DE1907117B2 - METHOD OF MANUFACTURING OXETANYL ESTERS - Google Patents
METHOD OF MANUFACTURING OXETANYL ESTERSInfo
- Publication number
- DE1907117B2 DE1907117B2 DE19691907117 DE1907117A DE1907117B2 DE 1907117 B2 DE1907117 B2 DE 1907117B2 DE 19691907117 DE19691907117 DE 19691907117 DE 1907117 A DE1907117 A DE 1907117A DE 1907117 B2 DE1907117 B2 DE 1907117B2
- Authority
- DE
- Germany
- Prior art keywords
- oxetanyl
- esters
- manufacturing
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/08—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Description
CH2 CH2 CH2 CH2 CH 2 CH 2 CH 2 CH 2
O OO O
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 2700C in Gegenwart eines Dehydrierungskatalysators erhitzt.in which R is a lower alkyl radical having 1 to 6 carbon atoms, is characterized in that 3 alkyl-3-hydroxymethyl-oxetane heated a corresponding liquid phase at temperatures between 190 ° and 270 0 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 führt.From 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
— O — CH, R - O - CH, R
C CC C
CH2 CH2 CH2 CH2 CH 2 CH 2 CH 2 CH 2
O OO O
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 27O°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 vorauszusehen.This different course of the dehydrogenation in the liquid phase could not be foreseen.
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 Dehydrierungskatalysatoren 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, S 494 ff " Georg Thieme-Verlag, Stuttgart, 1965, and French patent specification 11 22 903). As dehydrogenation catalysts can be used e.g. B. copper chromite, zinc chromite, cadmium chromite, silver contacts, are 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 ist.ίο 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 durch 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.The process products represent intermediate products of the others, for example by customary processes, z. B. by saponification, by reacting the carboxylic acid obtained by saponification 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 mit3500 g of 3-ethyl-3-hydroxymethyl-oxetane are with
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 2200C erhitzt. Während dieser Zeit wird eine rege Wasserstoffentwicklung beobachtet; gleichzeitig destillieren 670 g eines Gemisches aus Äthanol. Wasser, 2-Äthylacrolein und 2-Methylbutanol ab. Die Reaktionstemperatur wird anschließend 2 Stunden auf 2600C 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.0.21080C; π = 1,4576.140 g of a Cu / Cr / Ba-containing catalyst, the production of which in Houben - Weyl, methods of org. Chemie, Volume 4/2, page 182, is described, heated to 220 0 C for 4 hours. During this time, a vigorous evolution of hydrogen is observed; at the same time distill 670 g of a mixture of ethanol. Water, 2-ethyl acrolein and 2-methylbutanol. The reaction temperature is then increased to 260 ° C. for 2 hours. After filtration, the reaction product (2700 g) is distilled. There are 1,200 g of 3-Äthyloxetanyl- (3 | -carboxylic acid [3-ethyl-oxetanyl (3)] - get methylester Kp.0.2108 0 C; π = 1.4576..
Gewichtsanalyse in % für C12H20O4:Weight analysis in% for C12H20O4:
Berechnet: C 63,20, H 8,77, 0 28,05, MG 228;
gefunden^ 63,35, H 8,66, O 28,15, MG 223.Calculated: C 63.20, H 8.77, 0.28.05, MW 228;
Found ^ 63.35, H 8.66, O 28.15, MW 223.
3508 g 3-Methyl-3-hydroxymethyloxetan werden mit3508 g of 3-methyl-3-hydroxymethyloxetane are with
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 3-Methyl-oxetanyl-(3)-carbonsäure-[3-methyl-oxetanyl-(3)-methyl]-ester. Kp-oos 92-930C, η =1,4555, erhalten. 141 g of the catalyst given in Example 1 were heated under reflux conditions for 15 hours. The temperature of the reaction mixture increases slowly from 200 ° to 240 ° C. 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 3-methyl-oxetanyl- (3) -carboxylic acid [3-methyl-oxetanyl- (3) -methyl] ester are obtained. Kp-oos 92-93 0 C, η = 1.4555.
Gewichtsanalyse in % für G0H ,„Ο« (200)Weight analysis in% for G 0 H, "Ο" (200)
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 true DE1907117B2 (en) | 1977-06-02 |
| DE1907117C3 DE1907117C3 (en) | 1978-01-12 |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE1907117A1 (en) | 1970-09-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| EHV | Ceased/renunciation |