DE1002339C2 - Process for working up the reaction mixture formed in the oxidation of technical grade trans-decahydronaphthalene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

PATENT DOCUMENT 1002 REGISTRATION DAY:

NOTICE THE REGISTRATION AND ISSUE OF DESIGN S CHRIFT:

ISSUE OF PATENT LETTERING:

kl. 12 ο 25

INTERNAT. KL. C 07 C MAY 19, 1954

FEBRUARY 14, 1957 JULY 18, 1957

AGREES WITH EDITORIAL

1 002 339 (F 14758 IV b / 12 o)

Upon oxidation of at least about 90% trans-decalin containing decahydronaphthalene with oxygen or oxygen-containing gases to about a _20/0 aqueous turnover ° at elevated temperatures, optionally under elevated pressure and in the presence of catalysts obtained a mixture which, except for at least 80 ° / ₀ unconverted decahydronaphthalene, namely trans- / 3-keto kahydronaphthalene and trans - /? - oxyde kahydronaphthalene, also trans-a-keto kahydronaphthalene and trans-a-oxydronaphthalene as well as trans-9-oxyde kahydronaphthalene and some high-boiling substances, B. acids and esters, and optionally contains hydroperoxides.

The invention now relates to a method for working up such an oxidation mixture.

It has been found that such a mixture can be technically; can work up in an advantageous manner, that the unreacted decahydronaphthalene was largely and completely freed from acids Mixture of the oxidation products treated with appropriately diluted bisulfite solution not exceeding 20%, the precipitated bisulfite adduct of trans- / S-keto-kahydronaphthalene separates, washes with alcohol, decomposed with a dilute alkaline solution and that trans-jö-ketodekahydronaphthalene preferably through Distillation cleans. The remaining mixture of the oxidation products can be used as such, or the trans-a-keto-kahydronaphthalene is separated from it by oxime formation, removes the aqueous layer, distills that still contained in the organic layer, remaining decahydronaphthalene and optionally some of the oxydekahydronaphthalenes, expediently with reduced Pressure, cools the residue, separates the crystallized trans-a-ketodekahydronaphthalene oxime from, cleaves it if necessary in the usual way and purifies the trans-α-keto-kahydronaphthalene which is liberated in the process preferably by distillation. The mother liquor can then, if appropriate, according to known methods Methods, e.g. B. by fractional distillation, are worked up, while still having some trans-a-ketodekahydronaphthalene oxime or trans-a-keto kahydronaphthalene, trans-9-oxyde kahydronaphthalene, trans-a-oxyde kahydronaphthalene and trans-ß-Oxydekaliydronaphthalin receives.

It is best to remove from the mixture obtained during the oxidation of decahydronaphthalene, this is mainly about 90 to 95% unreacted, mainly trans-decahydronaphthalene and consists of about 5 to 10% of oxygen-containing oxidation products and an acid number of possesses about 2, first the acidic parts. For example, one passes the mixture, if necessary after previous Removal of solid catalyst particles by means of a washing tower which is filled with random packings or a stirring process for the processing of the

Oxidation of technical

trans-decahydronaphthalene formed

Reaction mixture

Patented for:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Dr. Herbert Simonis, Krefeld-Uerdingen, and Dr. Kurt Bauer, Holzminden, have been named as inventors

device and through which an alkaline washing liquid, ζ. B. aqueous, dilute sodium hydroxide solution, which is expediently saturated with common salt, flows through it in countercurrent. The washing liquid then contains After leaving the washing tower, in addition to small amounts of neutral parts, the acidic oxidation products in the form their salts. By acidification with a mineral acid, ζ. Β. Hydrochloric acid, the organic acids become free set and deposit as an oily layer on the aqueous layer. They can be easily separated and where appropriate after their esterification with lower alcohols are purified by distillation.

The acid-free mixture of organic compounds is then advantageous, optionally after previous filtration, e.g. B. over a little silica gel, in a or several high-stage extraction columns connected in series with a low-boiling, polar one Solvents, e.g. B. methanol in a ratio of 1 part of methanol to 3 to 4 parts of mixture, continuously im Treated countercurrent. The decahydronaphthalene leaving the last column only contains traces of Oxidation products and can - expediently after an intermediate water wash, whereby low Amounts of dissolved and entrained methanol are recovered - without further purification be fed back to a new oxidation.

The extract containing the neutral oxidation products is then in a column from the extractant, for. B. methanol, exempt. This can again for a new extraction can be used. The remaining concentrate, apart from the oxidation products still contains about 40% decahydronaphthalene is then worked up according to the invention as described above.

709 593/346

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The separation of the majority of the unreacted decahydronaphthalene and that contained in the mixture Acids can, however, also take place in a different order and in a different way than just now described. So you can z. B. also first a large part of the unreacted decahydronaphthalene separate or distill off the oxidation products from the crude mixture by extraction and then wash out the acids from the extract or residue obtained.

The processing of the now largely unreacted decahydronaphthalene and completely Acid-freed mixture of the oxidation products according to the present invention is given below an example described in more detail.

example

5 kg of a mixture, which ^{consists of} 3.8% low-boiling substances, 40.2% decahydronaphthalene, 47.8% oxy- and ketodecahydronaphthalenes and 8.2% higher-boiling substances, is mixed with an excess amount ( 3 1) an aqueous sodium bisulfite solution not exceeding 20%. A temperature of approximately 40 to 50 ° is advantageously maintained here. As a rule, this temperature is established by itself, because the reaction of the hydroperoxides usually still present in the starting mixture with bisulfite is exothermic and supplies the amount of heat required to achieve such a temperature.

After several hours of vigorous stirring, the aqueous layer is separated from the organic layer. The trans - /? - ketodecahydronaphthalene has deposited practically quantitatively in the form of its bisulfite adduct. The organic layer (3.8 kg) is removed, the filtered bisulfite adduct in a low-boiling alcohol, e.g. B. methanol or ethanol, suspended, filtered and sucked sharply dry (1250 g). It is then treated with an aqueous alkaline solution, e.g. B. with dilute sodium hydroxide solution or soda solution at a slightly elevated temperature, z. B. at 30 to 50 °, decomposed and the precipitating ketone purified by distillation. 680 g of chemically pure trans - /? - ketodecahydronaphthalene are obtained. It solidifies in the refrigerator after a few hours to form white crystals that melt at + 6 °. A small residue (35 g) remains, which can be recrystallized from benzene and then melts at about 120 °. His "analysis gives the same gross formula (C ₁₀ H ₁₆ O) _x . Its constitution, however, has not yet been clarified. However, it does not consist of trans-a-ketodecahydronaphthalene, the melting point of which is 32 to 33 °.

The mixture of the other oxidation products can then, if necessary, be separated as follows:

The now freed from / J-ketodekahydronaphthalene, organic layer (4.0 kg) is mixed with a slight excess (about 10%) of a strongly alkaline, aqueous Hydroxylamyl solution heated under reflux with vigorous stirring on the water bath for 1 to 2 hours. then the organic layer is separated off from the aqueous layer and the mixture is distilled under reduced pressure, expediently in a water jet vacuum, the unreacted remainder of the Dekahydronaph still contained in this layer

thalins (2.0 kg). · This can also be used for a new oxidation.

When the organic mixture (2.0 kg) cools down, most of the trans-a-keto-kahydronaphthalene oxime becomes crystalline from that washed with a little alcohol after recrystallizing once from alcohol pure melting point (melting point 165 °) is obtained (174 g). If necessary it can be converted into the free trans-a-keto-kahydronaphthalene be transferred.

ίο The remaining liquid mixture (1.8 kg) can z. B. worked up in the usual way by fractional distillation under reduced pressure will. Trans-9-Oxydekahydronaphthalin (melting point 54 °) (240 g), trans-α-Oxydekahydronaphthalene is obtained in two modifications, the mixture of which is liquid at room temperature (263 g), and trans- / I-oxydronaphthalene (Melting point 72 to 73 °) (784 g).

The residue (519 g) is diluted with about 1 liter of alcohol, the remaining trans-a-ketodecahydronaphthalene oxime (79 g) fails; which, as described above, can be cleaned and, if necessary, split.

The particular advantage of the method described is above all that by using a appropriately diluted, not more than 20% bisulfite solution, surprisingly, the traris-ß-ketodecahydronaphthalene can quantitatively separate from the trans-a-keto-kahydronaphthalene, since under these circumstances only the / J-ketone, but not the α-ketone, a bisulfite adduct forms.

Claims (1)

PATENT CLAIM: Process for working up the reaction mixture formed during the oxidation of technical trans-decahydronaphthalene with air, characterized in that the mixture of oxidation products, which has been largely freed from unreacted decahydronaphthalene and completely freed from acids, is treated with the precipitated bisulfite solution which is suitably dilute and not more than 20% strength The bisulfite adduct of the .trans-jS-keto-kahydronaphthalene is separated off, washed with alcohol, broken down in the usual way with a dilute, alkaline solution and the trans - /? - ketodekahydronaphthalene is purified, preferably by distillation, the remaining mixture of oxidation products is treated with hydroxylamine in the usual way, if necessary, the aqueous layer is separated off, the decahydronaphthalene still present in the organic layer and optionally some of the oxydekahydronaphthalenes are advantageously distilled off under reduced pressure, the residue is cooled and the trans-α-ketodecahydronaphthalene oxime which has crystallized out is cooled ^x separates, this optionally cleaves in the customary manner and the trans-ot-ketodekahydro-, naphthalene obtained is purified, preferably by distillation, and optionally the mother liquor by methods known per se, eg. B. by fractional distillation, broken down into trans-a-ketodekahydronaphthalene oxime or trans-a-ketodekahydronaphthalene, trans-9-oxydekahydronaphthalene, trans-a-oxydekahydronaphthalene and trans-ß-oxydekahydronaphthalene. © 609 770/424 2.57 (709 S93./346 7. 57)