches aus Äthanol, Wasser, 2-Äthylacrolein und 2-Methylbutanol ab. Die Reaktionstemperatur wird anschließend 2 Stunden auf 260° C erhöht Nach einer Filtration wird das Reaktionsprodukt (2700 g) destilliert. Es werden 1200 g 3-Äthyloxetanyl-(3)-carbonsäure-[3-äthyl-oxetanyl-(3)]-methylester erhalten. Kp^ 108° C; n« = 1,4576.3500 g of 3-ethyl-3-hydroxymethyl-oxetane are mixed with 140 g of a Cu / Cr / Ba-containing catalyst, its preparation in Houben - Weyl, methods of org. Chemie, Volume 4/2, page 182, is heated to 220 ° C. for 4 hours. During this time, a lively evolution of hydrogen is observed; at the same time, 67Og of a mixture of ethanol, water, 2-ethylacrolein and 2-methylbutanol distilled off. The reaction temperature is then increased to 260 ° C. for 2 hours. After filtration, the reaction product (2700 g) is distilled. 1200 g of 3-ethyloxetanyl- (3) -carboxylic acid [3-ethyl-oxetanyl- (3)] methyl ester are obtained. Bp ^ 108 ° C; n " = 1.4576.
Berechnet: C 63,20, H 8,77, O 28,05, MG 228;
gefunden^ 6335, H 8,66, 0 28,15, MG 223.Calculated: C 63.20, H 8.77, O 28.05, MW 228;
Found ^ 6335, H 8.66, 0.28.15, MW 223.
3508 g 3-Methyl-3-hydroxyrnethyloxetani werden mit 141 g des im Beispiel 1 angegebenen Katalysators 15 Stunden unter Rückflußbedingungen erhitzt Die Temperatur der Reaktionsmischung steigt langsam von 200° auf 240° C an. Während dieser Zeit destillieren 820 g leicht flüchtige Anteile ab, gleichzeitig entweicht Wasserstoff. Nach einer Filtration wird das Reaktionsprodukt (2564 g) destilliert Es werden 1800 g S-Methyl-oxetanyl-ßJ-carbonsäure-p-methyl-oxetanyl-(3)-methyl]-ester, Kp.0.05 92-93°C, η»= 1,4555, erhalten. 3508 g of 3-methyl-3-hydroxyrnethyloxetani are heated with 141 g of the catalyst given in Example 1 for 15 hours under reflux conditions. During this time, 820 g of volatile components distill off, and hydrogen escapes at the same time. After filtration, the reaction product (2564 g) is distilled. 1800 g of S-methyl-oxetanyl-βI-carboxylic acid p-methyl-oxetanyl- (3) -methyl] ester, boiling point 0.05 92-93 ° C., η »= 1.4555 obtained.
Berechnet: C 60,0, H 8,00, O 32,00;
gefunden: C 60,1, H 8,06, O 32,2.Calculated: C 60.0, H 8.00, O 32.00;
Found: C 60.1, H 8.06, O 32.2.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691907117 DE1907117C3 (en) | 1969-02-13 | Process for the preparation of oxetanyl esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691907117 DE1907117C3 (en) | 1969-02-13 | Process for the preparation of oxetanyl esters |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1907117A1 DE1907117A1 (en) | 1970-09-03 |
| DE1907117B2 DE1907117B2 (en) | 1977-06-02 |
| DE1907117C3 true DE1907117C3 (en) | 1978-01-12 |
Family
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