DE2146675A1 - Aziridinocarbonyl-quinoline-S-carboxylic acid derivatives and their acid addition salts, processes for their production and medicinal preparations - Google Patents

Description

¹¹ Aziridinocar "bonyl-ch.inolin-3 ~ carboxylic acid derivatives and their acid addition salts, process for their production" and medicinal products "

Priority: September 18, 1970, V.St.A., Fr.73669

The invention relates to new aziridinocarbonyl-quinoline-3-carboxylic acid derivatives of the general formula (I)

(D

in which Z is a hydroxyl group, a lower alkoxy radical, monocyclic aryloxy radical or a halogen atom, R- ^ ^e * ^{n is a} hydrogen atom or a lower alkyl radical and -Rg is a hydrogen or halo ζ enatorn, a lower alkyl, lower alkoxy, n-lower Alkenyl, monocyclic cycloalkyl, monocyclic aryl or haloalkoxy, a cyano or trihalomethyl group, ll-x, Rj, Rc and Rg are the same or different and V / as-

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Substance atoms, lower alkyl radicals or monocyclic aryl radicals, where no more than two of the radicals R ^, R. _f, Rc and R ^ are aryl radicals, and R ~ is a hydrogen atom, a lower alkyl, monocyclic aryl or aralkyl radical , as well as their acid addition salts.

In the compounds of the general formula (i), the aziridinocarbonyl radical and the radical R _{2 can} each be in the 6- or 7-position, but not at the same time in the same position.

P The term "lower alkyl radical" means straight-chain or branched alkyl radicals with up to 8 carbon atoms. Specific examples are the methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, isohexyl, Heptyl, 4,4-dimethylpentyl, octyl or 2,2,4-trimethylpentyl group. The lower alkyl radicals can also carry substituents, for example an aryl radical.

The halogen atoms include bromine, chlorine, iodine or fluorine atoms. Bromine and chlorine atoms are preferred.

The term "lower alkoxy radical" means of the above

derived,
called lower alkyl radicals / straight-chain or branched AIk-

oxy radicals with about 2 to 5 carbon atoms.

The "lower alkenyl radicals" are straight-chain or branched ones of the aforementioned lower alkyl radicals derived, monounsaturated hydrocarbon radicals.

Specific examples of trihalomethyl radicals are the trifluoromethyl, Trichi or methyl or tribrominethyl group.

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Examples of monocyclic aryl radicals are carbocyclic aryl radicals, e.g. phenyl groups or substituted phenyl groups, such as phenyl groups substituted with lower alkyl radicals, e.g. the tolyl, ethylphenyl or butylphenyl group, di- (lower alkyl) phenyl groups, e.g. the diinethylphenyl or 3,5-diethylphenyl group, Halogenphenyl groups, for example the chlorophenyl, bromophenyl or 2,4- _f 6-triehlophenyl group or the nitrophenyl group

e.g.

pe. The monocyclic aryloxy radicals are derived from / from the aforementioned Aryl residues.

The monocyclic ⁿ yiloalkylreste example, comprise 3 to 6 C-atone in the ring. Specific examples are the cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl groups.

In preferred compounds of the general formula I, R, a lower alkyl radical, R £ a hydrogen atom or a lower one Alkyl radical which is in the 7-position, R ,, Rg and Ry Wasserst off atoms and Z is a hydroxyl group or a halogen atom.

Those compounds of the general formula (I) in which Z is a hydroxyl group can also be used in the tautomeric keto form (la)

are present.

The compounds of the general formula (I) form with inorganic compounds and organic acids acid addition salts. Examples of suitable acids are halogenated hydrogen acids, e.g. bromic,

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Hydrochloric or hydriodic acid, sulfuric acid, nitric acid, Phosphoric acid, boric acid, acetic acid, oxalic acid, V / monic acid, malic acid, citric acid, succinic acid, benzoic acid, ascorbic acid, Salicylic acid, theophylic acid, camphor sulfonic acid, Alkanesulfonic acids, such as methanesulfonic acid or arylsulfonic acids, such as benzene or toluenesulfonic acid. Salt formation is often a suitable measure for purifying the desired compounds The free bases can be extracted from the salts by treatment with alkalis, such as alkali hydroxides, e.g. sodium hydroxide, to be set free again.

The invention also relates to a process for the preparation of the aziridinocarbonyl-quinoline-J-carboxylic acid derivatives of the general Formula (I) and its acid addition salts, characterized in that is that you have a nitrobenzoic acid of the general formula (II)

(II)

in which R _{2 has} the aforementioned meaning, to the aminobenzoic acid W of the general formula (III)

HoocJr

reduced, in which R _{2 has} the aforementioned meaning, the compound of the general formula (III) with an alkoxymethylene malonic acid or its ester of the general formula (IV)

R ₁ OC = C (COgR ₁ ) J, (IV)

2 09813/1823

in which R ^ and Ry have the aforementioned meaning to one Carboxyanilinomethylene malonic acid derivative of the general formula (V)

C (CO ₂ R ₁ ) ₂

(V)

in which R- ^, R £ and R ~ have the aforementioned meaning, condensed, the compound of the general formula (V) by heating to temperatures above about 200 ° C. to form a hydroxyquinoline of the general formula (Vl)

OH

(VI)

in which E ^ »% ¹²²¹ ^ ^- % ^ ^{e have the} aforementioned meaning, the compound of the general formula (VI) is cyclized with an alkali hydroxide and a halogenating agent to give a compound of the general formula (VIlJ

IaI

CO ₃ R ₁

(VII)

in which R-,, R £ and R ^ have the aforementioned meaning and Hai a Is halogen atom, or the compound of the general formula (VI) with a halogenating agent into the compound of the general formula (VIII).

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- (VIII)

in which R- ^, R £, Ry and Hal have the aforementioned meaning, transferred to the compound of the general formula (VII) or (VIII) with an ethyleneimine of the general formula (IX)

, - C.

NH

R C

in which R ,, R ,, R ^ and Rg have the aforementioned meaning, too condensed the compounds of the general formula (i), if appropriate those compounds of the general formula (I) in which Z is a hydroxyl group with an alkyl or Aryl halide or the corresponding sulfates to give those compounds of the general formula (I) in which Z denotes an alkoxy or aryloxy radical, and optionally the free bases with inorganic or organic acids in their Acid addition salts transferred.

The reduction of nitrobenzoic acid of the general formula (II) to the corresponding amine of the general formula (III) is preferably carried out with hydrogen in the presence of a catalyst, such as palladium- or platinum-on-charcoal, performed · The Condensation of aminobenzoic acid of the general formula (III) with the Alkoxym ethyl enmal on acid or the corresponding Ester of general formula (IV) is preferably used in

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2U6675

a molar ratio van (TU): (IV) of about 0.8: 1 to 1.2: 1 at temperatures of about 80 to 140 ^° C. The ring closure reaction of the carboxyanilinomethylene malonic acid derivative of the general formula (V) to give the hydroxyquinoline of the general formula (VI) takes place by heating for about 0.5 to 3 hours

over ₀
to temperatures of / about 200 C in an inert solvent such as Dowtherm, triethylene glycol or nitrobenzene. Suitable halogenating agents for converting the hydroxyquinoline of the general formula (VI) to the compounds of the general formulas (VII) and (VIII) are, for example, oxalyl chloride, thionyl chloride, phosphorus pentachloride, phosphorusentabromide, thionyl bromide or oxalyl bromide.

For the preparation of the compound of the general formula (VIl) is the alkali salt of the hydroxyquinoline of the general formula (Vl) with the halogenating agent, e.g. Oxalylehlorid or Thionyl bromide, in a col ratio of (Vl) ί (halogenating agent) from about 2: 1 to 50: 1 reacted at temperatures of about 20 to 90 ° C.

To prepare the compound of the general formula (VIII), the hydroxyquinoline of the general formula (VI) is mixed with the halogenating agent, for example oxalyl chloride or thionyl bromide, in a ratio of (VI) J (halogenating agent) of about 1: 1 to 20: 1 at temperatures brought from about 30 to 80 ⁰ C to the reaction.

The condensation of the compounds of the general formula (VII) or (VIII) with the ethyleneimine of the general formula (IX) takes place preferably with a fetch ratio of (VIQ or (VHI): (IX)

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from about 1: 1 "to 5: 1 in the presence of an organic or inorganic base, such as triethylamine, pyridine, ITatriumhydroxid, potassium hydroxide or ethyleneimine," at temperatures of about 0 to 30 ⁰ C.

The implementation of those compounds of the general formula (I) ₃

in which Z denotes a hydroxyl group, with the alkyl or aryl halide or the corresponding sulfates, preferably at a molar ratio of (I) ί (halide) or (sulfate) of about 1: 1 to 2: 1 in the presence of one of the aforementioned bases temperatures carried out from about 3 ° to 150 ⁰ C.

Those compounds of the general formula (I) in which R-. means a hydrogen atom, can by saponification of the corresponding Esters of the general formula (I), in which R- ^ a means lower alkyl radical, e.g. the methyl or ethyl group, under acidic or basic conditions by customary methods can be obtained.

Specific examples of nitrobenzoic acids of the general formula (II) are 3-nitro-o-methylbenzoic acid, 3-nitrobenzoic acid, 3-ethyl-4-nitrobenzoic acid, 4-nitro-o-methylbenzoic acid, 2-chloro-5-nitrobenzoic acid, 2-bromo-4-nitrobenzoic acid, 2-methoxy-4-nitrobenzoic acid, 2-cyclopropyl-4-nitrobenzoic acid, 2-cyclohexyl-5-nitrobenzoic acid, 2-phenyl-4-nitrobenzoic acid, 2-cyano-5-nitrobenzoic acid, 2-trifluoromethyl-5-nitrobenzoic acid or 2-ethenyl-4-nitrobenzoic acid.

Specific examples of compounds of the general formula (IX) are aziridine, 2-ethylaziridine, 2,2-dimethylaziridine, 2,2,3,3-tetramethylaziridine, 2,3-dimethylaziridine, 2-phenylaziridine,

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2,3-dipienylaziridine or 2-phenyl-2-ethylaziride in.

The compounds of the general formula (I) and their acid addition salts are suitable for the prevention and control of coccidiosis, a dysentery-like bowel disease that mainly is very common in poultry and from protozoa of the genus Eimeria, in particular E. tenella, E. necatrix and E. acervulina, is caused. Coccidiosis is a serious and common animal disease that affects poultry in particular can cause great economic losses.

In poultry farming it is common to feed prophylactically to add compounds effective against coccidiosis. In this case, the compounds of the general formula (I) or their salts are used in concentrations of about 0.05 percent by weight, based on the feed. In the therapy of coccidiosis Of course, the administration takes place in higher concentrations.

For administration, for example, one or more of the active ingredients are mixed with a carrier or diluent in solid or liquid form. Preferably, the active ingredients are mixed thoroughly with a larger part of the feed, which is in the form of chick feed, fattening feed or mixed laying feed for chicks , Roasting chickens, turkeys or other fattening or breeding poultry are fed.

The active ingredients can also be added to the The animal breeder then adds the feed to achieve the desired concentration of active substances, e.g. in a

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Quantity of around 450 g / ton of feed, added to the soil.

. As inert carriers or diluents, e.g. attapulgus clay, Bentonite or edible vegetable substances, such as grains from residues from alcohol distillation, corn flour or fermentation residues, suitable. Aqueous dispersions can be prepared using emulsifiers and / or surface-active agents Manufacture additives.

. The concentration of active substances in the feed or water is in general generally about 0.005 to 0.5 percent by weight, preferably about 0.02 to 0.04 percent by weight. In addition 'results in the additional Use of a tetraalkylthiuram disulfide such as tetramethyl thiuramdisul fid, often-an increase in effectiveness of the compounds of the general formula (I) or their salts, so that their concentration can be lowered. The total concentration the combination of active ingredients in the feed is, for example, about 0.005 to 0.1 percent by weight, preferably about 0.01 to 0.03 percent by weight. The two are grounded in the combination of active ingredients Active ingredients e.g. used in a weight ratio of 1: 1, but one also obtains with a weight ratio of quinoline derivative : Disulfide from about 1: 3 to 3: 1 gives satisfactory results. Preferred preparations contain either as active ingredients only the quinoline derivative or the quinoline derivative and tetraethylthiuram disulfide.

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The compounds of the general formula (I) and their acid addition salts are also effective nematocides that can be used, for example, to combat ascarids and oxyurs. For this purpose, about 0.05 percent by weight of the active ingredient is added to the feed of the infected animals.

The examples illustrate the invention.

example 1

Ethyl 6- (1- aziridinocarbonyl) -4-chloro-3-quinolinecarboxylic acid

(a) / Tp-Garboxyanilino) -niethylen7-n'ialorisäure-Diethylester A mixture of 13.7 g (0.1 mol) p-aminobenzoic acid and 21.6 g (0.1 mol) Ethoxymetliylenmalonsäurediethylester is slowly up to 130 ° C heated. At the onset of reflux, the reaction mixture gradually begins to solidify. The reaction mixture is kept at this temperature for about 30 minutes, after cooling, the solid product is thoroughly mixed with dietary ether, then the insolubles are filtered off. After recrystallization of the product (28 g) from methanol, the desired compound is obtained in the form of white needles with a melting point of 220 to 223 ° C, ΛΪΐί ⁰¹ 1760 cn " ¹ , broad C = O absorption; Tf) MSO) triplet at 8, 75 ^ (-CH ₅ ); multiplet "at 5.6-6.1T (CH ₂ ); 2 doublets 2.1 T, 2.67, J = 30 Hz (aromatic Η atoms), doublet 1.5 T, 1.74-T (-CH = C \), doublet -0.6, -0, 9T

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(UH), broad absorption at -2.6T (OH).

C H N

Analysis-C ₁₅ H ₁₇ IiO ₆ calcd .: 58.63 5.58 4.56

Found: 58.91 5.67 4.52.

(b) 4-Hydroxy-3, 6-quinolinedicarboxylic acid 3 - ethyl ester A mixture of 10 g (0.032 mol) of the ilalonic acid diethyl ester from (a) and 30 ml "Dowtherm" is refluxed for 3 hours at 250 to 260 ° C heated. After the reaction mixture has cooled and filtered, the filtrate is washed with hexane and methanol. After recrystallization from dimethylformamide to give the GeV / ünschte compound as white crystals, melting at 270 ⁰ C, ⁰¹ λίίϊϊ 1660-1730Cm ^"1, broad C = O absorption,

59 C. 4th H 5 N ber .: ■ 59 , 77 4th , 24 5 , 36 found : , 72 , 54 , 29

2520-272OCm " ¹ , -Η-linked OH.

analysis

(c) 6- (l-Aziridinocarbonyl) -4-chloro-3-quinolinecarboxylic acid-

ethyl ester

A suspension of 2 g of the quinoline carboxylic acid ester from (b) in 500 ml of ethanol is neutralized with 1 η potassium hydroxide solution using phenolphthalein as an indicator for Evaporated dry and dried under reduced pressure over phosphorus pentoxide. The dried potassium salt becomes one Mix the powder and mix it with a solution of 3 ml oxalyl chi ο rid in 50 ml x benzene treated. After stirring for 15 hours at room temperature, the insolubles are filtered off and the solution is concentrated. 1.1 g of 4-chloro-quinolinecarboxylic acid chloride are obtained.

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- 13 -.- - 2U6675

A mixture of 0.2 g of sodium hydroxide, 75 g of ice, 50 ml of benzene and 0.2 g of ethyleneimine is added dropwise with stirring to a suspension of this carboxylic acid chloride in 200 ml of benzene. The reaction temperature is kept at 0 to 5 ^{° C. for 2 hours.} Then the benzene schicut is separated off, washed with water, dried over magnesium sulphate and evaporated. 0.7 g of a yellowish-white pesticide from]? Is obtained. 90 to 100 G, which after recrystallization from acetonitrile has the following data: F. 107 - HO ⁰ C; A ^ ⁰¹ 1718cm "" ¹ (Ester C = O),

1653cm " ¹ (amide C = O) j ^ DCl ₅ ) 8.5 (tert-CH ^), 7.48 (aziridine-

Protons), 5.45 (CH ₂ ). . · '

C H H Cl

Analysis C ₁₅ H ₁₅ IT ₂ O ₅ Cl calcd .: 59.13 4.31 9.21 11.6

found: 58.91 4.49 9.15 11.9

example

Ethyl 6- (l-aziridinocarbonyl) -4-hydroxy- 3-ch inoline carboxylate

A suspension of 6 g of 4-hydroxy-3,6-quinolinedicarboxylic acid 3-ethyl ester from Example 1 (b) in 200 ml of anhydrous benzene and 100 ml of anhydrous chloroform is mixed with 18 ml of oxalyl chloride. The reaction mixture is refluxed for 2 hours. Hach evaporation of the solvent and the excess oxalyl chloride under reduced pressure gives an oil which when treated with g 2.5 of Diäthylather 4-Hydroxychinolincarbonsäurechlorids, mp 180 to 190 ⁰ C is obtained.

A mixture of 0.49 g of sodium hydroxide, 75 g of ice, 50 ml of benzene and 0.43 g of ethyleneimine is for 1 hour "at temperatures

\. 2 0 9 813/1823

from 0 to 5 C with stirring with a suspension of 2.5 g of this acid chloride in 200 ml of benzene. The reaction mixture is allowed to warm to room temperature and is then stirred for a further 30 minutes at room temperature. The benzene layer is separated, washed with water, dried over magnesium sulfate and _einge-: evaporated. 1.79 g of a solid are obtained which, after recrystallizing twice from acetonitrile, yellow crystals of 3 ?. 184

up to 187 ° C and shows the following data: ^ * - ^u D ^o1 at 1680 and 1660cm ~ with a shoulder at 1710cm (C = o) ^ CDCl ^ 8.6 (tert.-CHj), 7.6 (S, Aziridine protons), 5.7 (q, CH ₂ ), 2.5-1.8 (aromatic protons), .1.4 (d, vinyl) and 2.3 (d, IiH). The compound is in the tautomeric keto form.

Example 3

According to Example 1, using methoxymethylene. Dimethyl malonate of 6 "- (l-aziridinoearbonyl) - = 4-chloro-3-quinolinecarboxylic acid methyl ester manufactured.

Example 4 '

According to Example 2, using 2-propyl-4-aminobenzoic acid 7-propyl-6- (l-aziridinocarbonyl) -4-hydroxy-3-quinolinecarboxylic acid ethyl ester manufactured.

Example 5

According to Example 1, using 2-isobutoxy-4 - * aminobenzoic acid of 7-isobutoxy-6- (l-aziridinocarbonyl) -4-chloro

• -

3-quinolinecarboxylic acid ethyl ester produced.

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Example6

According to Example 2, using 2 — isobutoxy — 4— aminobenzoic acid. the 7-isobutoxy-6 ~ (l-aziridinocarbonyl) -4-hydroxy-3-quinolinecarboxylic acid ethyl ester manufactured.

Example 7

According to Example 1 using 2-Ethylaziridin the 6- (2-Ethyl-i-aziridinocarbonyl) ~ 4-clilor-3-quinolinecarboxylic acid ethyl ester manufactured.

Examples

Geraäss Example 1 is using 2- (ß-chloroethoxy) -4-aminobenzoic acid the 7- (β-chloroethoxy) -6- (aziridinocarbonyl) -4-chloro-3-quinolinecarboxylic acid ethyl ester manufactured.

Example 9

According to Example 2 is prepared by using 2,2,3,3-Tetramethylaziridin of 6- (2,2,3 '3-tetramethyl-l-aziridinocarbonyl) -4-h3 ^r droxy-3-quinolinecarboxylic acid ethyl ester.

Example 10

According to Example 1, using 2-phenylaziridine the 6- (2-phenyl-1-aziridinocarbonyl) -4-chloro-3-quinolinecarboxylic acid ethyl ester manufactured.

Example 11

According to Example 1, using dibutyl butoxymethylene malonate the 6- (l-aziridinocarbonyl) -4-chloro-3-quinolinecarboxylic acid butyl ester manufactured.

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Example 12

According to Example 1, using ethoxy-cUmethylmethylehmalonsäurediethylester the 2-methyl-6- (l-aziridinocarbonyl) -4-chloro-3-ghinoline carboxylic acid ethyl ester manufactured. Part of the ester is saponified to form the free acid.

Example 13

According to Example 1, using 2-cyelohexyl-4-aminobenzoic acid the 7-Cyeloh.exyl-6- (l-aziridinocarbonyl) -4-ehlor ^ -quinolinearboic acid ethyester manufactured.

Example 14

According to Example 1, using 2-phenyl-5-and.nobenzoic acid 6-phenyl-7- (l-aziridinocarbonyl) -4-chloro ~ 3- ■ quinoline carboxylic acid ethyl ester produced.

Examples 15 to 21

Worked according to Example 2 using those listed in Table I. Aminobenzoic acids of the general formula (III) the ethyl aziridinocarbonyl-quinoline-3-carboxylate also listed in Table I manufactured:

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- 17 Table I.

2U6675

Example-

No. "

HOOC R-

(III)

OH

\ N-C

11

: oc ₂ h ₅

15th

HOOC

CH ₂ = CH-CH ₂ *

HOOC ^ ^ / ^ NH CH ₂ = CH-CH ₂

C-OC ₂ H ₅

17th

HOOC.

NC

OH

O Il

18th

F ₃ C

\ HOOC ~ NH OH

P ₃ C

i-C It 0

'2

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Porting Table I.

Example (III)

'No. - ■ ■ ■ - -

(D

19th

HOOC

XX

20th

^H 5 ^C 2 °

HOOC

H ₅ C ₂ Q

OH

W ^COC 2 ^H 5

21st

HOOC

COC ₂ H ₅

Examples 22-28

The Aziridinocarbonyl-quinoline-3-carboxylic acid ethyl ester prepared in Examples 15 to 21 are listed in Table II with the alkyl or aryl halides of the general formula B ₈ -Hal in the presence of sodium hydroxide or Hatriumhydrid at temperatures of about 30 to 13O ⁰ C for reaction brought. The reaction products of the general formula (I) are also listed in Table II.

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- 19 Table II

Example no. R ₈ -HaI (D

22nd

CH ₃ Cl OCIL

N-C

O II COC ₂ H ₅

C ₃ H ₇ Br CH ₂ = CH-CH ₂

9

CiOC ₂ H ₅

24

C ₆ H ₅ Cl

NC

25th

CH ₃ C ₆ H ₅ Br

F ₃ C

N-C II O

II COC ₂ H ₅

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Port Settlement Table II

Example Mr.

26th

R ₈ -HaI

2H6675

(i)

27

NO ₂ C ₆ H ₅ Cl

H ₅ C ₂ O

28

^ -H CH-I 6 5 2

0CH _o C _c H._ έ ο 5

Examples 28 to 32

According to Examples 1 and 2, using the in Table III listed malonic acid esters of the general formula (IV) and the aminobenzoic acids of the general formula (III) 'the .Aziridinocarbonyl-quinoline-3-carboxylic acid esters of the general Formula (I), which are also listed in Table III.

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Table III

example
Mr. 2098 28
29 · 13 / 30th 1823 31
32

R ₁ OOC (CO.

(IY).

CH ₅

CH ₅

C ₄ H ₉ ^C 6 ^H 5 C ₂ H ₅ CH ₂ -C ₆ H ₅ C ₂ H ₅ C ₆ H ₄ -CH ₅ iC ₅ H _7i

C ₂ H ₅

OCH ₅ '

CW

CP ₅

OCH ₂ Cl

C ₄ H ₉
C ₂ H ₅

COOR

6-OCH ₅

7-CH

OH Cl OH

C ₂ H ₅ 6-CP ₅ C ₆ H ₄ -OH ₅ Br

OCH ₂ Cl

CO

B is ρ ie 1 33 6- (l-Aziridinocarbonyl) -4-chloro * -3-quinolinecarboxylic acid

A solution of 3 _f O5 g (0.01 mol) 6- (l-aziridinocarbonyl) -4- ■ chloro-3-quinoline carboxylic acid ethyl ester in 100 ml ethanol is mixed with 10 ml 0.1 η alcoholic sodium hydroxide solution. The reaction mixture is refluxed for 1 hour. After the reaction mixture has been concentrated under reduced pressure, the residue is neutralized with 0.1 n hydrochloric acid. This gives the desired 6- (l-aziridinocarbonyl) -4-chloro-3-quinolinecarboxylic acid, which can be recrystallized from dilute methanol

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Claims (7)

-23- 2U6675 patent claims 1. Aziridinocarbonyl-quinoline ^ -earboxylic acid derivatives of the general Formula (i) κΓ * Λ in which Z is a hydroxyl group, a lower alkoxy group, monocyclic aryloxy group or a halogen atom, E _{1 is} a hydrogen atom or a lower alkyl group and Rp ^e ^ ^{Xi is} hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower alkenyl, monoeyelic cycloalkyl -, monocyclic aryl or haloalkoxy radicals, a cyano or trihalomethyl group, R- *, Rj, Rc and Rg are identical or different and represent hydrogen atoms, lower alkyl radicals or monocyclic aryl radicals, with no more than two of the radicals R, , R, R, - and aryl radicals and Ro is a hydrogen atom, a lower alkyl, raonocyclic aryl or aralkyl radical, as well as their acid addition salts. 2. Compounds according to claim 1, characterized in that Z is a hydroxyl group. 3. Compounds according to claim 1, characterized in that Z is a halogen atom. 4. Compounds according to claim 2, characterized in that R _{1 is} an ethyl group and R ₂ , R3, R /, Rc, Rg and R represent hydrogen atoms. 209813/1823 ' - ^ - 2U6675 5. Compounds according to claim 3, characterized in that Rj_ a. Is ethyl group, R ₂ , R *, R ^, Rc »Rg and R ^ represent hydrogen atoms and Z means a chlorine atom. 6. Process for the preparation of the aziridinocarbonyl-quinoline-3-carboxylic acid derivatives and its acid addition salts according to claim 1 to 5 »characterized in that one nitrobenzoic acid of the general formula (II) (II) in which R _{2 has} the aforementioned meaning for the aminobenzoic acid of the general formula (III) (III) reduced, in which R ₂ has the abovementioned meaning, which connects dung ¹ of the general formula (III) with a Alkoxyme- W thylenmalonsäure or its ester of the general formula (IV) in which R ^ and Ry have the aforementioned meaning to one Carboxyanilinomethylene malonic acid derivative of the general red I (V) 209813/182 3 _(v) in the R ^, R2 and R ™ have the abovementioned meanings, the compound of general formula (V) is condensed by heating to temperatures above about 200 ⁰ C to a hydroxy quinoline f of the general formula (VI) (VI) in which R- ,, R2 and R ^ have the aforementioned meaning, cyclized, the compound of the general formula (VI) with an alkali metal hydroxide and a halogenating agent to form a compound of the general formula (VII) Shark CO ₂ R ₁ (VII) in which R ,, R ₂ and R ^ have the aforementioned meaning and Hal is a halogen atom, or the compound of the general formula (VI) is converted with a halogenating agent into the compound of the general formula (VIII) (VIII) ' ^omiNAL in the R ^, R £ i% ¹ ^ ¹ ^ ^ ie. have the above meaning, via> leads, the compound of the general formula (VII) or (VIII) with an ethyleneimine of the general formula (IX) (IX) in which R ^, R *, R ^ and Rg have the aforementioned meaning to the Compounds of the general formula (I) condensed, if appropriate those compounds of the general formula (I) in which Z represents a hydroxyl group with an alkyl or aryl halide or the corresponding sulfates to those compounds of the general formula (I), in which Z denotes an alkoxy or aryloxy radical, and optionally the free bases converted into their acid addition salts with inorganic or organic acids. 7. Medicinal preparations consisting of a compound according to claim 1 to 5 and, if necessary, customary, pharmacologically * acceptable raw materials and diluents. ORIGINAL INSPECTED