DE1668533C - - Google Patents

Description

'V

COOR

Il

OCH ₃
an aldehyde of the general formula

in which X has the meaning given above, mii

in which X stands for a halogen and R door a lower alkyl group with 1 to 4 carbon atoms, thereby marked dall one jAlO-Trioxo-l ^^ Wa ^ a.lO-octahydroanthracene the general form! II

(11)

OCH,

in which X has the meaning given above, with an aldehyde of the general form

O = CH - COOR

in which R has the meaning given above. is reacted in the presence of a magnesium alkoxide in an inert, hydroxyl-free solvent and in an inert gas atmosphere at temperatures between about 80 and 12O ¹ C and the product of general formula I formed is isolated in a manner known per se.

2. The method according to claim 1, characterized in that the reaction with 0.1 to 1, OMoI magnesium methoxide per mole of the compound of the formula Π is carried out in ₄ to 24 hours.

The invention relates to a process for the preparation of trioxooctahydroanthracene derivatives of the general formula 1

CH

COOR

C) O
OCH,
in which X for a halogen and R for a lower O = CH - COOR

in which R has the meaning given above.

in the presence of a Magnesiuiiialkoxids in one. inert, hydroxyl group-free solvent uiv! in an inert. Gas atmosphere at temperatures between about 80 and 120 C converts and the formed Product of the general formula I isolated in a manner known per se.

A work (Chemiker-Zeitung, vol. 80, p. 446 ff. 1. in which the reaction mechanism of the aldol condensation is examined, shows that the course of Starting material and catalyst depends in a way that is not yet transparent. It should according to of this literaturstcllc (p. 446, 1st column, paragraph 3) in an aldol condensation catalyzed by acids in particular the α, / ί-unsaturated carbonyl compounds, d. H. the products intended according to the invention, willow. According to p. 446. r. Split. Paragraph 4 should prevent aldol condensation in the presence of aluminum alcoholates, according to the journal At the. Chcm. Soc, 69. p. 2606, Tab. II, on the other hand, phenylacetaldehyde with Al-Mg-ethylate gives the corresponding Aldol or acrolein. As the above literature shows, it was therefore by no means foreseeable whether and under what conditions the starting materials of the claimed process to the desired Condensation can be brought.

The presence of a magnesium alkoxide leading to chclate formation with the tricyclic triketone leads, surprisingly, that the implementation is smooth and reproducible and with satisfactory yields.

so The magnesium alkoxide concentration is not critical within the range given below. the The presence of only trace amounts is sufficient to catalyze the reaction. Generally will but molar amounts of 0.1 to 1.0 mol of metal,

5; based on the tricyclic triketone used. Larger or, as stated above, smaller amounts can be applied to the implementation without any harmful effect. Are others active Hydrogen atoms in addition? .U den normally

do present in the iricyclic triketon, so becomes I equivalent of magnesium methoxide per additional active water solute added. Under "reaction-inert solvent" in the above cited sense becomes a solvent

(l.s understood that the Reakttonsleilnchmer dissolves but with the reactants or the products does not react to a noticeable extent under the conditions described. As examples of

such solvents which are free of hydroxyl groups are benzene, xylene and toluene. Dioxane, 1,2-dimethoxyethane, Diethylene glycol dimethyl ether and dimethylformamide called.

The implementation is in an inert atmosphere. z. B. a stick substance atmosphere, carried out at about 80 to 120 ⁰ C for ¹ / _A to about 24 hours.

The previously prepared metal chelate of the iricyclic Triketons can also be used in the presence of an acid or base. Mixtures of non-chelated and chelated tricyclic triketone can be used. Have such "mixtures compared to the use of the previously prepared chelate has the advantage that it, as such, the amount of the metal present and often facilitate the extraction of the end product.

The compounds according to formula 1 of the present invention are in particular as chelier.Je. sequestering and complexing agents of value for polyvalent metal ions. The ones with the few Metal ions formed complexes are particularly stable and in various organic Solvents usually quite soluble. These properties naturally make them door one Suitable for a variety of purposes where the contamination of the metal ion poses a problem such as B as stabilizers for various organic Systems such as saturated and unsaturated lubricating oils and hydrocarbons. Fatty acids and waxes, in which the contamination by transition metal ions leads to oxidative decomposition and discoloration accelerated, in biological experiments and in metal extraction. she are also involved in the analysis of polyvalent metal ions which form complexes with these materials. for their extraction and as a metal carrier of value. The connections can also be used for other purposes, for which Koniplcxbiidende means are generally used.

The new products also serve as intermediates in the manufacture of pharmaceuticals Products, especially in the case of agents for combating microbes.

The 3,4.10-tri-0x0-1,2.3,4.4a. ^ AJO-octahydroanlhracenes used as starting material can be prepared by conventional methods.

For example, methyl 3-methoxybenzoate is converted to methyl (3-methoxybenzoyl) acetal by reaction with methyl acetate in dimethylformamide in the presence of sodium hydride. This reaction product is further converted to dimethyl- (3'-methoxybenzoyl) succinate by treatment with methyl bromoacetal and sodium hydride, and the succinal is again treated with ethyl acrylate to form methylethyl-carbomethoxy. mcth- y, oxybenzoyl) adipate reacting the latter compound to 3- (3'-methoxy benzo γ]) is through Säurehydrolysc and DccaiKmlierung -... converted to adipic acid by hydrogenolysis over palladium / du u corresponding Bcnzyhcrbindung is reduced <> o This 3- (2'-Metl "ioxybenzyl | -adipic acid is then dissolved in i'ssigsiiurc with formation of 3- (2'-chloro-5'-mct! V-methoxy-4'-chlorobenzene-adipine; iure chlorinated. After treatment with anhydrous liquid fluorine-hydrogen these mixed clilorbcticyladipic acids form "- (r .'-Carbcixyiithvli - ^ - melhoxy-S-chloi · - 4-tctralcn and the enispnxliende n-Chloi-7-met!) - oxytetralone, which get due to their different solubility in chloroform runs can be. The 8-halo-tetralone noted above is used in the subsequent steps. 2- (2'-Carboxyethyl) -8-chloro-5-methoxy-4-tetralone is converted to the methyl ester and treated with dimethyl oxalate to form l-carbomethoxy-e-chloro-5 - methoxy - 3,4,10 - trioxo - 1,2,3,4,4 a, 9,9a, 10 - octahydroanthracene condensed. Treatment of the 2-carboxy-5-methoxy derivative obtained in this way with glacial acetic acid, concentrated hydrochloric acid and water at elevated temperatures leads to 8-chloro-5-mei.hoxy - 3,4,10 - trioxo - 1,2,3, 4.4a, 9.9a, 10 - octahydroanthracene.

example 1

2-carbobutoxymethylidene-5-methoxy-8-chloro-3.4.10-lricr.o-l, 2.3,4,4 a.Q ^ a. '. O-octahydroanthracene

Under a nitrogen atmosphere, a solution of 500 mg (1.7 m mol) of S-methoxy-S-chloro-SAlO-trioxol, 2.3,4,4a.9,9a, 10-octahydroanthracene, 83 mg (1.0 m-mol) Magnciiiummethoxyd, 500 mg (3.8 m mol) of n-butyl glyoxylate, and 20 cc of xylene heated for 3 hours at 105 to 110 C ^1. The red-brown mixture is evaporated to dryness under reduced pressure and the residue is shaken with a mixture of chloroform and 2N hydrochloric acid. The chloroform solution is washed with water, decolorized with activated charcoal, dried over anhydrous sodium sulfate, filtered and evaporated to give a reddish oil. After silica chromatography (dilution with chloroform) or by crystallization from a solution of ether and hexane, 2-carbobutoxymethylidene-5-methoxy-8-chloro-3,4.10-trioxo-l, 2.3,4.4a, 9.9a, 10-octahydroane is obtained ! hracen; Melting point: 12! up to 124 C (impure). By recrystallizing the material twice, an analytical sample is obtained in the form of small, yellow-orange crystals with a melting point of 127.5 to 128 C.

Analysis for C ₂₁ H ₂₁ O ₁₁ CI (404.8):

Calculated ... C 62.30. H 5.23, Cl 8.76;
found .... C 62.58. Il 5.55. Cl 8.87.

Example 2

2-Caι ■ bobutoxymcthyliden-5-methoxy-8-chloro-3.4.10-trio \ o-l.2.3.4,4a, 9,9a.l0-octahydroanthraccine

In one with a mechanical stirrer, a Slieksiol inlet and a reflux condenser (which is equipped with a separator) equipped flask 13.9 g (0.0476 mol) of 5-methoxy-8 - chlorine - 3.4.10 - trioxo -1,2,3,4,4a, 9,9 a, 10 - octahydroanlhracene, 1.03g (0.012MoI) magncsium methoxide. 13.9 g (0.107 mol) n-But> li: lyo \ ylate and 11 xylene 2 hours at reflux during this period the mixture becomes darkclorangc. and water collects in the collecting vessel. The mixture is then cooled and intermittently with (Sn-Sal /. Acid shaken for 5 minutes. The organic layer is poured twice with water and once with saturation Sodium chloride solution washed over anhydrous Sodium sulfate dried, treated with activated charcoal, filtered through diatonic earth and closed a viscous red >> 'oil evaporated. The oil will ir rint! limited amount of ether dissolved, and the

Solution is inoculated with unsaturated ester. After crystallization has started, more ether is added. After crystallization overnight, the orange-colored solid is filtered off and washed with ether which contains a small amount of ethyl acetate. The unsaturated ester (9.3 g) is obtained in the form of small ijelborane-colored crystals; Melting point: 120 23 ⁰ C., analytical sample bij: 127-128 C. An additional Estermenge can be obtained by chromatography of the mother liquor of magnesium silicate and washing with carbon tetrachloride and chloroform in the ratio of 1: 1 are obtained. Dilution with carbon tetrachloride alone gives the geometric isomer of the unsaturated ester (melting point: 134 to 135 ° C.). Washing with chloroform gives the hydroxyesler n-butyl-5-me (hoxy-8-chloro-3,4.IO-triox0-! .2.3.4.4 a.9.9a.) 0-octahydroanthracene - 2 - (. < - hydroxy) - acetal; Melting point: 180 to 182 C.

Following the procedure of Examples 1 and 2, the following compound was also prepared:

"T

CH, m.p.
161 to 168 C

maximum (H ^T ) 367 (13 600)

λ (ΠΙμ)

maximum (C) Ii

444 (9740)

Analysis for C ₁₈ H ₁₅ Ot ₁ Cl:

Calculated ... C 59.60. H 4.15%; found .... C 60.26, H 4.38.

The reactants for this compound are the same as in Example 1.

Claims (1)

Palent claims: 1. Process for the preparation of trioxooctahydroanthracene derivatives of the general formula 1 Alkyl group having 1 to 4 carbon atoms, characterized in that a 3,4,10-trioxo-l, 2,3,4,4a. 9.9a, 10-octahydroanthracene of the general formula 1!