DE2034921B

DE2034921B - Process for the production of 1,8-naphthalaldehyde acid

Info

Publication number: DE2034921B
Authority: DE
Inventors: Anatolij Tichonowitsch; Pokrowskaja Inna Jewgenewna; Pospelow Michail Walerjewitsch; Jakowlewa Antonina Karpowna; Moskau Menjajlo
Original assignee: Nautschno-Issledowatelskij Institut Sintetitscheskich Spirtow I Organitscheskich Produktow, Moskau

Description

3 43 4

Methyläthylketon sowie andere wasserlösliche Ketone Die Ausbeute an 1,8-Naphthalaldehydsäure beträgtMethyl ethyl ketone and other water-soluble ketones The yield of 1,8-naphthalaldehyde acid is

verwenden. 23 g (87 % der Theorie).use. 23 g (87% of theory).

Normalerweise wird die ausgeschiedene 1,8-Naph- . .Usually the excreted 1,8-naph-. .

thalaldehydsäure mit Wasser gewaschen, man kann Beispiel 4thalaldehyde acid washed with water, you can Example 4

aber diese Operation mit einem anderen dazu geeig- 5 In den im Beispiel 1 beschriebenen Reaktor bringtbut this operation with another suitable 5 In the reactor described in Example 1 brings

neten Lösungsmittel, zum Beispiel Butylalkohol, aus- man 20 g Azenaphthylen, 60 g Wasser, 200 ml AzetonNeten solvent, for example butyl alcohol, from 20 g of azenaphthylene, 60 g of water, 200 ml of acetone

führen. ein und setzt 20 g Bariumhydroxid zu. Ozonisierungto lead. and uses 20 g of barium hydroxide. Ozonization

Um ein reineres Produkt zu erhalten, wird und Behandlung der Reaktionsprodukte führt man wie 1,8-Naphthalaldehydsäure der Umkristallisation aus im Beispiel 1 durch. Die Ausbeute an 1,8-Naphthal-Benzol oder Toluol unterzogen. Der Schmelzpunkt io aldehydsäure beträgt 24,2 g (92% der Theorie),
des umkristallisierten Produktes beträgt 169 bis 170° C. . .
Aus der vorliegenden Beschreibung ist ersichtlich, Beispiels
daß das erfindungsgemäße Verfahren zur Herstellung In den im Beispiel 1 beschriebenen Reaktor bringt von 1,8-Naphthalaldehydsäure in der Industrie des- man 20 g Azenaphthylen, 60 g Wasser, 200 ml Azeton, wegen einfach und ohne jede Gefahr zu realisieren ist, 15 10 g Bariumhydroxid ein. Ozonisierung und Behandweil die sich bei Ozonisierung bildenden explosiven lung der Reaktionsprodukte führt man wie im Beispiel 1 Peroxidverbindungen direkt im Reaktionsgemisch in durch. Die Ausbeute an 1,8-Naphthalaldehydsäure Gegenwart von Erdalkalihydroxid zersetzen. Infolge- beträgt 22,4 g (85% der Theorie),
dessen entfällt die Operation der Ausscheidung der- . .
selben, und der ganze Prozeß wird dadurch vereinfacht. 20 B e 1 s ρ 1 e l ο
Außerdem ermöglicht die Erfindung, die Ausbeute an Man ozonisiert 20 g Azenaphthylen in 200 g Endprodukt im Vergleich zu dem bekannten Verfahren Methylalkohol in Gegenwart von 20 g Bariumbeinahe zu verdoppeln. hydroxid. Die Reaktionsprodukte behandelt man wieIn order to obtain a purer product, the reaction products are treated and the recrystallization from Example 1 is carried out in the same way as 1,8-naphthalaldehyde acid. The yield subjected to 1,8-naphthalene benzene or toluene. The melting point of io aldehydic acid is 24.2 g (92% of theory),
of the recrystallized product is 169 to 170 ° C. .
From the present description it can be seen, example
that the process according to the invention for production in the reactor described in Example 1 brings 1,8-naphthalaldehyde acid in the industry because 20 g of azenaphthylene, 60 g of water, 200 ml of acetone can be implemented easily and without any risk, 15 10 g barium hydroxide. Ozonization and treatment The explosive development of the reaction products formed during ozonization is carried out, as in Example 1, peroxide compounds directly in the reaction mixture. The yield of 1,8-naphthalaldehyde acid decompose in the presence of alkaline earth hydroxide. As a result, is 22.4 g (85% of theory),
which eliminates the operation of excretion of the-. .
same, and the whole process is simplified. 20 B e 1 s ρ 1 el ο
In addition, the invention makes it possible to almost double the yield of ozonated 20 g of azenaphthylene in 200 g of end product compared to the known method of methyl alcohol in the presence of 20 g of barium. hydroxide. The reaction products are treated as

Zur Illustration des erfindungsgemäßen Verfahrens im Beispiel 1. Die Ausbeute an 1,8-Naphthalaldehyd-To illustrate the process according to the invention in Example 1. The yield of 1,8-naphthalaldehyde

werden konkrete Beispiele seiner Ausführung ange- 25 säure beträgt 20,5 g (78 % der Theorie).concrete examples of its implementation are acidic is 20.5 g (78% of theory).

führt. _n . . , _leads. _n . . , _

Example 7

Beispiel 1 Man ozonisiert Azenaphthylen analog Beispiel 6,Example 1 Azenaphthylene is ozonated analogously to Example 6,

jedoch im Medium von 200 g Äthylalkohol. Diebut in the medium of 200 g of ethyl alcohol. the

In einen mit Rührwerk, Kühler und Gasleitungsrohr 30 Ausbeute an 1,8-Naphthalaldehydsäure beträgt 21gIn a 30 with stirrer, condenser and gas line tube, the yield of 1,8-naphthalaldehyde acid is 21 g

versehenen Reaktor bringt man 20 g Azenaphthylen, (80 % der Theorie).provided reactor brings 20 g of azenaphthylene, (80% of theory).

60 g Wasser, 200 ml Azeton und 35 g Kalzium- . 1060 g water, 200 ml acetone and 35 g calcium. 10

hydroxid ein. Durch die erhaltene Suspension wird e 1 s ρ 1 ehydroxide a. The suspension obtained becomes e 1 s ρ 1 e

danach der 2 bis 5 % Ozon enthaltende Sauerstoff bei 20 g Azenaphthylen werden analog Beispiel 6,then the 2 to 5% ozone-containing oxygen in 20 g of azenaphthylene are analogous to Example 6,

Raumtemperatur unter kräftigem Rühren durchge- 35 jedoch im Medium von 200 g Propylalkohol ozoni-Room temperature with vigorous stirring, but in the medium of 200 g propyl alcohol ozoni-

lassen. Peroxidprodukte sind im Reaktionsgemisch siert. Die Ausbeute an 1,8-Naphthalaldehydsäureleave. Peroxide products are sated in the reaction mixture. The yield of 1,8-naphthalaldehyde acid

nicht vorhanden (Gehalt am aktivem Sauerstoff in beträgt 21,5 g (85% der Theorie).not available (content of active oxygen in is 21.5 g (85% of theory).

Gewichtsprozent = 0). Der Niederschlag wird ab- . . . _q Weight percent = 0). The precipitate is from. . . _q

filtriert, zur Entfernung der Spuren von Azenaphthy- Beispiel yfiltered to remove traces of azenaphthy example y

len mit Azeton gewaschen und mit 10%iger wäßriger 40 Azenaphthylen wird analog Beispiel 6, jedoch imlen washed with acetone and with 10% aqueous 40 azenaphthylene is analogous to Example 6, but in

Salzsäurelösung behandelt. Die niedergeschlagene Medium von 200 g Butylalkohol ozonisiert. Die Aus-Hydrochloric acid solution treated. The precipitated medium of 200 g of butyl alcohol is ozonated. From-

1,8-Naphthalaldehydsäure wird abfiltriert, zur Ent- beute an 1,8-Naphthylaldehydsäure beträgt 22,4 g1,8-naphthalaldehyde acid is filtered off; the amount of 1,8-naphthylaldehyde acid is 22.4 g

fernung von Spuren der Salzsäure mit Wasser ge- (85% der Theorie),removal of traces of hydrochloric acid with water (85% of theory),

waschen und aus Benzol umkristallisiert. Schmelzpunkt . . . „wash and recrystallized from benzene. Melting point. . . "

des umkristallisierten Produktes ist 169 bis 17O⁰C. Die 45 B e 1 s ρ 1 e 1 iuof the recrystallized product is 169 to 17O ⁰ C. The 45 B e 1 s ρ 1 e 1 iu

Ausbeute an 1,8-Naphthalaldehydsäure beträgt 24,5 g In den im Beispiel 1 beschriebenen Reaktor bringtThe yield of 1,8-naphthalaldehyde acid is 24.5 g. Bring into the reactor described in Example 1

(98% der Theorie). man 20 g Azenaphthylen, 20 g Wasser, 200 g Butylalkohol und 20 g Kalziumhydroxid ein. Das Gemisch(98% of theory). one 20 g of azenaphthylene, 20 g of water, 200 g of butyl alcohol and 20 grams of calcium hydroxide. The mixture

Beispiel 2 wird durchgerührt.Example 2 is carried out.

50 Durch die erhaltene Suspension wird der 5% Ozon50 The suspension obtained becomes the 5% ozone

Man ozonisiert Azenaphthylen analog Beispiel 1, enthaltende Sauerstoff durchgelassen, bis die Absorp-Azenaphthylene is ozonated analogously to Example 1, containing oxygen passed through until the absorption

jedoch in Gegenwart von 35 g Bariumhydroxid. Die tion des Ozons beendigt ist.but in the presence of 35 g of barium hydroxide. The ozone tion is terminated.

Reaktionsmasse wird wie im Beispiel 1 behandelt. Der Niederschlag wird abfiltriert und mit heißemThe reaction mass is treated as in Example 1. The precipitate is filtered off and washed with hot

Die Ausbeute an Naphtlulaldehydsäure beträgt 94% Butylalkohol zur Entfernung von Azenaphthylender Theorie. 55 spuren gewaschen. Die nachfolgende Behandlung derThe yield of naphtholaldehyde acid is 94% butyl alcohol to remove azenaphthylenes Theory. 55 tracks washed. The subsequent treatment of the

_ . it Reaktionsprodukte wird analog dem Beispiel 1 vorge-_. it reaction products is prepared analogously to Example 1

Beispiel i nommen. Die Ausbeute an 1,8-NaphthalaldehydsäureExample i took. The yield of 1,8-naphthalaldehyde acid

Man ozonisiert Azenaphthylen analog Beispiel 1, beträgt 23,6 g (90% der Theorie),Azenaphthylene is ozonized as in Example 1, is 23.6 g (90% of theory),

jedoch in Gegenwart von 35 g Magnesiumhydroxid. In allen angeführten Beispielen sind keine Reak-Die Reaktionsmasse wird wie im Beispiel 1 behandelt. 60 tionsperoxidprodukte nachgewiesen worden.but in the presence of 35 g of magnesium hydroxide. There are no react-dies in any of the examples The reaction mass is treated as in Example 1. 60 tion peroxide products have been detected.

Claims

1 2 In accordance with the goal, the claim was made: there would be the process for the production of 1,8-naphthalaldehyde acid by ozonation of

1. Process for the preparation of 1,8-Naphth'al-Azenaphthylen so perfect that one aldehydic acid by ozonization of azenaph- 5 the end product without excretion of explosive perthylenes In an organic solvent, the oxide products are preserved and thus the process goes through a great deal characterized in that it is made technically feasible.

Ozonization in the presence of 0.5 to 1.5 wt. According to the invention, the object was set

share alkaline earth hydroxide per part by weight of Azenaph- dissolved by a process for the production of ethylene a) in the medium of a lower aliphatic io 1,8-naphthalaldehyde acid by ozonization of Alcohol, optionally mixed with water, azenaphthylene in an organic solvent, or b) in the medium of a lower aliphatic which is characterized in that the ozo-ketone is used carried out with water, the solids ab- nization in the presence of 0.5 to 1.5 parts by weight separates this to remove the alkaline earth metal hydroxide per part by weight of azenaphthylene treated with hydrochloric acid and the remaining 15 a) in the medium of a lower aliphatic alcohol, 1,8-naphthalaldehyde acid to remove, if appropriate in a mixture with water, or b) im Hydrochloric acid washes away. Medium of a lower aliphatic ketone with

2. The method according to claim 1, characterized by carrying out water, separating the solids, this for draws that the ozonization in the medium removal of the alkaline earth metal hydroxide with hydrochloric acid treated by water and a lower aliphatic 2c and the remaining 1,8-naphthalic alcohol in a weight ratio of 1:10. aldehydic acid to remove traces of hydrochloric acid

3. The method according to claim 1, characterized by washing.

draws that the ozonization is carried out in the medium according to a preferred embodiment

of water and a lower aliphatic one the ozonization in the medium of water and Ketone in the weight ratio 1: 2 or 3 by 25 a lower aliphatic alcohol in the weight

leads. ratio 1:10 through.

4. The method according to claim 3, characterized in that it is also useful that the ozonization is drawn, that the ketone is acetone or methylation in the medium of water and a lower ethyl ketone is used. aliphatic ketone in weight ratio or

30 performs 1: 2 to 3.

The preferred ketone used is acetone or

j methyl ethyl ketone.

Other mineral acids are for the separation

unusable. Sulfuric acid, for example, forms with

35 alkaline earth hydroxide an insoluble precipitate what

The invention relates to a method for manufacturing the deposition of the end product difficult. Nitric

of 1,8-naphthalaldehyde acid. 1,8-naphthalaldehyde acid attacks the equipment and worsens it

Acid can easily be converted into naphthalic acid and naphthalic grade 1,9-naphthalaldehyde acid.

Acid anhydride are converted, which is excreted in the pro- The 1,8-naphthalaldehyde acid

production of synthetic resins and real dyes 40 washed and washed to remove traces of hydrochloric acid

for different fibers as well as in the production of then, if necessary, recrystallized. Man

Plasticizers are widely used. The leads the process at room temperature and atmo-

plasticizer made from naphthalic acid through phärendurck. The reaction is selective and

have a high heat resistance and low runs according to the following scheme:
Volatility. 45

It is a method of making 1,8 naph \ \ /

thalaldehyde acid by ozonation of Azenaph- O ₃

ethylene known (C a 11 i g h a η R., Tarker M., Me (OH)

Wilt MJ, Org. Formerly 26, 1370, 1961; _v / / "' ² \

Call igh to R., Tarker M., Wilt M. J., 50 1

Org. Formerly 27, 765, 1962). CHO COOH

The process is carried out in the medium of carbon tetrachloride or butyl alcohol at subzero levels where Me means an alkaline earth metal atom.
Temperatures through. The reaction takes place under The alkaline earth metal hydroxide is used to reduce the peroxides, ozonides, and polymeric peroxides formed when explosive peroxide products are formed: alkoxyhydro- 55 Ozonization of azenaphthylene. These peroxide-peroxide compounds decompose. Barium, calcium or magnesium glacial acetic acid and potassium iodide can be used as alkaline earth products through a special treatment with hydroxide for 10 to 12 hours.

excreted and decomposed, and the formed The ozonization of azenaphthylene is in the medium

1,8-naphthalaldehyde acid is isolated, the 60 of a lower aliphatic alcohol, for example!

Yield is 49.9 percent by weight of theory. Ethyl, methyl, propyl, butyl alcohol or im

The process mentioned is multi-stage, process water-alcohol-medium, i. H. in a mixture of technically complicates and closes the process of carrying out the said alcohol with water. In Excretion of explosive products, which in this case, it is desirable to the weight ratio Use of this process in industry has to adhere to a ratio of 1:10 from water to alcohol. If the restricts. Ozonization carried out in a water-ketone medium

The aim of the present invention consisted in the weight ratio or 1: 2 to 3

Elimination of the disadvantages mentioned. be. The aliphatic ketone can be acetone,