DE1147937B - Process for the production of linalyl acetate - Google Patents
Process for the production of linalyl acetateInfo
- Publication number
- DE1147937B DE1147937B DED33274A DED0033274A DE1147937B DE 1147937 B DE1147937 B DE 1147937B DE D33274 A DED33274 A DE D33274A DE D0033274 A DED0033274 A DE D0033274A DE 1147937 B DE1147937 B DE 1147937B
- Authority
- DE
- Germany
- Prior art keywords
- linalyl acetate
- linalool
- acetate
- production
- ketene
- 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.)
- Pending
Links
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 title claims description 34
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 32
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 16
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims description 16
- 229930007744 linalool Natural products 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 241000158147 Sator Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000008451 emotion Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 6
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 6
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 5
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Linalylacetat. Dieses Verfahren ist dadurch gekennzeichnet, daß man Linalool bei einer Temperatur unter 30° C in Gegenwart eines sauren Veresterungskatalysators mit Keten in Berührung bringt.The invention relates to a process for the production of linalyl acetate. This procedure is thereby characterized in that one linalool at a temperature below 30 ° C in the presence of an acidic esterification catalyst brings in contact with keten.
Das Verfahren kann zweckmäßigerweise durchgeführt werden, indem man Keten in ein Reaktionsgefäß einleitet, das das Linalool und den sauren Veresterungskatalysator enthält. Der saure Veresterungskatalysator kann z. B. p-Toluolsulfonsäure oder Schwefelsäure sein.The process can conveniently be carried out by introducing ketene into a reaction vessel containing the linalool and the acidic esterification catalyst contains. The acidic esterification catalyst can, for. B. p-toluenesulfonic acid or sulfuric acid.
Das hergestellte Linalylacetat kann isoliert werden, indem man das Verfahrensprodukt nach Neutralisieren des sauren Veresterungskatalysators abdestilliert.The linalyl acetate produced can be isolated by neutralizing the process product of the acidic esterification catalyst is distilled off.
In der USA.-Patentschrift 2 794 826 wird ebenfalls die Herstellung von Linalylacetat beschrieben. Bei diesem bekannten Verfahren wird jedoch jeweils eine Mischung von Linalylacetat und Geranylacetat erhalten, die anschließend durch fraktionierte Destillation getrennt werden muß. Diese destillative Trennung ist auf Grund der verhältnismäßig ähnlichen Siedepunkte der beiden Verbindungen nicht sehr einfach, und es werden daher nach dem bekannten Verfahren nur geringere Ausbeuten an reinem Linalylacetat erhalten, als es erfindungsgemäß möglich ist.US Pat. No. 2,794,826 also describes the preparation of linalyl acetate. at this known process, however, a mixture of linalyl acetate and geranyl acetate is obtained in each case, which must then be separated by fractional distillation. This separation by distillation is not very easy due to the relatively similar boiling points of the two compounds, and it therefore only lower yields of pure linalyl acetate are obtained by the known process, than is possible according to the invention.
Linalylacetat ist als brauchbares Parfümierungsmittel bekannt.Linalyl acetate is known to be a useful perfuming agent.
In den nachfolgenden Beispielen sind die angeführten Prozentsätze Gewichtsprozente.In the following examples, the percentages given are percentages by weight.
Verfahren zur Herstellung
von LinalylacetatMethod of manufacture
of linalyl acetate
Es wurde Keten in ein Reaktionsgefäß geleitet, das auf 20° C gehalten wurde und 100 Gewichtsteile Linalool sowie 1 Gewichtsteil p-Toluolsulfonsäure enthielt. Keten und Linalool reagierten miteinander und lieferten Linalylacetat.Ketene was passed into a reaction vessel kept at 20 ° C. and 100 parts by weight of linalool and 1 part by weight of p-toluenesulfonic acid. Keten and Linalool reacted with each other and provided linalyl acetate.
Bei der Reaktion wurden 0,83 Mol Keten pro Mol Linalool absorbiert. Die Umwandlung des Linalools in Linalylacetat betrug 73,5 °/o; die Ausbeute an Linalylacetat war 86,5%, bezogen auf das verbrauchte Linalool. Es wurde kein Geranylacetat festgestellt.In the reaction, 0.83 moles of ketene was absorbed per mole of linalool. The transformation of the linalool in linalyl acetate was 73.5%; the yield of linalyl acetate was 86.5% based on the consumed Linalool. No geranyl acetate was found.
Das Verfahren des Beispiels 1 wurde wiederholt, wobei 500 Gewichtsteile Linalool und 5 Gewichtsteile p-Toluolsulfonsäure verwendet wurden.The procedure of Example 1 was repeated, using 500 parts by weight of linalool and 5 parts by weight p-Toluenesulfonic acid were used.
Bei der Reaktion wurden 0,8 Mol Keten pro Mol Linalool absorbiert. Die Ausbeute an Linalylacetat betrug 84%, bezogen auf das verbrauchte Linalool. Es wurde kein Geranylacetat festgestellt.In the reaction, 0.8 moles of ketene was absorbed per mole of linalool. The yield of linalyl acetate was 84%, based on the linalool consumed. No geranyl acetate was found.
Anmelder:Applicant:
The Distillers Company Limited,
Edinburgh (Großbritannien)The Distillers Company Limited,
Edinburgh (Great Britain)
Vertreter: Dr. W. Schalk, Dipl.-Ing. P. Wirth,Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,
Dipl.-Ing. G. E. M. DannenbergDipl.-Ing. G. E. M. Dannenberg
und Dr. V. Schmied-Kowarzik, Patentanwälte,and Dr. V. Schmied-Kowarzik, patent attorneys,
Frankfurt/M., Große Eschenheimer Str. 39Frankfurt / M., Große Eschenheimer Str. 39
Beanspruchte Priorität:
Großbritannien vom 7. Mai 1959 (Nr. 15 629)Claimed priority:
Great Britain 7 May 1959 (No. 15 629)
Peter Nayler, Willerby, East YorkshirePeter Nayler, Willerby, East Yorkshire
(Großbritannien),
ist als Erfinder genannt worden(Great Britain),
has been named as the inventor
Das Verfahren des Beispiels 1 wurde wiederholt, wobei jedoch das Reaktionsgefäß, das das Linalool und die p-Toluolsulfonsäure enthält, auf einer Temperatur von 0° C gehalten wurde.The procedure of Example 1 was repeated, however, the reaction vessel containing the linalool and p-toluenesulfonic acid is at one temperature was kept at 0 ° C.
Keten und Linalool reagierten miteinander und lieferten Linalylacetat; es wurde weder Geraniol noch Geranylacetat festgestellt.Ketene and linalool reacted to give linalyl acetate; it was neither geraniol nor Geranyl acetate noted.
Im Gegensatz zu diesen das erfindungsgemäße Verfahren erläuternden Beispielen bestand das Produkt, das durch Einführung von Keten in ein auf 50° C gehaltenes Reaktionsgefäß, das 250 Gewichtsteile Linalool und 2,5 Gewichtsteile p-Toluolsulfonsäure enthielt, erhalten wurde, aus einer Mischung von Linalool, Linalylacetat, Geranylacetat, Dehydratisierungsprodukten und hochsiedenden Harzen.In contrast to these examples illustrating the process according to the invention, the product that by introducing ketene into a kept at 50 ° C Reaction vessel containing 250 parts by weight of linalool and 2.5 parts by weight of p-toluenesulfonic acid, obtained from a mixture of linalool, linalyl acetate, geranyl acetate, dehydration products and high boiling resins.
Die Ausbeute an Linalylacetat betrug nur 32,5 %, bezogen auf das verbrauchte Linalool. Die Trennung des Geranyl- und Linalylacetats konnte nur mittels sorgfältiger Destillation erzielt werden.The yield of linalyl acetate was only 32.5%, based on the linalool consumed. The separation the geranyl and linalyl acetate could only be obtained by careful distillation.
309 578/279309 578/279
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1147937X | 1959-05-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1147937B true DE1147937B (en) | 1963-05-02 |
Family
ID=10877701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED33274A Pending DE1147937B (en) | 1959-05-07 | 1960-05-05 | Process for the production of linalyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1147937B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019121453A1 (en) | 2017-12-18 | 2019-06-27 | Basf Se | Preparation of acetate compounds via a ketene compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2794826A (en) * | 1952-11-18 | 1957-06-04 | Process of manufacturing linalyl | |
| GB788303A (en) * | 1954-08-27 | 1957-12-23 | Hoffmann La Roche | A novel acetoacetate and a process for the manufacture thereof |
-
1960
- 1960-05-05 DE DED33274A patent/DE1147937B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2794826A (en) * | 1952-11-18 | 1957-06-04 | Process of manufacturing linalyl | |
| GB788303A (en) * | 1954-08-27 | 1957-12-23 | Hoffmann La Roche | A novel acetoacetate and a process for the manufacture thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019121453A1 (en) | 2017-12-18 | 2019-06-27 | Basf Se | Preparation of acetate compounds via a ketene compound |
| US11091424B2 (en) | 2017-12-18 | 2021-08-17 | Basf Se | Preparation of acetate compounds via a ketene compound |
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