DE2303997A1 - Vinyl acetic acid and butyrolactone prepn - by catalytic reaction of allyl alcohol, ethers or esters with carbon monoxide - Google Patents
Vinyl acetic acid and butyrolactone prepn - by catalytic reaction of allyl alcohol, ethers or esters with carbon monoxideInfo
- Publication number
- DE2303997A1 DE2303997A1 DE19732303997 DE2303997A DE2303997A1 DE 2303997 A1 DE2303997 A1 DE 2303997A1 DE 19732303997 DE19732303997 DE 19732303997 DE 2303997 A DE2303997 A DE 2303997A DE 2303997 A1 DE2303997 A1 DE 2303997A1
- Authority
- DE
- Germany
- Prior art keywords
- allyl
- acetic acid
- vinyl acetic
- butyrolactone
- carbon monoxide
- 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.)
- Withdrawn
Links
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 12
- 150000002148 esters Chemical class 0.000 title claims 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title abstract 4
- 229930188620 butyrolactone Natural products 0.000 title description 3
- 238000006555 catalytic reaction Methods 0.000 title 1
- 150000002170 ethers Chemical class 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- -1 allyl ethers Chemical class 0.000 claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 7
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 claims abstract description 6
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- QNBDJTKBKITRJI-UHFFFAOYSA-N prop-2-enyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCC=C QNBDJTKBKITRJI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004694 iodide salts Chemical class 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 101100189618 Caenorhabditis elegans pdi-2 gene Proteins 0.000 abstract 1
- 229910021588 Nickel(II) iodide Inorganic materials 0.000 abstract 1
- 229910021606 Palladium(II) iodide Inorganic materials 0.000 abstract 1
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 abstract 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 abstract 1
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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 carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Verfahren zur Herstellung von Vinylessigsäure und p-Butyrolacton Zusatzanmeldung zu Patentanmeldung P 22 17 534.4 (HOHE 72/F 117) Gegenstand des Patents ... ... ... (Patentanmeldung P 22 17 534.4) ist ein Verfahren zur Herstellung von Vinylessigsäure, das dadurch gekennzeichnet ist, daß man Verbindungen vom Typ Allyl-R, worin R bevorzugt eine Hydroxyl-, eine CarbonsXureester- oder -0ther gruppe darstellt, mit Kohlenmonoxid in Gegenwart von Schwermetallkatalysatoren der VI., VII. und/oder VIII. Nebengruppe des Periodensystems zur Reaktion bringt und gegebenenfalls in Gegenwart von Wasser arbeitet.Process for the production of vinyl acetic acid and p-butyrolactone Additional application to patent application P 22 17 534.4 (HOHE 72 / F 117) The subject of the patent ... ... ... (patent application P 22 17 534.4) is a process for the preparation of vinyl acetic acid, which is characterized in that compounds of the allyl-R type, in which R is preferably a hydroxyl ester, a carboxylic acid ester - Or -0ther group, reacts with carbon monoxide in the presence of heavy metal catalysts of the VI., VII. and / or VIII. subgroup of the periodic table and optionally works in the presence of water.
Bevorzugte Schwermetallkatalysatoren sind dabei etwa Kobalt, Nickel , Rhodium und Palladium in Form der Halogenide oder Carbonyle. Weitere Merkmale des Verfahrens sind, daß man in der Regel bei Temperaturen zwischen 50 und 3000C und bei Kohlenmonoxid-Drucken zwischen 0,5 und 500 atü arbeitet, sowie gegebenenfalls dem Reaktionsgemisch 0,01 bis 20 Mol Wasser pro Mol Allylverbindung zusetzt.Preferred heavy metal catalysts are, for example, cobalt and nickel , Rhodium and palladium in the form of the halides or carbonyls. Other features of the process are that one usually at temperatures between 50 and 3000C and works at carbon monoxide pressures between 0.5 and 500 atmospheres, as well as optionally 0.01 to 20 moles of water per mole of allyl compound are added to the reaction mixture.
Es hat sich nun herausgestellt, daß die neben dem Hauptprodukt Vinylessigsäure gebildeten, bisher unbekannten, hochsiedenden Reaktionsprodukte im wesentlichen aus /-Butyrolacton bestehen und daß die Menge des gebildeten Lactons insbesondere von der Zusatzmenge an Wasser abhängt, wobei Carbonsäureallylester die bevorzugten Allylverbindungen sind. Dieser Befund ist überraschend, da das {-Butyrolacton offenbar nicht durch Cyclisieren der Vinylessigsäure entsteht, sondern in einer bisher unbekannten Reaktion gebildet wird.It has now been found that in addition to the main product vinyl acetic acid educated, hitherto unknown, high-boiling Reaction products consist essentially of / -butyrolactone and that the amount of lactone formed in particular depends on the amount of water added, allyl carboxylates the preferred allyl compounds are. This finding is surprising since the {-butyrolactone apparently not formed by cyclization of vinyl acetic acid, but in one previously unknown reaction is formed.
Die weitere Ausbildung des Verfahrens zur Herstellung von Vinylessigsäure nach Patent . ... ... (Patentanmeldung P 22 17 534.4) ist somit dadurch gekennzeichnet, daß man zur gleichzeitigen Gewinnung von Vinylessigsäure und (-Butyrolacton einen Carbonsäureallylester mit überschüssigem Kohlenmonoxid und 3 bis 30 Mol Wasser, vorzugsweise 8 bis 20 Mol Wasser,pro Mol Allylester in Gegenwart eines Schwermetallkatalysators der VI II. Gruppe des Periodensystems umsetzt.The further development of the process for the production of vinyl acetic acid according to patent. ... ... (patent application P 22 17 534.4) is thus characterized by that one for the simultaneous production of vinyl acetic acid and (-butyrolactone a Carboxylic acid allyl ester with excess carbon monoxide and 3 to 30 mol of water, preferably 8 to 20 moles of water per mole of allyl ester in the presence of a heavy metal catalyst the VI II. group of the periodic table implements.
Als Schwermetallkatalysatoren kommen die Elemente Rhodium, Palladium, Iridium, Platin, Kobalt und Nickel sowie deren Gemische und Verbindungen in Betracht. Bevorzugt werden Rhodium, Palladium und Nickel in Form der Halogenide, wie besonders Chloride oder Jodide und deren Hydrate. Sie werden im allgemeinen -ia Mengen zwischen 0,02 und 3 g Schwermetall, vorzugsweise zwischen 0, 1 und 2 g Schwermetall pro Mol Allylester eingesetzt.The elements rhodium, palladium, Iridium, platinum, cobalt and nickel as well as their mixtures and compounds can be considered. Preference is given to rhodium, palladium and nickel in the form of the halides, such as especially Chlorides or iodides and their hydrates. They will generally be -ia amounts between 0.02 and 3 g heavy metal, preferably between 0.1 and 2 g heavy metal per mole Allyl ester used.
Als Allylester kommen diejenigen in Betracht, deren Säurerest keine Olefin-Bindung oder Acetylenbindung enthält und von einer gesättigten aliphatischen Carbonsäure mit 2 bis 18 Kohlenstoffatomen im Molekül oder von einer aromatischen Carbonsäure mit 7 bis 11 Kohlenstoff atomen im Molekül stammt. Wegen der leichten Zugänglichkeit ist Allylacetat neben Allylpropionat oder Allylisobutyrat bevorzugt.Suitable allyl esters are those whose acid radicals do not have any Contains olefin bond or acetylene bond and from a saturated aliphatic Carboxylic acid with 2 to 18 carbon atoms in the molecule or of an aromatic one Carboxylic acid with 7 to 11 carbon atoms in the molecule. Because of the light Allyl acetate is preferred in addition to allyl propionate or allyl isobutyrate.
Kohlenmonoxid wird in größerem molaren Überschuß und unter erhöhtem Druck zur Reaktion gebracht. Dabei sind die Grenzen des einzuhaltenden Druckbereichs sehr weit gespannt und liegen zwischen 5 und 500 atü, vorzugsweise zwischen 20 und 250 atü.Carbon monoxide is in greater molar excess and under increased Pressure reacted. The limits of the pressure range to be adhered to are here very wide and are between 5 and 500 atmospheres, preferably between 20 and 250 atm.
Die Reaktionstemperaturen liegen zwischen 800 und 2800C, vor-0 0 zugsweise zwischen 100 und 180 0.The reaction temperatures are between 800 and 2800C, preferably before-0 0 between 100 and 180 0.
Das erfindungsgemäße Verfahren kann wie das Verfahren gemäß Patent . ... ... (Patentanmeldung P 22 17 534.4) kontinuierlich oder diskontinuierlich betrieben werden. Dabei kann der Katalysator in der Reaktionsmischung gelöst-,suspendiert oder gegebenenfalls in Form eines Trägerkatalysators eingesetzt werden. Geeignete Trägerstoffe sind Kieselsäure, Zirkondioxid, Aluminiumoxid, Aktivkohle, Molsiebe.The method according to the invention can be like the method according to patent . ... ... (patent application P 22 17 534.4) continuously or discontinuously operate. The catalyst can be dissolved or suspended in the reaction mixture or optionally used in the form of a supported catalyst. Suitable Carriers are silica, zirconium dioxide, aluminum oxide, activated carbon, molecular sieves.
Das bei dem erfindungsgemäßen Verfahren gewonnene g-Butyrolacton wird als Vorprodukt zur Herstellung von Polyestern verwendet.The g-butyrolactone obtained in the process according to the invention is used as a preliminary product for the production of polyesters.
Beispiel 1 100 g Allylacetat, 1 g Rhodiumjodid und 200 g Wasser werden in einen mit Tantal ausgekleideten 1 l-Schüttelautoklaven gegeben. Man gibt Kohlenmonoxid bis zu einem Druck von 143 Atmosphären zu und heizt dann die Mischung unter stetem Schütteln innerhalb von 40 Minuten auf 1420C auf. Nach 115 Minuten wird der Versuch abgebrochen, die Reaktionslösung rasch abgekühlt und auf Normaldruck entspannt. Die Reaktionslösung enthält 27 g &-Butyrolacton und 13 g Vinylessigsäure.Example 1 100 g of allyl acetate, 1 g of rhodium iodide and 200 g of water are used placed in a 1 l shaking autoclave lined with tantalum. They give carbon monoxide up to a pressure of 143 atmospheres and then heats the mixture under constant Shake to 1420C within 40 minutes. After 115 minutes the attempt aborted, the reaction solution cooled rapidly and let down to normal pressure. The reaction solution contains 27 g of & -butyrolactone and 13 g of vinyl acetic acid.
Beispiel 2 200. g Allylacetat werden zusammen mit 360 g Wasser, 1 g RhC13 H20 und 2 g NiJ2 . 6 H20 in einen 1 l-Edelstahl-Schüttelautoklaven gegeben. Man gibt Kohlenmonoxid bis zu einem Druck von 126 Atmosphären zu und heizt unter Schütteln rasch auf 14500.Example 2 200 g of allyl acetate, together with 360 g of water, 1 g RhC13 H20 and 2 g NiJ2. 6 H20 were placed in a 1 l stainless steel shaking autoclave. Carbon monoxide is added up to a pressure of 126 atmospheres and the mixture is heated under Shake quickly to 14500.
Nach 2 Stunden wird das Reaktionsgemisch abgekühlt und analysiert. Es werden 51,6 g -Butyrolacton und 20,6 g Vinylessigsäure gefullden.After 2 hours the reaction mixture is cooled and analyzed. 51.6 g of butyrolactone and 20.6 g of vinyl acetic acid are filled.
Beispiel 3 114 g Allylpropionat werden zusammen mit 162 g Wasser und 0,9 g Palladiumchlorid in einem 1 l-Edelstahl-Schüttelautoklaven gegeben. Man gibt Kohlenmonoxid bis zu einem Druck 0 von 160 Atmosphären zu, heizt auf 159 C und hält diese Temperatur für 65 Minuten. Nach dem Abkühlen und Entspannen wird die Reaktionslösung gaschromatographisch analysiert. Sie enthält 18,7 g Butyrolacton und 11 g Vinylessgisäure.Example 3 114 g of allyl propionate together with 162 g of water and 0.9 g of palladium chloride was placed in a 1 l stainless steel shaking autoclave. One gives Carbon monoxide to a pressure of 0 of 160 atmospheres, heats to 159 C and holds this temperature for 65 minutes. After cooling and releasing the pressure, the reaction solution becomes analyzed by gas chromatography. It contains 18.7 g butyrolactone and 11 g vinylessgic acid.
Beispiel 4 Man arbeitet wie in Beispiel 3, setzt aber anstelle von Allylpropionat 128 g Allylisobutyrat ein und erhält 19,1 g dr-Butyrolacton und 10,6 g Vinylessigsäure.Example 4 You work as in Example 3, but instead of Allyl propionate 128 g of allyl isobutyrate and receives 19.1 g of dr-butyrolactone and 10.6 g vinyl acetic acid.
Beispiel 5 Man arbeitet wie in Beispiel 3, setzt aber anstelle von Allylpropionat 156 g Allylcapronat ein und erhält 16,6 g ;r-Butyrolacton und 11,8g Vinylessigsäure.Example 5 You work as in Example 3, but instead of Allyl propionate 156 g of allyl caproate and receives 16.6 g; r-butyrolactone and 11.8 g Vinyl acetic acid.
Beispiel 6 100 g Allylacetat werden, wie im Beispiel 1 angegeben, jedoch in Gegenwart von 4 g H2IrC16 anstelle von RhJ3 mit Kohlenmonoxid umgesetzt. Die gaschromatographische Analyse ergibt die Bildung von 6,2 g g-Butyrolacton und 10,2 g Vinylessigsäure.Example 6 100 g of allyl acetate are, as indicated in Example 1, but reacted with carbon monoxide in the presence of 4 g H2IrC16 instead of RhJ3. Gas chromatographic analysis shows the formation of 6.2 g of g-butyrolactone and 10.2 g of vinyl acetic acid.
Beispiel 7 162 g Allylbenzoat, 180 g Wasser und 25 g eines Trägerkatalysators, der auf 100 g Aktivkphle 1,65 g Rhodiumchlorid enthält, werden bei 145ort 45 Minuten lang Unter einem Kohlenmonoxid-Druck von 140 atü in einem 1 l-Tantalautoklaven geschüttelt. Nach Ablauf dieser Zeit wird das Reaktionsgemisch abgekühlt, entspannt und gaschromatographisch analysiert. Es werden 22,3 g FButyrolacton und 9 g Vinylessigsäure gefunden.Example 7 162 g of allyl benzoate, 180 g of water and 25 g of a supported catalyst, which contains 1.65 g of rhodium chloride per 100 g of activated active ingredient, 45 minutes at 145 ° Long shaken under a carbon monoxide pressure of 140 atm in a 1 l tantalum autoclave. After this time, the reaction mixture is cooled, let down and gas chromatographically analyzed. 22.3 g of butyrolactone and 9 g of vinyl acetic acid are found.
Beispiel 8 Man arbeitet wie in Beispiel 7, setzt aber anstelle des Benzoats 170 g des Allylesters der p-Toluylsäure ein. Man erhält 21.2 g ftButyrolacton und 8.8 g Vinylessigsäure.Example 8 Work as in Example 7, but instead of the Benzoate 170 g of the allyl ester of p-toluic acid. 21.2 g of ft-butyrolactone are obtained and 8.8 g of vinyl acetic acid.
Claims (7)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732303997 DE2303997A1 (en) | 1973-01-27 | 1973-01-27 | Vinyl acetic acid and butyrolactone prepn - by catalytic reaction of allyl alcohol, ethers or esters with carbon monoxide |
| CA168,421A CA1026355A (en) | 1972-04-12 | 1973-04-05 | PROCESS FOR THE MANUFACTURE OF VINYL ACETIC ACID AND OPTIONALLY OF .alpha.-BUTYROLACTONE |
| NL7304827A NL7304827A (en) | 1972-04-12 | 1973-04-06 | |
| CH506973A CH613181A5 (en) | 1972-04-12 | 1973-04-09 | |
| US05/348,992 US3980671A (en) | 1972-04-12 | 1973-04-09 | Process for the manufacture of vinyl acetic acid and optionally of γ-b |
| JP48040124A JPS497214A (en) | 1972-04-12 | 1973-04-10 | |
| GB1759973A GB1430415A (en) | 1972-04-12 | 1973-04-12 | Process for the manufacture of vinyl acetic acid and optionally of ypsilon-butyrolactone |
| FR7313221A FR2180021B1 (en) | 1972-04-12 | 1973-04-12 | |
| US05/666,313 US4140865A (en) | 1972-04-12 | 1976-03-12 | Process for the manufacture of vinyl acetic acid |
| CH1098278A CH617655A5 (en) | 1972-04-12 | 1978-10-24 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732303997 DE2303997A1 (en) | 1973-01-27 | 1973-01-27 | Vinyl acetic acid and butyrolactone prepn - by catalytic reaction of allyl alcohol, ethers or esters with carbon monoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2303997A1 true DE2303997A1 (en) | 1974-08-08 |
Family
ID=5870116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19732303997 Withdrawn DE2303997A1 (en) | 1972-04-12 | 1973-01-27 | Vinyl acetic acid and butyrolactone prepn - by catalytic reaction of allyl alcohol, ethers or esters with carbon monoxide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2303997A1 (en) |
-
1973
- 1973-01-27 DE DE19732303997 patent/DE2303997A1/en not_active Withdrawn
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