DE1543902A1 - Process for the production of organic products - Google Patents
Process for the production of organic productsInfo
- Publication number
- DE1543902A1 DE1543902A1 DE19661543902 DE1543902A DE1543902A1 DE 1543902 A1 DE1543902 A1 DE 1543902A1 DE 19661543902 DE19661543902 DE 19661543902 DE 1543902 A DE1543902 A DE 1543902A DE 1543902 A1 DE1543902 A1 DE 1543902A1
- Authority
- DE
- Germany
- Prior art keywords
- hydrogenation
- production
- organic products
- catalysts
- products
- 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
Classifications
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- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von organischen Prdulcten Die vorliegende Erfindung betrifft ein @-rf@hr@n zur Herstellung von perhydrierten oder auch partiell hydrieten Produkten der nachstehendenFormel in der @n eine ganze Zahl im Bereich von 1 bis 17 bedeutet und nachstehende Bezeichnungen folgendes : y'*undX'=tetrahydrofuranyloderfuranyl X'oder X'= CH OH oder 0 und/oder Z = (CH2)n iso (CH (CH2) n (CH-CH) iso (CH2) n (CH = CH)n Es ist bekannt olefinische ,aromatische, quasiaromatische Ketone zu den entsprechenden perhydrierten oder partiell hydrierten Reaktionsprodukten zu hydrieren. Dabei können die Üblichen Hydrierkt-. r gtoran sowie Metalle der IV. Nebengruppe, gegebenenfalls mit Zuschlägen der I. Gruppe angewandt werden. Solche Hydrierungsreaktionen lassen sich auch an Furfuryliden-und Difurfurylldenketonen anwenden. Bisher wurden solche Hydrierungen überwiegend in alkoholischer Lösung durchgeführt. der ITachteil dieser Verfahren besteht darin, da3 zusatzliche Aufarbeitungslmaßnahmen, wie z. B. Entfernen des Lösungsmittels, erforderlich werden. Mit don Hydriervorgang sind exotherme Wärmetonungen verbunden (Hydrierwärme). Diese läßt sich beim bekannten Verfahren 'nur ungünstig abführen.Process for the production of organic products The present invention relates to a @ -rf @ hr @ n for the production of perhydrated or partially hydrated products of the formula below in which @n denotes an integer in the range from 1 to 17 and the following designations: y '* andX' = tetrahydrofuranyloderfuranyl X 'or X' = CH OH or 0 and / or Z = (CH2) n iso (CH (CH2 ) n (CH-CH) iso (CH2) n (CH = CH) n It is known to hydrogenate olefinic, aromatic, quasi-aromatic ketones to the corresponding perhydrogenated or partially hydrogenated reaction products Subgroup IV, optionally with additions from Group I. Such hydrogenation reactions can also be used on furfurylidene and difurfuryl denetones. Up to now, such hydrogenations have been carried out predominantly in alcoholic solution. B. Removal of the solvent. The hydrogenation process is associated with exothermic heat generation (heat of hydrogenation), which can only be dissipated in an unfavorable manner in the known process to lead.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von organischen Verbindungen der eingangs genannten Formel durch Hydrierung von Furfuryliden-oder Difurfurylidenketonen.The invention relates to a process for the production of organic Compounds of the formula mentioned at the outset by hydrogenation of furfurylidene or Difurfurylidene ketones.
Das Verfahren besteht darln, daß man als Lösungsmittel bei der DurchfUhrung der Reaktion eine Verbindung verwendet, die der eingangs genannten allgemeinen Formel entaprichtt FUr die vorliegende Erfindung ist also wesentliche daß man systemeigene Losungsmittel anwendet. Als solche kommen in Betracht Difuranylalkanone, Furanylalkanone, Difuranylalkanole, Furanylalkanole, Di-tetrahydrofuranylalkanone, Di-tetrahydrofuranylalkanole. Die vorgenannten Losungsmittel kUnnen universel eirigesetzt werden. Das bedeutete daß man bei der Perhydrierung partiell hydrierte Produkte im vorgenannten Sinne, aber auch das perhydrierte Produkt selbst als Lösungsmittel verwenden kann. Anderseits kann man bei einer partielle Hydrierung ein perhydriertes Produkt oder ein partiell hydriertes Produkt, dieses gleichfalls im vorgenannten Sinne, als Lösungsmittel verwenden.The method consists darln that one as a solvent in the implementation the reaction uses a compound that corresponds to the general formula mentioned at the outset For the present invention it is essential that one is native to the system Solvent applies. Difuranylalkanones, furanylalkanones, Difuranyl alkanols, furanyl alkanols, di-tetrahydrofuranyl alkanols, di-tetrahydrofuranyl alkanols. The aforementioned solvents can be used universally. That meant that in the perhydrogenation partially hydrogenated products in the aforementioned sense, but can also use the perhydrogenated product itself as a solvent. On the other hand a perhydrogenated product or a partial hydrogenation can be used in the case of partial hydrogenation hydrogenated product, this also in the aforementioned sense, as a solvent use.
Als Katalysatoren sind alle als Bydrierkatalysatoren bekanrlten Stoffe verwendbar. Es kommen also die im einleitenden Absatz genannten Katalysatoren in Betracht. Besonders bevorzugt ist die Verwendung von Nickel auf den üblichen Trägersubstanzen von Aluminiumoxyd, Bimmstein, Kohle usw. aber auch Nickelmiscrkatalysatoren wie z. B. Nickel-Chromoxyd auf den bekannten Trägermaterialien sind gut geeignet.All substances known as hydrogenation catalysts are used as catalysts usable. The catalysts mentioned in the introductory paragraph come in Consideration. The use of nickel on the usual carrier substances is particularly preferred of aluminum oxide, pumice stone, coal, etc., but also nickel mix catalysts such as z. B. nickel-chromium oxide on the known carrier materials are well suited.
Speziell fUr die Perhydriertzs ist es zweckmäßig, vcr aliel-n Edelmetallkatalysatoren zu verwenden. Diese Kontakte ermöglichen es, in einer Stufe unmittelbar bis zum perhydrierten Reaktionsprodukt zu gelangen. Die anderen Hydrierkatalysatoren ermöglichen es, Hydrierungsstufen einzuhalten, wie z. B. die partielle Hydrierung zum Furanyl-oder zum Difuranylalkanon nowie zum Difuranylalkanol als auch dem Furanylalkanol.Especially for perhydration it is advisable to use many noble metal catalysts to use. These contacts make it possible to go straight to the to arrive perhydrogenated reaction product. The other hydrogenation catalysts allow it to adhere to hydrogenation stages, such as. B. the partial hydrogenation to the furanyl or to the difuranylalkanone nowie to the difuranylalkanol and the furanylalkanol.
Katalysatoren dieser Art sind beispielsweise das genannte Niokel allein auf TrKgern, oder Kupferchromitkatalysatoren. Catalysts of this type are, for example, the aforementioned Niokel alone on carriers, or copper chromite catalysts.
Allgemein soll die Hydrierungstemperatur zwisahen 0 und 180 °C liegen. Will aan speziell zu partiell hydrierten Produkten gelangen, so ist bevorzugt der Temperaturbereich von 0 -50 °C einzuhalten. Bei der Perhydrierung wird man die hdheren Temperaturen im vorgenannten Bereich wählen. In general, the hydrogenation temperature should be between 0 and 180 ° C. If aan especially wants to arrive at partially hydrogenated products, the is preferred Maintain a temperature range of 0 -50 ° C. In the case of perhydration, one becomes the harder Select temperatures in the aforementioned range.
Als Druckbereich ist höherer Druck im Bereich bis zu 500 atü zweckmäßig, bevorzugt 10-300 atü. A higher pressure in the range up to 500 atü is appropriate as a pressure range, preferably 10-300 atm.
B e i s p i e l e 1. 214 Difurfurylidenaceton (1 Mol) vom Fp 60-610C werdeii nit 2 Mol (456 g) 1, 5 Bis-(Tetrahydrofuranyl5-pentanol-3 gelöst. Als Katalysator werden eingesetzt 10 Kol % Raney-Nickel. EXAMPLE 1. 214 difurfurylidene acetone (1 mol), mp 60-610C 1.5 bis (tetrahydrofuranyl5-pentanol-3) are dissolved with 2 mol (456 g). As a catalyst 10 col% Raney nickel are used.
Der Versuch wird in einem Autoklaven von 2 l Inhalt gefuhrt. werden 7 Mol Wasserstoff bei 150 atü und einem Temperaturbereich von 20-120°C aufgedrückt. Die Hydierzeit beträgt 3 Stunden. Man erhält in 90-%iger Ausbeute 1,5-Bis-(tetrahydrcfuranyl)-pentanol-3'Aus diesem Produkt braucht durch einfache Separation lediglich der Katalysator entfernt zu werden. Eine nachfolgende Destillation ist nicht erforderl. ich, da das Produkt einen sehr hohen Reinheitsgrad aufweist. The experiment is carried out in an autoclave with a capacity of 2 l. will 7 mol of hydrogen at 150 atmospheres and a temperature range of 20-120 ° C. are applied. The hydrogenation time is 3 hours. 1,5-Bis- (tetrahydrcfuranyl) -pentanol-3'Aus is obtained in 90% yield This product only needs to remove the catalyst by simple separation to become. A subsequent distillation is not necessary. i since the product has a very high degree of purity.
2. Nach Verfahren 1 werden 242 g =1 Mol 4-Äthyl-difurfurylidenaceton in 486 g = 2 Mol 4-Athyl-difuranyl-pentadien-1, 4-on-3 mit 10 % Kupferchromit, bezogen auf die eingesetzte Vengez bei 120°C und 100 atü hydriert. In 95 %-iger Ausbeute entsteht 4-Äthyl-difurwanyl-pentadien-1,4-ol-3.2. According to method 1, 242 g = 1 mole of 4-ethyl-difurfurylidene acetone in 486 g = 2 mol of 4-ethyl-difuranyl-pentadiene-1,4-one-3 with 10% copper chromite, based hydrogenated to the used Vengez at 120 ° C and 100 atm. In 95% yield 4-ethyl-difurwanyl-pentadien-1,4-ol-3 is formed.
Wie bei Verfahren 1 werden 176 g 1-Furanyl-5-methyl-hexadien-1,4-on-3 in 558 g = 3 Mol 1-Tetrahydrofuranyl-5-methyl-hexanol-3 gelöst und mit 10 Mol Mickel auf Kieselgur bei 50°C und 5 atü hydrier. Als partiell hydriertes Produkt erhält man in 90-piger husbeute nach destillativer Trennung im Vakuurr das 1-Furanyl-5-methyl-hexanon-3.As in Method 1, 176 g of 1-furanyl-5-methyl-hexadien-1,4-one-3 dissolved in 558 g = 3 mol of 1-tetrahydrofuranyl-5-methyl-hexanol-3 and with 10 mol of Mickel hydrogenated on kieselguhr at 50 ° C and 5 atm. Obtained as a partially hydrogenated product 1-furanyl-5-methyl-hexanone-3 is obtained in 90-piger husks after separation by distillation in vacuo.
4. Entsprechend der,-, Verfahren nach 1 hydriert man 216 g = 1 Mol 2-Furfuryliden-3,3,3-trimethyl-cyclohexen-5-on-1 und 2 Hol = 452 g 2-Tetrahydrofurfuryl-335-trimethyl-cyolohexanol-1mit02% Platin auf Kchie bezogen auf die eingesetzte Menge der ungesättigtenVerbindung, bei 75°C und 6 atü. Nach 5-stündiger Reaktion erhält rr. an das hydrierte Produkt in 88-iger kusbeute.4. According to the, -, process according to 1, 216 g = 1 mol are hydrogenated 2-furfurylidene-3,3,3-trimethyl-cyclohexen-5-one-1 and 2 Hol = 452 g of 2-tetrahydrofurfuryl-335-trimethyl-cyolohexanol-1 with 02% Platinum in terms of the amount of unsaturated compound used, at 75 ° C and 6 atm. After 5 hours of reaction, rr. to the hydrogenated product in 88 kus loot.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DESC039156 | 1966-06-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1543902A1 true DE1543902A1 (en) | 1970-04-30 |
Family
ID=7435024
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19661543902 Pending DE1543902A1 (en) | 1966-06-22 | 1966-06-22 | Process for the production of organic products |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1543902A1 (en) |
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1966
- 1966-06-22 DE DE19661543902 patent/DE1543902A1/en active Pending
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