DE2064279B2 - Process for the preparation of acenaphtenes substituted by oxygen-containing groups - Google Patents

Description

NV _Au J 7_Formylacenaphthen can be

in which χ a formyl or hydroxyl group 30 _ru * _s, for example in the presence of hydrogenation catalysts,

referred to as hydrants containing copper, nickel or cobalt

It has also been found that 7-formyl catalysts can be used at elevated temperatures ζ B. Tempe-

acenaphthene is advantageously obtained if one has acenaphtha of 40 to 150 ° C, optionally below

Thvlen with carbon monoxide and hydrogen at high pressure, τ. B. from 5 to 300 at, ⁷ ^ rOXy-

temperatures of 50 to 150 ° C and under pressures of 35 methylacenaphthen produce in good yields.

100 to 1000 at in the presence of rhodium carbonyl It has proven to be particularly advantageous if one

complex implements. which occurs in the hydroxylation of a ^ naphthene

The new process has the advantage that you can keep the reaction mixture without the then contained Separate 7-formylacenaphthene in technically usable form rhodium carbonyl complexes in counter-bags in an easy way. 4 ° the carbon monoxide and hydrogen waited for temperature

The new process is remarkable in that it is heated to temperatures of 140 to 200 C,

than 7-formylacenaphthene contained when using cobalt carbonylcompaction mixture

plexen for the hydroformylation of acenaphthylene then hydrogenated to 7-hydroxymethylacenaphthene. the end

essentially a hydrogenation occurs and which the reaction mixture receives.man pure 7-hydroxy-

Yields of 7-formylacenaphthen are so low, "methylacenaphthen according to the usual procedure, z. B.

that they meet the requirements with regard to yield distillation,

ten to a process in technology not meet. From 7-formyl- or 7-hydroxymethylacenaphthene

Carbon monoxide and hydrogen are generally obtained by reacting with mono- or disubstimeins in a volume ratio of 1: 4 to 4: 1, the amines involved the corresponding ammo-methylsoaders in a volume ratio of 1: 1 to 1: 2 one-50 acenaphthenes, the valuable pharmaceutical proprietary stocks, z. B. antihypertensive effects.

The reaction is carried out at temperatures of 50 to 150.degree. C. in the parts given in the following examples. Particularly good results are obtained in parts by weight, they relate to the space you keep if you keep temperatures of 80 to 140 ° C dividing like kilograms to liters. Furthermore, the reaction is carried out at pressures of ₅₅ B bis ρ ie 1 1 100 to IGOu at. Particularly advantageous ^v _rJ, u, pressures have been found at from 200 to 700. In a high pressure vessel made of stainless steel

The reaction is carried out in the presence of carbonyl 1000 parts by volume, 250 parts of acenaph-

complex of rhodium carried out. Preferred ethylene, 250 parts of benzene and 0.05 part of dimeric wise to apply 0.0001 to 0.1 percent by weight, 60 cyclooctadiene-l, 5-rhodium chloride presented and at

in particular 0.0005 to 0.05 percent by weight 100 ° C with an equimolecular mixture

Rhodium, calculated as metal, based on the one carbon monoxide and hydrogen under a B.ack

set acenaphthylene. It is possible that implemented by 700 at. After 6 hours of reaction

Carbonyl complexes before the oxo reaction, the reaction mixture is cooled down and deconstructed or the starting materials for the carbonyl ₆ . tensioned and then the solvent was distilled off. De:

complex, such as halides, oxides, chelates or fat- remaining residue is fractionated in a vacuum

acidic salts of rhodium, separated from the reaction. 162 parts are obtained (54% of theory)

respectively. The catalyst then forms 7-Formylacenaphthcn of its own accord with a boiling point of 133 to 136 ° C

3 4

at 0.2 mm Hg. The 2,4-dinitrophenylhydrazone deslates and the residue is fractionally distilled. Man

7-FormyIacenaphthens melts at 186 to 188 ° C. Receives 37 TeUe of 7-Hydroxymethylacenaphthen vom

B ε i s η i e 1 9 boiling point 127 ° C at 0.1 mm Hg and from the melting point

^^,.,, ^. ^p point 105 to 108 ° C.

65 Teens 7-Fonnylacenaphthen together become 5

with 50 parts of methanol and 5 parts with methanol ³ ^ ¹

washed Raney nickel in a high pressure calculation

barrel of 220 room parts content presented. After carbon 84.8%

Purging with nitrogen will be hydrogen 6 5% at room temperature

50 at hydrogen is injected. Then, 8.7% oxygen is added.

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

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

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

Reaction mixture, the solvent is distilled off - oxygen 8.9%

Claims (1)

under the reaction conditions. Particularly preserved patent claim: Process for the preparation of 7-formyl Hydrogen at temperatures of 80 to 150 ° C meres Cyclooctacl ^ J ^^ üum ^ ig or and suppressing 100 to 1000 at in the presence of ^^^ tS ^ S ^^ lZ ^ i wart of Rhoduimcarbonylkomplexen. ^ JJ ^ ÄoSrine, Phosphite, Arsine, Arsenite, Amines, pyrrolidines, to modify the catalysis tors are added. The implementation is generally carried out in From the literature only two isomeric units of a Y ^ f ^^ / S ^ Formylacenaphthene known, namely 1-formyl- 15 z. B. benzene, toluene, or xylene also acenaphthen (see Journal of the American Chemical Tetrahydrofuran _: * ^ & ^ ^ Us ^ ™ ¹ ™? L ° - Society, Vol. 62? 1940, pp. 49 to 52) and 3-formyl- solvent works, leads to the conversion in acenaphthen (see Journal of the Chemical Society, melted Acenaphthy enidurch (F ^, - ^ 92 C). 1936 S 339 344 and 346) That in the Hydroformyuenmg of Acenapnth} Ιεη ^ S to1 £ bd4 is the manufacture of the raised ^^^^^ ZSffSSZ G bitit you sew ^ S to1 £ bd4 is the manufacture ^ substituted by oxygen-containing groups next by Ahh d Fl danr given turned L _m . _; in the form, e.g. B. by D, g. 25 In addition to 7-formylacenaphthen, a by-product M 7Hdoxymethylacenaphthen is obtained through S pp next through Destd ationv ^ y ^ Acenaohthene of the formula then, optionally after separating off the associated Acenaontnene of the formula used solvent the 7-Fonnylacenaphthylen x _m . _; in the form, e.g. B. by distillation obtained. hh falls l Nbdk In addition to 7-formylacenaphthene falls as a by-product '\ A eeringe amount of 7-Hydroxymethylacenaphthen. j; i A small amount of acenaphthene is added to the