CH314487A - Process for the production of S-guaia gulets - Google Patents
Process for the production of S-guaia guletsInfo
- Publication number
- CH314487A CH314487A CH314487DA CH314487A CH 314487 A CH314487 A CH 314487A CH 314487D A CH314487D A CH 314487DA CH 314487 A CH314487 A CH 314487A
- Authority
- CH
- Switzerland
- Prior art keywords
- guaia
- reaction mixture
- water
- sulfur
- production
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000011541 reaction mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000001927 guaiacum sanctum l. gum oil Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 229960001867 guaiacol Drugs 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- FWKQNCXZGNBPFD-UHFFFAOYSA-N Guaiazulene Chemical compound CC(C)C1=CC=C(C)C2=CC=C(C)C2=C1 FWKQNCXZGNBPFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000147041 Guaiacum officinale Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001545 azulenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940091561 guaiac Drugs 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- TWVJWDMOZJXUID-QJPTWQEYSA-N guaiol Natural products OC(C)(C)[C@H]1CC=2[C@H](C)CCC=2[C@@H](C)CC1 TWVJWDMOZJXUID-QJPTWQEYSA-N 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/47—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing ten carbon atoms
- C07C13/52—Azulenes; Completely or partially hydrogenated azulenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/46—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with sulfur or a sulfur-containing compound as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/30—Azulenes; Hydrogenated azulenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von S Guajazulen
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von S-Guajazulen (I). Die ehemische Konstitution von 1 ist : durch Plattner und Mitarbeiter (Helv. 32, 4137, 2452, 2464 ; 1949) durch Synthese sichergestellt worden. Es handelt sieh um 1, 4-Dimethyl-7-isopropyl-azulen der Formel
EMI1.1
Während die Herstellung anderer Azulene durch Synthese oder ihre Gewinnung aus Na turprodukten sehr schwierig oder sehr kostspielig ist, gelingt es, I verhältnismässig einfaeh und aus einem preislich günstigen Rohmaterial, dem Guajakholzöl, herzustellen.
Die ehemischen Grundlagen dieses Verfahrens gehen aus einer Arbeit von Ruzieka und Mitarbeiter (Helv. 6, 855 ; 1923) hervor. Demnaeh erhält man aus dem Guajakholzöl durch Kochen mit Ameisensäure ein Produkt, dessen Dehydrierung mit Schwefel ein intensiv blau gefärbtes öl mit Siedepunkt 130 bis 1600 C bei 1. 2 mm ergibt, Das Verfahren gemäss Erfindung basiert auf dieser Methode und ist dadurch gekennzeichnet, dass man Guajakholzöl in Gegenwart von Sehwefel auf max.
220 C erhitzt und das Reaktionsgemisch anschliessend destilliert, wobei ein etwa 20 /e Gsuaaazulen enthaltendes Produkt erhalten wird.
Zweelmässigerweise wird wie folgt vorgegangen :
10 kg Guajakholz¯l werden in einem Behälter mit 3-4 kg Schwefel auf 130 C erwärmt. Von dieser Temperatur an wird die Erwärmung sehr langsam fortgesetzt, bis eine spontane Temperatursteigerung im Reaktions- gemisch bemerkbar wird. Bei max. 220 C wird die Heizung entfernt und ein Stickstoff- strom in das Reaktionsgefäss eingeleitet.
Zwei Reaktionen laufen nebeneinander ab : Die Wasserabspaltung aus dem tertiären, im Guajakholzol enthaltenen Alkohol Guajol unter Bildung von Guajen und die Dehydrierung desselben zu I gemäss der Reaktion :
EMI1.2
EMI2.1
Der Stiekstoffstrom dient zum leichteren Abtreiben des Wasserdampfes, welcher sonst ein lästiges Stossen und. Spritzen im Reaktionsgemiseh hervorrufen würde. Zudem muss das Reaktionsgefäss überall eine Temperatur über 100 aufweisen, damit kein Kondenswasser in das Reaktionsgemiseh zurüekfliessen kann.
Die Entfernung von Wasserdampf kann statt durch Einleitung von Stickstoff auch durch ein geringes Vakuum von 200-400 mm er leichtert werden ; das Vakuum darf aber nicht so hoeh sein, dass Teile des Reaktionsgemisches zu destillieren beginnen. Mit dem Wasser- dampf zusammen entsteht durch die Dehydrierung aueh Schwefelwasserstoff, welcher in Wasehgefässen oder Trockentürmen als Alkali-, Erdalkali-oder Metallsulfid gebunden wird.
Die spontane Temperatursteigerung im Reaktionsgemisch hört bald auf, und die Heizung wird fortgesetzt bis zu max. 220 C. Die Heizung wird so reguliert, dass die gleich- mässige Entwicklung von Schwefelwasserstoff gesichert wird. Wenn die Gasentwieklung auf- hört, wird die Heizung abgestellt, bis die Temperatur auf etwa 120 C sinkt. Jetzt wird das Reaktionsgemisch unter Vakuum, bei 1 bis 20 mm abdestilliert. Als Destillat wird ein tiefblaues Öl gewonnen, 6-7 kg mit etwa 20 Gehalt an I.
Das Destillat wird in der fünf-bis zehnfaehen Menge Petroläther gelöst, mit Natronlauge von sulfidartigen Ver unreinigungen befreit und mit Wasser neutral gewaschen. Nachher wird die Petroläther- lösung mit 10-15 Liter 62 /Nger Schwefel- säure intensiv durchgemiseht, bis das Azulen in Form einer Additionsverbindung von der Säure aufgenommen ist und der Petroläther die blaue Farbe verliert. Die Verbindung I befindet sieh nun von Nebenprodukten und Verunreinigungen befreit in der Sehwefel- säure.
Dieser wird nun unter energischem Rühren so viel Eis und Natronlauge zugefügt, dass als Endergebnis eine etwa 7 /oige, mit Natriumsulfat gesättigte Schwefelsäure entsteht. Dureh die Verdünnung wird das Azulen aus der Additionsverbindung freigesetzt und befindet sieh nun in Form einer Emulsion.
Aus dieser Emulsion wird das Azulen mit 5 bis 10 Liter reinem Petroläther ausgezogen und nach der Regenerierung des Petroläthers destilliert. Bis auf einen lleinen Vor-und Naehlauf destilliert das reine I bei 167 bis 169 C lmter 12mm Vakuum. Die Ausbeute beträgt je nach Qualität des verwendeten Guajakholzols 10-15"Ah
Bei dem Verfahren gemäss Erfindung wird also die Wasserabspaltung und die Dehydrierung in einem Arbeitsgang durehgeführt. Die erzielte Ausbeute ist gleich oder höher als bei der Herstellung in zwei Stufen. Die Reinigungsoperationen können in einer Sehüttel vorriehtung durehgeführt werden.
Als Endprodukt wird durch Destillation reines (99"/) Guajazulen gewonnen.
Process for the preparation of S guaia gulets
The present invention relates to a process for the preparation of S-guaia gulins (I). The former constitution of 1 is: by Plattner and coworkers (Helv. 32, 4137, 2452, 2464; 1949) secured by synthesis. It is about 1,4-dimethyl-7-isopropyl-azulene of the formula
EMI1.1
While the production of other azulenes by synthesis or their extraction from natural products is very difficult or very expensive, it is possible to produce I relatively easily and from an inexpensive raw material, guaiac wood oil.
The former basis of this process is based on a work by Ruzieka and colleagues (Helv. 6, 855; 1923). Accordingly, a product is obtained from the guaiac wood oil by boiling with formic acid, the dehydration of which with sulfur gives an intensely blue-colored oil with a boiling point of 130 to 1600 C at 1.2 mm. The method according to the invention is based on this method and is characterized in that Guaiac wood oil in the presence of sulfur to max.
220 ° C. and the reaction mixture is then distilled, a product containing about 20% of Gsuaaazulen being obtained.
The procedure is as follows:
10 kg of guaiac wood are heated to 130 ° C. in a container with 3-4 kg of sulfur. From this temperature on, the heating is continued very slowly until a spontaneous increase in temperature is noticeable in the reaction mixture. At max. The heating is removed at 220 ° C. and a stream of nitrogen is introduced into the reaction vessel.
Two reactions take place side by side: the elimination of water from the tertiary alcohol guajol contained in the guaiac wood oil with the formation of guaiene and the dehydrogenation of the same to I according to the reaction:
EMI1.2
EMI2.1
The nitrogen stream serves to facilitate the expulsion of the water vapor, which would otherwise be an annoying puff and. Would cause splashing in the reaction mixture. In addition, the reaction vessel must have a temperature above 100 everywhere so that no condensation can flow back into the reaction mixture.
The removal of water vapor can also be facilitated by a low vacuum of 200-400 mm instead of by introducing nitrogen; however, the vacuum must not be so high that parts of the reaction mixture begin to distill. Together with the steam, the dehydrogenation also produces hydrogen sulfide, which is bound in washing vessels or drying towers as alkali, alkaline earth or metal sulfide.
The spontaneous increase in temperature in the reaction mixture soon stops, and heating is continued up to max. 220 C. The heating is regulated in such a way that the even development of hydrogen sulfide is ensured. When the evolution of gas stops, the heating is switched off until the temperature drops to around 120 ° C. The reaction mixture is now distilled off in vacuo at 1 to 20 mm. A deep blue oil is obtained as a distillate, 6-7 kg with about 20 I.
The distillate is dissolved in the five to tenfold amount of petroleum ether, freed of sulfide-like impurities with sodium hydroxide solution and washed neutral with water. Then the petroleum ether solution is mixed thoroughly with 10-15 liters of 62 / Nger sulfuric acid until the azulene has been absorbed by the acid in the form of an addition compound and the petroleum ether loses its blue color. Compound I is now freed from by-products and impurities in the sehulphuric acid.
With vigorous stirring, enough ice and sodium hydroxide solution are then added to this that the end result is about 7% sulfuric acid saturated with sodium sulfate. Through the dilution, the azulene is released from the addition compound and is now in the form of an emulsion.
The azulene is extracted from this emulsion with 5 to 10 liters of pure petroleum ether and distilled after the petroleum ether has been regenerated. With the exception of a small fore and aft run, the pure I distills at 167 to 169 C lmter 12 mm vacuum. The yield is 10-15 "Ah, depending on the quality of the guaiac wood oil used
In the method according to the invention, the elimination of water and the dehydration are carried out in one operation. The yield achieved is the same as or higher than in the case of production in two stages. The cleaning operations can be carried out in a shaker.
Pure (99 ") guaia gulene is obtained as the end product by distillation.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH314487T | 1953-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH314487A true CH314487A (en) | 1956-06-15 |
Family
ID=4495616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH314487D CH314487A (en) | 1953-01-29 | 1953-01-29 | Process for the production of S-guaia gulets |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH314487A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4047003A1 (en) | 2021-02-18 | 2022-08-24 | UMICORE AG & Co. KG | Metal complexes with 4-h-, 6-h- or 8-h-dihydroazulenyl ligands and their use |
| WO2022175112A1 (en) | 2021-02-18 | 2022-08-25 | Umicore Ag & Co. Kg | Noble metal complexes with dihydroazulenyl ligands and use thereof |
| EP4098643A1 (en) | 2021-06-01 | 2022-12-07 | UMICORE AG & Co. KG | Precious metal complexes with dihydroguajazulenyl ligands and their use |
-
1953
- 1953-01-29 CH CH314487D patent/CH314487A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4047003A1 (en) | 2021-02-18 | 2022-08-24 | UMICORE AG & Co. KG | Metal complexes with 4-h-, 6-h- or 8-h-dihydroazulenyl ligands and their use |
| WO2022175111A1 (en) | 2021-02-18 | 2022-08-25 | Umicore Ag & Co. Kg | Metal complexes having 4-h, 6-h or 8-h dihydroazulenyl ligands and use thereof |
| WO2022175112A1 (en) | 2021-02-18 | 2022-08-25 | Umicore Ag & Co. Kg | Noble metal complexes with dihydroazulenyl ligands and use thereof |
| EP4098643A1 (en) | 2021-06-01 | 2022-12-07 | UMICORE AG & Co. KG | Precious metal complexes with dihydroguajazulenyl ligands and their use |
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