DE2064279C3 - Process for the preparation of acenaphtenes substituted by oxygen-containing groups - Google Patents

Description

So far only two isomeric formylacenaphthenes are known from the literature, namely 1-formylacenaphthene (see Journal of the American Chemical Society, Vol. 62, 1940, pp. 49 to 52) and 3-Formyl · acenaphthen (see Journal of the Chemical Society, 1936, pp. 339, 344 and 346).

The invention relates to the production of groups substituted by oxygen-containing groups Acenaphthenes of the formula

in the χ a formyl or hydroxymethyl group designated.

It has also been found that 7-formylaccnaphthene advantageously obtained when acenaphthylene with carbon monoxide and hydrogen at temperatures from 50 to 150 ° C and under pressures from 100 to 1000 at in the presence of rhodium carbonyl complexes implements.

The new process has the advantage that 7-formylacenaphthene can be obtained in industrially usable yields in an easy way.

The new process is noteworthy in this respect when it comes to the use of cobalt carbonyl complexes for the hydroformylation of acenaphthylene essentially a hydrogenation occurs and the Yields of 7-formylacenaphthene are so low that they meet the requirements with regard to the yields to a process in technology does not meet.

Carbon monoxide and hydrogen are generally in a volume ratio of 1: 4 to 4: 1, in particular used in a volume ratio of 1: 1 to 1: 2.

The reaction is carried out at temperatures from 50 to 150.degree. Gets particularly good results if you keep temperatures of 80 to 140 ° C. Furthermore, the implementation is activated when pressing 100 to 1000 at performed. Pressures of 200 to 700 atm have proven particularly advantageous.

The reaction is carried out in the presence of carbonyl complexes of rhodium. It is preferable to use 0.0001 to 0.1 percent by weight, in particular 0.0005 to 0.05 percent by weight rhodium, calculated as metal, based on the one * set acenaphthylene. It is possible to separate the carbonyl complexes before the oxo reaction to manufacture or the starting materials for the carbonyl complexes, such as halides, oxides, chelates or fatty acid salts of rhodium, to be fed separately to the reaction. The catalytic converter then blanks itself under the reaction conditions. Square planar materials have proven particularly useful as starting materials Rhodium complexes in the reaction mixture are homogeneously soluble, such as dimeric rhodium carbonyl chloride, Rhodium-carbonyl-bis-triphenylphosphine chloride, Tristriphenylphosphine-rhodium-chloride, dimeric Cyclooctadienyl-1,5-rhodium-chloride or rhodium-carbonylacetylacetonate proved. The reactionary geroic In addition, complex

Formers such as phosphines, phosphites, arsines, arsenites, amines, pyrrolidines, to modify the catalyst can be added.

The reaction is generally carried out in the presence of a solvent such as hydrocarbons,

z. B. benzene, toluene, or xylene, also ether, z. B. Tetrahydrofuran. If you work without a solvent, you carry out the reaction in molten Acenaphthylene through (Γρ. = 92 ° C). That in the hydroformylation of acenaphthylene

^ao obtained reaction mixture is generally first freed from the catalyst by distillation and then optionally after separating off the solvents used, the 7-formylacenaphthylene in pure form, eg. B. by distillation obtained.

^a 5 In addition to 7-formylacenaphthene, a small amount of 7-hydroxymethylacenaphthene is obtained as a by-product. A small amount of acenaphthene is obtained as a forerun.

From 7-formylacenaphthene, S'ch allows hydration

tion z. B. in the presence of hydrogenation catalysts such as copper. Hydrogenation catalysts containing nickel or cobalt at elevated temperature, e.g. B. Temperatures of 40 to 150 ° C, optionally under increased Pressure, e.g. B. from 5 to 300 at, 7-Hydroxymethylacenaphthen produce in good yields. It has proven to be particularly advantageous to use that obtained in the hydroformylation of acenaphthene Reaction mixture without separating off the rhodium carbonyl complexes contained therein, in the presence heated by carbon monoxide and hydrogen to temperatures of 140 to 200 ° C. That in the reaction mixture 7-Formylacenaphthen contained therein is then hydrogenated to 7-Hydroxymethylacenaphthcn. the end the reaction mixture is obtained pure 7-hydroxymethylacenaphthene according to the usual procedure, for. B. Distillation.

7-Formyl- or 7-Hydroxymethylacenaphthen is obtained by reacting with mcno- or disubstituted Amines the corresponding Amino-methylacenaphthene, the valuable pharmaceutical properties, z. B. antihypertensive effects.

The parts given in the following examples are parts by weight; they relate to parts by volume like kilograms to liters.

example 1

250 parts of acenaphthylene, 250 parts of benzene and 0.05 part of dimeric

Cyclooctadiene-l, 5-rhodium chloride submitted and at 100 ° C with an equimolecular mixture of Carbon monoxide and hydrogen reacted under a pressure of 70 at. After a reaction time of 6 hours, the reaction mixture is cooled and

tensioned and then the solvent was distilled off. The remaining residue is fractionated in vacuo. 162 parts (54% of theory) of 7-formylacenaphthene with a boiling point of 133 ° to 136 ° C. are obtained

3 4

at 0.2 mm Hg. The 2,4'Dinitrophenylhydrazone des Hert and the residue fractionally distilled, Man

7-FormylBcenaphthens melts at 186 to 188 ⁰ C. receives 37 parts of 7-hydroxymethylacenaphthen from

_D. ,, "Boiling point 127 ° C at 0.1 mm Hg and from the melting point

^{B els} P » ^e ' ² point 105 to 108 ° C.

65Teile 7-Formylacenaphthen together 5 A _na i _VSE.

with 50 parts of methanol and 5 parts with methanol ■ »·» ** '- ·

washed Raney nickel in a high pressure calculation

barrel of 220 room parts content presented. After the carbon 84.8 Vo

Purging with nitrogen, hydrogen is 6.5% at room temperature

50 at hydrogen is injected then on «oxygen 8.7%

60 ⁰ C heated and found the hydrogen pressure to 100 at:

elevated. After 3 hours the reaction mixture becomes carbon 84.6 Ve

cooled down and relaxed. From the hydrogen obtained in this way 6.4%

The solvent is distilled off as a result of the reaction. Oxygen 8.9Vo

Claims (1)

Claim: Process for the production of 7-FormyI-acenaphthen, characterized in that acenaphthylene with carbon monoxide and hydrogen at temperatures of 80 to 150 ° C and under pressures of 100 to 1000 at in the presence of rhodium carbonyl complexes.