DE1165592B - Process for the production of fluorenone by the oxidation of fluorene - Google Patents
Process for the production of fluorenone by the oxidation of fluoreneInfo
- Publication number
- DE1165592B DE1165592B DER30779A DER0030779A DE1165592B DE 1165592 B DE1165592 B DE 1165592B DE R30779 A DER30779 A DE R30779A DE R0030779 A DER0030779 A DE R0030779A DE 1165592 B DE1165592 B DE 1165592B
- Authority
- DE
- Germany
- Prior art keywords
- fluorene
- oxidation
- fluorenone
- production
- nitric acid
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
- C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
- C07C49/675—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system having three rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Fluorenon durch Oxydation von Fluoren Es ist bekannt, Fluoren durch Oxydation in Fluorenon umzuwandeln. Hierfür sind katalytische Verfahren vorgeschlagen worden (vergleiche z. B.Process for the production of fluorenone by the oxidation of fluorene It is known to convert fluorene into fluorenone by oxidation. For this are catalytic Procedure has been proposed (see e.g.
USA.-Patentschriften 1 764023, 1 892768), denen zufolge Fluoren bei 300 bis 500O C über Kontakten mit Luft behandelt wird. Dabei tritt aber zum Teil Bildung von Phthal- und Maleinsäureanhydrid ein, also Aufspaltung des Fluorenmoleküls. Die Oxydation mittels Selendioxyd ist umständlich und unwirtschaftlich. Bei der Oxydation mittels Kaliumbichromat ist die Anwendung eines erheblichen Überschusses an Oxydationsmittel und das Arbeiten in Eisessig notwendig (vgl. Beilsteins Handbuch der organischen Chemie, 4.Auflage, VII.Band, 5. 465; ferner Chemisches Zentralblatt, 1956, S. 3318).USA. Patents 1 764023, 1 892768), according to which fluorene in 300 to 500O C is treated through contacts with air. But this occurs in part Formation of phthalic and maleic anhydride, i.e. splitting of the fluorene molecule. The oxidation by means of selenium dioxide is cumbersome and uneconomical. In the Oxidation by means of potassium dichromate is the application of a considerable excess of oxidizing agents and working in glacial acetic acid is necessary (see Beilstein's handbook of organic chemistry, 4th edition, VII. Volume, 5. 465; also Chemisches Zentralblatt, 1956, p. 3318).
Es wurde nun gefunden, daß man die Oxydation des Fluorens in betrieblich einfacher Weise und mit guten Ausbeuten mittels verdünnter wäßriger Salpetersäure durchführen k-ann, ohne daß eine merkliche Aufspaltung zu beobachten ist. Eine Nitrierung tritt nur in untergeordnetem Maße ein, die entstehenden Nebenprodukte lassen sich durch einfache Vakuumdestillation vom entstandenen Fluorenon trennen, das so unmittelbar in reiner Form erhalten wird. It has now been found that the oxidation of fluorene can be carried out on an operational basis easily and with good yields using dilute aqueous nitric acid can be carried out without any noticeable splitting. A nitration occurs only to a minor extent, the by-products formed can be separate from the fluorenone formed by simple vacuum distillation, this immediately is obtained in pure form.
Beispiel Fluoren wird mit der zur Fluorenonbildung notwendigen Menge etwa 100/oiger Salpetersäure, von der ein etwa 100/oiger Überschuß eingesetzt wird, im Autoklav auf 2000 C etwa 2 Stunden erhitzt, wobei sich ein Druck von ungefähr 55 atü einstellt. Das Verhältnis HNOS zu Fluoren vor Beginn der Reaktion wird zweckmäßig auf 2,1: 3 eingestellt. Nach beendeter Reaktion wird der Autoklavinhalt mit etwa 1000 C Temperatur entleert, die wäßrige Phase abgetrennt und der ölige, unterhalb 1000 C festwerdende Anteil im Vakuum destilliert. Nach Abnahme eines Vorlaufes (etwa 20/0) erhält man bei 10 bis 12 mm eine Hauptfraktion bei 195 bis 1960 C, die aus Fluorenon vom Fp. 82 bis 830 C (98 bis 100°/o rein) besteht. Die Ausbeute beträgt 78 O/o. Der Destillationsrückstand enthält etwa 12 0/o 2-Nitrofluorenon und etwa 7 ovo verkokte Anteile. Example Fluorene is used in the amount necessary for the formation of fluorenone about 100% nitric acid, of which about 100% excess is used, heated in the autoclave to 2000 C for about 2 hours, with a pressure of about 55 atü is set. The ratio of HNOS to fluorene before the start of the reaction becomes appropriate set to 2.1: 3. After the reaction has ended, the contents of the autoclave are approx 1000 C emptied temperature, the aqueous phase separated and the oily, below 1000 C solidified portion distilled in vacuo. After accepting a preliminary run (approx 20/0), at 10 to 12 mm, a main fraction at 195 to 1960 C is obtained, the one from Fluorenone has a melting point of 82 to 830 ° C. (98 to 100% pure). The yield is 78 O / o. The distillation residue contains about 12 0 / o 2-nitrofluorenone and about 7 ovo coked shares.
Die nach der Oxydation abgetrennte wäßrige Salpetersäure hat die Dichte 1,005 = 1,250/oig; sie kann nach Aufkonzentrierung mit starker HNOS wieder zu weiteren Ansätzen verwendet werden. The aqueous nitric acid separated off after the oxidation has the Density 1.005 = 1.250 / oig; it can come back after concentrating with strong ENT can be used for further approaches.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER30779A DE1165592B (en) | 1961-07-19 | 1961-07-19 | Process for the production of fluorenone by the oxidation of fluorene |
| DER31437A DE1201339B (en) | 1961-07-19 | 1961-11-10 | Process for the production of fluorenone by the oxidation of fluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER30779A DE1165592B (en) | 1961-07-19 | 1961-07-19 | Process for the production of fluorenone by the oxidation of fluorene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1165592B true DE1165592B (en) | 1964-03-19 |
Family
ID=7403379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER30779A Pending DE1165592B (en) | 1961-07-19 | 1961-07-19 | Process for the production of fluorenone by the oxidation of fluorene |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1165592B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2441746A1 (en) * | 2009-06-11 | 2012-04-18 | Taoka Chemical Co., Ltd. | Noncrystalline form of fluorene derivative and process for preparation thereof |
-
1961
- 1961-07-19 DE DER30779A patent/DE1165592B/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2441746A1 (en) * | 2009-06-11 | 2012-04-18 | Taoka Chemical Co., Ltd. | Noncrystalline form of fluorene derivative and process for preparation thereof |
| EP2441746B1 (en) * | 2009-06-11 | 2017-04-05 | Taoka Chemical Co., Ltd. | Noncrystalline form of fluorene derivative and process for preparation thereof |
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