DE2325038A1 - 5-HYDROXY (MERCAPTO) ALKYLIDENRHODANINE DERIVATIVES, THE PROCESS FOR THEIR MANUFACTURING AND MEDICINAL PREPARATIONS CONTAINING THESE COMPOUNDS - Google Patents

Description

¹¹ 5-Hydroxy (mercapto) alkylidene rhodanine derivatives, process for their preparation and medicinal preparations containing these connecting rods ^H

Priority: May 18, 1972, V.St "A. _r no.254 363

The invention relates to 5-hydroxy (mercapto) alkylidenrhodaninde derivatives of the general formula I

R-N

(I)

in which R is a straight-chain or branched lower alkyl radical with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, an alkenyl group with 3 to 5 carbon atoms, an optionally substituted phenyl radical, a phenylalkyl radical having 7 to 9 carbon atoms, a Monohalophenyl, dichlorophenyl, alkylphenyl, methylchlorophenyl, or Pyridylmethy! Rest, R. a branched or straight chain lower alkyl radical with 1 to 4 carbon atoms, a phenylalkyl radical with 7 to 9 carbon atoms, its.

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Alkyl radical can be straight-chain or branched, a monochlorobenzyl or monomethylbenzyl radical and Y is an oxygen or Sulfur atom. Means. -

Examples of cycloalkyl radicals are the cyclopropyl and cyclohexyl groups, for alkenyl radicals the allyl or pearethylallyl group, for monohalophenyl radicals the monochloro, monobromo or monofluorophenyl group, for dichlorophenyl radicals the 2,6-dichlorophenyl or 3,4-dichlorophenyl group, for alkylphenyl radicals the Tolyl group, for methylchlorophenyl radicals the Z-chloro ^ -methylphenyl group and for pyridylmethyl radicals the 2-, 3- or 4-pyridylmethyl group. . .

In preferred compounds of the general formula I, R denotes the methyl, ethyl, propyl, butyl, phenyl or monochlorophenyl group. Particularly preferred are compounds in which R is the 2'- or A -'-chlorophenyl, cyclohexyl or benzyl group, R ^ the methyl, ethyl, benzyl or phenethyl group and Y is an oxygen atom. ^

The invention also relates to a method for producing the Compounds of the general formula I, which is characterized in that a rhodanine which is unsubstituted in the 5-position with an orthoester in acetic anhydride and the resulting 5-alkoxyalkylidenrhodanine

a) for the preparation of the compounds in which Y is an oxygen atom means hydrolyzed under alkaline conditions and then acidified or

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b) for the preparation of the compounds in which "Y is a sulfur atom means that it is reacted with sodium sulfide in aqueous ethanol and then acidified. ~

The preparation of the compounds in which Y is an oxygen atom means can be represented by the following reaction scheme

C (OR ₂ ) 3 I U _0R

2) ^ Γ 1 U-OH

in which R and R ^ have the meaning given above and Rp denotes the methyl or ethyl group.

The implementation of the 5-unsubstituted rhodanine derivative with an orthoester is preferably carried out for 4 to 20 hours at the reflux temperature of the reaction mixture. The intermediate product is: separated and in a solvent, e.g. a mixture of dioxane or methanol with water, with an aqueous, alkaline-reacting solution, e.g. a sodium hydroxide solution, preferably some at room temperature Hydrolyzed for hours. After acidifying the reaction mixture the 5-hydroxyalkylidene rhodanine derivative is obtained with dilute hydrochloric acid.

The 5-alkoxyalkylidene rhodanine derivatives serving as intermediates can also be added by heating the rhodanine derivatives unsubstituted in the 5-position for 1½ to 3 hours. an orthoester to temperatures of around 150 ⁰ C in good

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get booty.

For the preparation of the compounds in which Y is a sulfur atom is preferably a 5-alkoxyalkylidene rhodanine derivative 15 to 60 minutes with sodium sulfide at room temperature

sets, and the reaction mixture is then acidified with hydrochloric acid.

The rhodanine derivatives unsubstituted in the 5-position and used as starting compounds are either known or can be prepared in the following way from isothiocyanates or dithiocarbamates. For example, isothiocyanates of the general formula RN = C = S are condensed with excess mercaptoacetic acid in the presence of triethylamine by heating to 100 to 140 ° C. in an autoclave for 1 to 4 hours. The corresponding isothiocyanates are prepared, for example, by reacting an amine of the general formula RNH ₂ with thiophosgene of the formula CSCl ₂ . Another possibility for preparing the rhodanine derivatives substituted by R in the 3-position consists in the condensation of a dithiocarbamate of the general formula R-NH-C-SH, preferably as a triethylamine salt,

Il

with chloroacetic acid or a chloroacetic acid ester and then Treatment with a mineral acid.

,. The orthoesters required can be prepared by known methods from the corresponding cyanides, for example according to the following reaction scheme: /

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HCl ^C 2 ^H 5 ^OH _> RC (OC ₂ H ₅ ) ₃

in which R has the meaning given above.

Various 5-hydroxymethylene rhodanines are known from Chemical Reports, Vol. ₀ 91 (1958), p. 2773. From JA ₀ CA, Vol. 76 (1954), p. 1482 5-methoxymethylene 5-ethoxymethylene = _s 5-ethoxyethylidene and 5-ethoxypropylidene rhodanine are known. So far it has not been reported that these rhodanine derivatives are suitable for biological applications. No significant anti-arthritis effect was found with any of these derivatives «

In contrast, the compounds according to the invention are valuable medicinal substances with an anti-arthritic effect.

The invention therefore also relates to medicinal preparations consisting of at least one compound of the general formula I and customary Carriers and / or diluents and / or auxiliaries. '

In studies on rats with inflamed hind paws leaves found that in animals treated with oral doses of 12.5 to 100 mg / kg / day compared to control animals the Paw volume decreases.

The compounds of the invention become medicinal preparations in the usual manner assembled. Preferably a dose contains

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unit about 10 to 200 mg of a compound of the general formula I. Suitable carriers are solids such as lactose, Kaolin, sucrose, talc, gelatin, agar, pectin, gum arabic, magnesium stearate or stearic acid, and liquids such as syrup, peanut oil, olive oil or water. It can too Substances are added that cause a delayed release of active substances, such as glyceryl monostearate or glyceryl distearate, if applicable together with a wax.

The medicinal products can be administered in various forms are present. If solid carriers are used, they can be made up, for example, into tablets, hard gelatine capsules containing powder or granules, or lozenges. The amount of solid carrier can vary widely, preferably it is about 25 mg to 1 g per administration unit. When using liquid carriers, syrups, emulsions, soft gelatine capsules, sterile injection liquids can be used or aqueous or non-aqueous liquid suspensions are prepared.

The medicinal preparations are given in such doses that one adequate anti-arthritic effect without serious side effects entry. It can be administered orally or parenterally, preferably orally. Preferably 1 or 2 doses per day with a total daily dose of about 10 to 400 mg administered. Under these conditions it becomes anti-arthritic Effect achieved with a minimum of side effects.

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The medicinal preparations are made according to the usual pharmacological procedures such as mixing, granulating, pre-pressing and / or dissolving the ingredients.

Example 1 ■

A mixture of 27 g (O 16 ₉ mol) of p-chlorophenyl isothiocyanate, 33 ml (42.5 g, 0.475 moles) mercaptoacetic acid and 5 drops of triethylamine is heated -2 1/2 hours at 120 to 130 ⁰ C in a pressure vessel. The reaction mixture is then left to stand overnight and filtered off. The crude product obtained gives after recrystallisation from ethanol 3- (4> chlorophenyl) -rhodanine, melting at 124.5 to 126 ⁰ C ₀

A mixture of 50 g (0.2 mol) of the rhodanine derivative obtained and 140 g (0.86 mol) of ethyl orthoacetate in 350 ml of acetic anhydride is refluxed for 4 hours. The reaction mixture is cooled and filtered after washing the obtained product with 100 ml 70prozentiger aqueous acetic acid = is obtained 3- (4 ⁱ = chlorophenyl) ~ 5- (1 ⁵ ° äthoxyäthyliden) -rhodanine, melting at 168-171 ⁰ C.

A mixture of 32 g (0.1 mol) 3- (4 '= chlorophenyl) -5- (1 ^! -Äthoxyäthyliden) -rhodanin in 400 ml of water and 250 ml of methanol is mixed with 85 ml of 5% sodium hydroxide solution, and the resulting suspension is stirred for 5 hours at room temperature. The reaction mixture is then filtered off and the filtrate is decolorized. After acidification with dilute hydrochloric acid, 3- (4 ^! -Chlorophenyl) ~ 5- (1'-hydroxyethylidene) -rhodanine with a melting point of 200 to 2O5 ° C is obtained

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Example 2

According to Example 1, propyl orthoacetate is reacted for 5 1/2 hours with 3- (4'-chlorophenyl) -rhodanine in acetic anhydride to give 3- (4'-chlorophenyl) -5- (i'-ethoxypropylidene) -rhodanine. A suspension of 25 g (0.0765 mol) of the latter compound in 200 ml of dioxane and 200 ml of water is mixed with 50 ml of a 10 percent sodium hydroxide solution. The mixture is stirred for 4 hours at room temperature and then ^{evaporated at 40 to 45 °} C. under reduced pressure. The remaining solution is washed with diethyl ether, decolorized and acidified with dilute hydrochloric acid. 3- (4'-Chlorophenyl) -5- (1'-hydroxypropylidene) rhodanine vom-F is obtained. 145 to 149 ° C

Example 3

According to Example 1, orthophenyl acetic acid ethyl ester is reacted with 3- (4'-chlorophenyl) rhodanine in acetic anhydride for 12 hours to give 3- (4'-chlorophenyl) -5- (1'-ethoxy-2'-phenylethylidene) rhodanine. A suspension of 15 g (0.0385 mol) of the last-mentioned compound in 100 ml of dioxane and 1.00 ml of water is mixed with 22 ml of 10 percent sodium hydroxide solution. The mixture is stirred for 3 hours at room temperature and then ^{evaporated at about 40 °} C. under reduced pressure. The remaining solution is washed with diethyl ether and then decolorized. The 'aqueous phase is acidified with dilute hydrochloric acid and the precipitate is taken up in methylene chloride. The solution obtained is washed with water, dried and evaporated under reduced pressure. The residue is dissolved in 10 percent sodium hydroxide solution. The solution obtained is washed with diethyl ether and then mixed with

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acidified with dilute hydrochloric acid. 3- (4'-Chlorophenyl) -5- (i »-hydroxy-2'-phenylethylidene) rhodanine is obtained of mp 134 Ms 137 ° C

Example 4

A suspension of 5 g (0.091 mol) 3- (4 ^l -chlorophenyl) -5- (i ⁽ -ethoxypropylidene) -rhodanine in 15 ml of ethanol is treated with a solution of sodium sulfide in 10 ml of water, and the resulting mixture at room temperature The mixture is stirred for 15 to 20 minutes until a solution is formed. This solution is added to 100 ml of water, left to stand for 15 minutes and then filtered. The filtrate is acidified with 2 η hydrochloric acid. This gives 3_ (41-chlorophenyl) -5- (1 '-mercaptopropyliden) -rhodanine from the temperature to 165 ° C

Example 5

A mixture of 25 g (0.12 mol) of 3-phenylrhodanine, 80 g (0.34 mol) of ethyl orthophenylacetate (prepared according to JACS, Vol. 68 (1946), p. 1917) and 240 ml of acetic anhydride is refluxed for 20 hours . The solution obtained is then evaporated under reduced pressure. The residue is filtered off and the filtrate is stirred for 4 hours with 160 ml of dioxane, 160 ml of water and 40 ml of 10 percent sodium hydroxide solution. The solution obtained is evaporated under reduced pressure at 35 to 40 ° C. to remove the dioxane. The residue is washed with diethyl ether, decolorized with activated charcoal and then acidified with dilute hydrochloric acid. The solid obtained is purified by chromatography. One receives 5-0 ^l -hydroxy-2 ¹ -phenyläthyliden) -3-phenylrhodanin vom

M.p. 146 to 148 ° C. *

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This compound is also obtained when a mixture of 6 g (0.029 mol) of 3-phenylrhodanine, 15 g (0.063 mol) of ethyl orthophenylacetate and 15 ml of n-butyl ether is heated under reflux. The mixture is then ^{heated to 150 °} C., the volatile constituents being drawn off. After heating to 150 ^° C. for 1 hour, a further 5 g of orthoester are added and heating is continued for a further 30 minutes. The reaction mixture obtained is mixed with 5 ml of acetic anhydride and heated for a further 5 minutes. The reaction mixture is then evaporated under reduced pressure. The residue obtained is purified by chromatography on a column loaded with silica gel using a mixture of cyclohexane and benzene (2: 1) as the eluent. ^{5- (1 l} -ethoxy-2'-phenylethylidene) -3-phenylrhodanine can be obtained from the initial eluate. from the F. 119 to 1.-21 ⁰ C isolate. After alkaline hydrolysis of this product in the manner described above, the corresponding hydroxy derivative is obtained. -

Examples

A mixture of 7.5 g (0.05 mol) 3-ethylrhodanine, 25 g (0.128 mol) of methyl orthophenylacetate and 80 ml of acetic anhydride is refluxed for 18 hours. The solution is evaporated under reduced pressure and the residue chromatographed on silica gel using a 50 percent solution of benzene in cyclohexane as the eluent. 3-Ethyl-5- (1'-methoxy-2'-phenylethylidene) rhodanine is obtained from P. 120 to 122 ° C.

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2 g (0.0068 mol) of the rhodanine derivative, substituted in the 5-position, are stirred with 25 ml of dioxane, 20 ml of water and 8 ml of 10 percent sodium hydroxide solution for 2 1/2 hours 40 ^° C. evaporated under reduced pressure. The aqueous solution is washed with diethyl ether and then acidified with dilute hydrochloric acid. 3-Ethyl-5-O ^s "hydroxy-2'-phenylethylidene) rhodanine of .F. 74 to 76 ⁰ C _{0 is obtained}

Example 7

A mixture of 5 g (0.033 mol) of 3-ethylrhodanine, 12 ml of ethyl orthoacetate and 35 ml of acetic anhydride is refluxed for 18 hours. The solution is then evaporated under reduced pressure. The cooled residue is filtered off and the solid obtained is dissolved in diethyl ether. The ether solution is washed with water, dried and evaporated under reduced pressure. 5-0'-Ethoxyethylidene) -3-ethylrhodanine is obtained. This product (3 ₅ 6 g) is stirred with 15 ml of dioxane, 15 ml of water and 15 ml of 10 percent sodium hydroxide solution for 4 hours. The resulting solution is evaporated at 40 ° C under reduced pressure and the aqueous solution with

Diethyl ether ",. ' _Tj _' ..

/ washed, decolorized and acidified with dilute hydrochloric acid. The precipitate is dissolved in 10 percent sodium hydroxide solution and washed with diethyl ether. The solution is then acidified with dilute hydrochloric acid. 3-Ethyl-5-O'-hydroxyethylidene) rhodanine vonrT is obtained. 93 ⁰ C.

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Examples

A mixture of 8.4 g (0.04 mol) of 3-phenylrhodanine, 21 g (0.12 mol) of ethyl orthopropionate and. 80 ml of acetic anhydride is refluxed for 6 hours, cooled and filtered. The solid obtained is washed with 50 percent aqueous acetic acid. This gives 5- (i'-Äthoxypropyliden) -3-phenylrhodanine, melting at 178 to 181 ⁰ C.

10 g (0.034 mol) of the ethoxy derivative obtained are stirred for 4 hours in 80 ml of dioxane, 80 ml of water and 20 ml of 10 percent sodium hydroxide solution. The resulting solution is evaporated at 35 to 40 ° C. under reduced pressure and the aqueous solution is washed with diethyl ether and acidified with dilute hydrochloric acid. Obtained "5- (i'-hydroxypropylidene) -3-phenylrhodanine, melting at 105-111 ⁰ C.

Example 9

A mixture of 24.4 g (0.1 mol) 3- (4'-chlorophenyl) rhodanine, 80 g of ortho-ß-phenylpropionic acid methyl ester (prepared according to J.A.C.S., 69: 2665 (1947)) and 150 ml of acetic anhydride is refluxed for 18 hours. When the mixture is left to stand at room temperature, a solid precipitates. This is filtered off and washed with acetic acid. 3- (4'-Chlorophenyl) -5- (1 · ethoxy-3'-phenylpropylidene) rhodanine is obtained » This product (20 g, 0.052 mol) is in 250 ml of dioxane, 250 ml of water and 35 ml of 10 percent strength at room temperature for 2 hours Stirring sodium hydroxide solution. The solution is then evaporated at 40 ° C under reduced pressure and the residue with Washed diethyl ether. The aqueous solution is again at

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4O ° C evaporated under reduced pressure and the "residue washed again with diethyl ether. The aqueous solution is with acidified with dilute hydrochloric acid. 3- (4'-Chlorophenyl) - '5- (1'-hydroxy-3'-phenylpropylidene) rhodanine with a melting point of 170 to 173 ° C.

• Example 10

According to Example 1, a mixture of 6.12 g (0.04 mol) of p-fluorophenyl isothiocyanate, 4.15 ml (5.5 g, 0.06 mol) of mercaptoacetic acid and 5 drops of triethylamine for 3 hours in a pressure vessel at 110 - heated to 130 ^{0 C.} After cooling and filtering, 3- (4'-fluorophenyl) rhodanine with a melting point of 155 to 158 ° C. is obtained.

By analogous implementation of this rhodanine (0.2 mol) with 140 g

C,

(0.86 mol) of ethyl orthoacetate in 350 ml of acetic anhydride and subsequent alkaline hydrolysis of the 5- (1'-ethoxyethylidene) -3- (4'-fluorophenyl) rhodanine obtained as an intermediate 3- (4-fluorophenyl) -5- (1 "-hydroxyethylidene) rhodanine is obtained.

B e i s ρ i e 1 11

A solution of 4.73 g (0.05 mol) of chloroacetic acid in 40 ml of water a solution of "2.7 g (0.025 mol) of sodium carbonate in 20 ml of water is added. The resulting solution is mixed with cooled in an ice bath and over the course of 5 minutes in portions with 14.2 g (0.05 mol) of the triethylamine salt of p-tolyldithiocarbamic acid offset. The resulting mixture is stirred for 1 1/2 hours at room temperature and then with water brought a volume of 150 ml. The mixture is then heated on a steam bath for 5 "minutes and then filtered off.

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The filtrate obtained is acidified with 40 ml of 6 η hydrochloric acid, heated to 95 ° C., cooled and filtered. After washing the solid with water to give 3- (4'-tolyl) -rhodanine, melting at 164-165 ⁰ C.

According to Examples 1 and 2, ethyl orthopropionate is converted into 5- (1'-ethoxypropylidene) -3- (4'-tolyl) rhodanine with 3- (4'-ToIyI) -rhodanine in acetic anhydride implemented. The latter compound is hydrolyzed with 10 percent sodium hydroxide solution. After working up, 5- (1'-hydroxypropylidene) -3- (4'-tolyl) rhodanine is obtained. * ^

Example '12

A mixture of 6.12 g (0.03 mol) of 3,4-dichlorophenyl isothiocyanate, 2.8 ml ( 3.68 g, 0.04 mol) of mercaptoacetic acid and a few drops of triethylamine is heated to 110 to 130 for 2 hours in a pressure vessel ° C '. The reaction mixture is then cooled and filtered. To give 3- (3 ', 4'-dichlorophenyl) -rhodanine, melting at 176 to 178 ⁰ C.

This rhodanine derivative is reacted according to Example 1 and 3 with ethyl orthophenylacetate in acetic anhydride to give 3- (3 ', 4 -'-dichlorophenyl) -5- (1'-ethoxy-2'-phenylethylidene) rhodanine, which is converted in an analogous manner to 3- (3 ', 4'-dichlorophenyl) -5- (i' -hydroxy-2 ¹ -phenylethylidene) -rhodanine is hydrolyzed.

Using 2-chloro-4-methylphenyl isothiocyanate, 3- (2 ^l -chloro-4'-methylphenyl) -rhodanine is obtained in the manner described, which is mixed with ethyl orthophenylacetate.

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is set. The 5-alkoxy derivative obtained as an intermediate becomes 3- (2'-chloro-4-methylphenyl) -5- (1'-hydroxy-2'-phenylethylidene) -rhodanine hydrolyzed.

B e i s ρ i e Components 1 13th mg / tablets 3- (4ι-chlorophenyl) -5- (1'-hydroxy-3 ' phenylpropylidene) rhodanine C-J Calcium sulfate dihydrate 150 Sucrose ' 25th strength 15th Talc 5 Stearic acid 3

Sucrose, calcium sulfate and 3- (4'-chlorophenyl) -5- (1'-hydroxy-3'-phenylpropylidene) -rhodanine ' mixed thoroughly and granulated with hot 10 percent gelatin solution. The moistened The mass is passed through a sieve with a mesh size of 3.35 mm directly into a drying tray. The granules will dried at 49 ° C, passed through a sieve with a mesh size of 0.83 ram, mixed with starch, talc and stearic acid and compressed into tablets.

Example 14 Ingredients mg / capsule

3_ (4'-Chlorophenyl) -5- (1'-hydroxy- _3'-150 phenylpropylidene) rhodanine

Magnesium stearate .5

Lactose -_. 300

The aforementioned ingredients are passed through a sieve with a mesh size of 0.42, mixed and filled into hard gelatine capsules No. 0.

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Examples 15 to 35

According to the methods described above, the 5- (1'-Hydroxyalkylidene) -rhoda- listed in the following table -nine derivatives from the corresponding 5- (1'-ethoxyalkylidene) rhodanine intermediates manufactured. The intermediates are made in the following ways:

(A) 1 mol of a 3-substituted rhodanine derivative, 3 mol of a corresponding orthoester and about 5 mol of acetic anhydride are refluxed for 16 to 18 hours. The reaction mixture is evaporated under reduced pressure to remove the acetic anhydride. Then will the product crystallized by adding petroleum ether ". Another possibility is to remove the residue chromatographically below on a column filled with silica gel Purify elution with mixtures of cyclohexane and benzene.

(B) A rhodanine derivative substituted in the 3-position is Heated for 2 to 3 hours with 2 to 3 mol of a suitable orthoester to temperatures of 150 to 155 ° C. The further work-up is carried out according to (A).

These intermediate products are in a mixture of 3 to 5 parts by volume of dioxane and 3 parts by volume of 10 percent sodium hydroxide solution and 3 parts by volume of water hydrolyzed. The reaction mixture takes 1 to 2 hours for complete hydrolysis stirred at room temperature. Then by evaporation under reduced pressure - most of the dioxane removed. The remaining solution is extracted with diethyl ether

and the product is precipitated by acidification with dilute hydrochloric acid.

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Tabel

Q CD CO JPy to

example R. R ₁ Ethoxy intermediate
Procedure F. G 118 - 120 Hydroxy compound
F. ⁰ C 135. 15th 4-chlorophenyl 4-chlorobenzyl B. ¹ 165- - 166 133 - 140 16 4-chlorophenyl 4-methylbenzyl B. 105 · -. 106 139 - 93 17th Isopropyl Benzyl B. 106 - 107 '■ 91. - 170 18th 4-chlorophenyl Isobutyl B. 66 = 68 168 - 69 ■ 19th n-propyl Benzyl B. syrup 68 - 93 20th Isobutyl Benzyl " B. 111 - 116 91 - 110 21 Benzyl Benzyl B. 62 - 64 ' 108 - 46 22nd ethyl ethyl B. 55- ' 57 45 - 56 23 Isopropyl ethyl A. 98 - 99 55 - 93 24 ■ Benzyl ethyl A. 60 - 61 74 25th Allyl ethyl A. 59 - , 61. 72 - 79 26th Isobutyl ethyl A. 75 - 78 78 - 1> 03 27 Cyclopropyl ethyl 'B 39 - 41 52 28 n-butyl ethyl A. 91 - 93 50 - 101 29 Cyclohexyl ethyl A. 97- 98 100 - 119 30th Phenethyl ethyl 'b syrup 118 - 31 sec-butyl ethyl B. 52 - 54 syrup 69 32 n-propyl ethyl B. 96 - 98 68 - 98 33 methyl Ethyl ^: B. 86 - 88 95 - 186 34 3-pyridylmethyl ethyl ■ A ' 82 - 83 216 35 2-pyridylmethyl ethyl A ' 215 -

Claims (20)

Claims Vf is 5-hydroxy (mercapto) of the general alkylidenrhodaninderivate my formula I. R-N -YH R ₁ . (D in which R is a straight-chain or branched lower alkyl radical with 1 to 4 carbon atoms, a cycloalkyl radical with 3 Ms 6 carbon atoms, an alkenyl radical with 3 to 5 carbon atoms, an optionally substituted phenyl radical, a phenylalkyl radical with 7 to 9 carbon atoms, a monohydric phenyl, dichlorophenyl -, alkylphenyl, methylchlorophenyl or pyridylmethyl _{radical, R 1 is} a branched or straight-chain lower alkyl radical with 1 to 4 carbon atoms, a phenylalkyl radical with 7 "to 9 carbon atoms, the alkyl radical of which can be straight-chain or branched, a monochlorobenzyl or monomethylbenzyl radical and Y an oxygen - or means sulfur atom.; 2.. Compounds according to Claim 1, characterized in that Y denotes an oxygen atom. 3. Compounds according to claim 2, characterized in that that R is a lower alkyl radical, the phenyl, monochlorophenyl, Means cyclohexyl or benzyl group. 4. Compounds according to claim 3, characterized in that that R ^ denotes the methyl, ethyl, benzyl or phenethyl group. 3 0 98 4 9/1207 , ''" ¹⁹ ■"'7325038 5. A compound according to claim 4, characterized in that R is the 4'-chlorophenyl group and R _{1 is} the "methyl group. 6. A compound according to claim 4, characterized in that R is the 4 »-chlorophenyl group and R _{1 is} the ethyl group. 7. A compound according to claim 4, characterized in that R is the 4'-chlorophenyl group and R _{1 is} the benzyl group. 8. A compound according to claim 4, characterized in that R is the 4'-chlorophenyl and R _{1 is} the phenethyl group. 9. A compound according to claim 4, characterized in that R is the phenyl group and R _{1 is} the ethyl group. 10. A compound according to claim 4, characterized in that R is the phenyl and R _{1 is} the benzyl group. 11. A compound according to claim 4, characterized in that R is the ethyl group and R _{1 is} the benzyl group. 12. A compound according to claim 4, characterized in that R and R ^ each represent the benzyl group. 13. A compound according to claim 4, characterized in that R is the benzyl group and R _{1 is} the ethyl group. · 14. A compound according to claim 4, characterized in that R is the methyl group and R _{1 is} the ethyl group. 309849/1207 ^Γ ·. - 20 - 7325038 15. A compound according to claim 4, characterized in that R is the n-propyl group and R _{1 is} the ethyl group. * 16. A compound according to claim 4, characterized in that; that κ .5 R denotes the n-butyl group and R ₁ denotes the ethyl group. 17. A compound according to claim 4, characterized in that R is the cyclohexyl group and R ^ is the ethyl group. 18. A compound according to claim 4, characterized in that R denotes the ESenzyl group and R ^ denotes the ethyl group. 19. A process for the preparation of the compounds according to claim 1, characterized in that one in the 5-position un ~ * 15- substituted rhodanine with an orthoester in acetic anhydride and the resulting 5-alkoxyalkylidenrhodanine a) hydrolyzed under alkaline conditions for the preparation of the compounds in which Y is an oxygen atom . and then acidified or b) for the preparation of the compounds in which Y is a sulfur atom, reacted with sodium sulfide in aqueous ethanol and then acidified. 20. Medicinal preparations consisting of at least one compound according to claim 1 and customary carriers and / or diluents and / or auxiliaries. 3 0 d 8 U 9 / I 2 U 7