DE2744353A1 - HYDANTOIN DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE - Google Patents

Description

The invention relates to new hydantoin derivatives which have a quaternary ammonium group attached to one of the ring nitrogen atoms contain. These quaternary ammonium salts of hydantoin are valuable antistatic agents. Some These quaternary ammonium salts of hydantoin also have a bactericidal and / or fungicidal effect. The invention therefore also includes germicidal compositions with a broad spectrum of bactericidal and fungicidal activity which are effective Ingredients containing certain quaternary ammonium salts of hydantoin.

For a long time, the chances of survival for the human population were essentially a measure of human ability dependent on protecting oneself and one's surroundings against harmful effects. In view of the ever increasing There is an ongoing need for both the effectiveness of the methods and the population of the earth To improve substances that give protection against unwanted fungi and bacteria. Such improvements can

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in a more effective control of the bacteria and / or fungi using lesser amounts of substances with lesser amounts Time and effort are involved. Various compounds of the invention containing these compounds Compositions and methods of using them represent a major step forward in these directions represent.

As is apparent from U.S. Patent 3,228,829, hydrous organic mixtures such as emulsified cutting oils, latices, latex paints, aqueous adhesives, hydraulic Liquids and pulp dispersions used in papermaking are more effective in the absence Germicides subjected to attack by contaminating bacteria, in particular those of the species Pseudomonas and Aerobacter, which lead to a deterioration in the desired properties, foul smell, sludge formation and in people who work with Bypassing these materials can also lead to skin infections. When it comes to the preservation of water-based systems A variety of problems arise from microbial degradation. To find substances that meet the numerous requirements extensive research has already been carried out. The multitude of for this A means offered for an end is, to a certain extent, proof that none is without its disadvantage.

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The first requirement for a preservative is, of course, that it is effective against the attacking organisms. In addition, there is its persistence and its lasting effect in the system in which it is used. To be effective in these To unfold systems, the preservative must have a certain water solubility. When the aqueous system requires handling, the preservative should not be irritating to the skin under the conditions of use works. For environmental reasons it has also become increasingly important that the toxicity of these preservatives compared People and fish is relatively small.

With regard to the main restrictions placed on the use of bactericides such as hexachlorophene, the invention represents a promising alternative.

The main aim of the invention are bactericidal and fungicidal compounds with a broad spectrum of activity, the use of which requires smaller amounts than has generally been the case up to now were required. Another aim is a new class of compounds with special surface-active properties and of compounds with antistatic properties.

The quaternary ammonium salts of hydantoin according to the invention have the general formula:

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4 ι Τ (D

R ₁ N _y N

in which R ₁ and R- are identical or different and are hydrogen atoms, lower alkyl groups with 1 to 6 carbon atoms, -CH ₀ OH or
η zn

- (CH ₂ J ₃ NR ₅ *

^R 6

represent, where at least one of the substituents R- and R _{2 has} the meaning

R-

R, and R _{4 are} identical or different and denote hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, phenyl groups or together a cycloaliphatic group with 4 or 5 carbon atoms, R ₅ , R ₆ and R _{7 are} identical or different and are benzyl groups

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or -CH ₂ .. represent, X is a physiologically acceptable anion, η is an integer from 1 to 4 and ρ is an integer from 1 to 24.

One of the embodiments of the invention comprises compounds of the general formula (I) in which, when R. is = -C H-OH, R_ the meaning

^R 7

NR ₆ X

^R 5

has, and if R. has the meaning

^R 7

- (CH ₂ ) 3 NR ₆ X

has, R.,; = -C H-OH. λ η 2η

A further embodiment of the invention comprises compounds of the general formula (I) in which R ₁ and R-, which can be identical or different, have the meaning

^R 7

NR ₅ X

to have.

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Another embodiment of the invention comprises compounds of the general formula (I) in which one of the substituents R _{1 and R 1 is} hydrogen or a lower alkyl group having 1 to 6 carbon atoms and the other is the meaning

^R 7

^R 6

Preferred hydantoin derivatives according to the invention are the quaternary ones Ammonium salts of 5,5-disubstituted hydantoin, where R, and R, which can be the same or different, are alkyl groups with 1 to 6 carbon atoms, phenyl groups or together a cycloaliphatic group with 4 or 5 carbon atoms represent. The 5,5-dimethylhydantoin derivatives are particularly preferred.

Preferably R ₇ = -CH ₂ .., where ρ represents an integer from 8 to 24 and in particular from 12 to 18, while R ₅ and R 1 mean lower alkyl groups with 1 to 6 carbon atoms, in particular the methyl group.

These salts have antistatic properties and can be used to Example during the finishing stage in textile materials,

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such as carpets, socks and underwear are incorporated to give them antistatic and softening properties. The salts also have surface-active properties and are useful wetting agents. Those salts in which R ₁ or R "= -CH" OH and η = 1 form formaldehyde-releasing agents.

The incorporation of these monoquaternary ammonium salts of hydantoin in aqueous organic mixtures, such as cosmetic Preparations, as well as the application of these salts to the skin, gives an effective germicidal protection and reduces Damage to the preparations or the skin caused by bacteria or fungi, or excludes such Damage. Bacterial and fungal infections can be combated or prevented with the compounds according to the invention will.

Compounds according to the invention with bactericidal and / or fungicidal The general formulas have an effect:

Γ ³

? 12 ^H 25 ^CH 3 <f <ί = 0 _? 12 ^H 25

N (CH ₉ ). NN (CH ₉ KN CH-. Z

2'3

^CH 3 «fj ^CH 3 (II)

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CH-

C N

- N

CH

(CH ₃ J ₃ -

CH.

CH ₃ C

^C 12 ^H 25 N CH.

N N-

Z (HD and

or

CH.

CH,

Il

(CH ₇ ) -, N

'2'3

CH.

CH.

(IV)

where Rq = -C H "OH and Z is a physiologically acceptable anion and η has the meaning given above.

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Suitable physiologically acceptable anions are the halogen
ions, especially the bromide, chloride or iodide and sulfate. The halogen anions are preferred and of these
especially the bromide.

Of course, when sulfate anions are present, there is only one half a mole of anion per mole of cation present.

Examples of the many quaternary ammonium salts of the
3- (3'-aminopropyl) hydantoin compounds of the general
Formula (I) are:

1-methylol-N, N-dimethyl-N-dodecyl-quaternary-ammonium bromide, i-Methylol-NfN-dimethyl-N-dodecyl-quaternary-ammonium chloride, 1-methylol-N, N, N-trimethyl-quaternary-ammonium iodide,

1-methylol-N, N-dimethyl-N-dodecyl-quaternary-ammonium iodide,

1-methylol-N, N-dimethyl-N-benzyl-quaternary-ammonium chloride, i-methylol-N-methyl-N-ethyl-N-dodecyl-quaternary-ammonium bromide, i-methylol-N-methyl-N-ethyl-N-dodecyl-quaternary-ammonium chloride, 1-methylol-N-methy1-N-benzyl-N-dodecyl-quaternary-ammonium bromide, i-Methylol-NjN-dibenzyl-N-dodecyl-quaternary-ammonium bromide, 1 -Methylol-N-N-dimethyl-N-octadecyl-quaternary-ammonium bromide, 1-methylol-N, N-octadecyl-quaternary-ammonium chloride,

1-methylol-N, N-dimethyl-N-hexadecyl-quaternary-ammonium chloride, 1-methylol-N, N-dimethyl-N-hexadecyl-quaternary-ammonium bromide,

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1- (ß-Hydroxyethyl) -N, N-dimethy1-N-dodecyl-quaternary ammonium chloride,

1- (ß-Hydroxyethyl) -NjN-dimethyl-N-dodecyl-quaternary-iranonium bromide,

1- (ß-Hydroxyethyl) -Ν, Ν-dimethyl-N-benzyl-quaternary ammonium chloride,

1- (ß-Hydroxyethyl) -N, N-dimethy1-N-dodecyl-quaternary ammonium iodide,

1- (ß-Hydroxyethyl) -N-methyl-N-ethyl-N-dodecyl-quaternary ammonium bromide,

1- (β-Hydroxyethyl) -N-methyl-N-ethyl-N-dodecyl-quaternary-ammonium chloride and the

1- (β-Hydroxyethyl) -N, N-dimethyl-N-hexadecyl-quaternary-ammonium bromide.

Examples of the many monoquaternary ammonium salts of the 3- (3'-aminopropyl) hydantoin compounds according to the invention are these:

N, N-dimethyl-N-dodecyl-quaternary-ammonium bromide, NfN-dimethyl-N-dodecyl-quaternary-ammonium chloride, Ν, Ν-dimethyl-N-benzyl-quaternary-ammonium chloride, Ν, Ν-dimethyl-N-dodecyl-quaternary-ammonium iodide, N-methyl-N-ethyl-N-dodecyl-quaternary-ammonium bromide, N-methyl-N-ethyl-N-dodecyl-quaternary-ammonium chloride, N-methyl-N-benzyl-N-dodecyl-quaternary-ammonium bromide, N, N-dibenzyl-N-dodecy1-quaternary-ammonium bromide,

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N, N-dimethyl-N-octadecyl-quaternary-ammonium bromide, NjN-dimethyl-N-hexadecyl-quaternary-ammonium chloride and that N, N-dimethyl-N-hexadecyl-quaternary-ammonium bromide.

The compounds listed above represent only a few representative members of the compounds encompassed according to the invention represent.

This selection of salts applies to hydantoin, 5-monosubstituted and 5,5-disubstituted hydantoins, 5-methylhydantoin and 5,5-dimethylhydantoin included.

Examples of the many bis-quaternary ammonium salts of the 1,3-di- (3'-aminopropyl) hydantoin compounds according to the invention are these:

N, N-dimethyl-N-dodecyl-quaternary-ammonium bromide, NjN-dimethyl-N-dodecyl-quaternary-ammonium chloride, Ν, Ν, Ν-trimethyl-quaternary-ammonium iodide, N, N-dimethyl-N-dodecyl-quaternary-ammonium iodide, N, N-dimethyl-N-benzyl-quaternary-ammonium chloride, N-Methy1-N-ethyl-N-dodecyl-quaternary-ammonium bromide, N-methyl-N-ethyl-N-dodecyl-quaternary-ammonium chloride, N-methyl-N-benzyl-N-dodecyl-quaternary-ammonium bromide,

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N, N-dibenzyl-N-dodecyl-quaternary-anunonium bromide,
NjN-dimethyl-N-octadecyl-quaternary-ammonium bromide,
NjN-dimethyl-N-octadecyl-quaternary-ammonium chloride,
N ^ -Dimethyl-N-hexadecyl-quaternary-ammonium chloride and the N, N-dimethyl-N-hexadecyl-quaternary-ammonium bromide.

Again, these salts represent only a representative selection of the salts for hydantoin, 5-monosubstituted and 5,5-disubstituted Hydantoins, 5-methylhydantoin and 5,5-dimethylhydantoin locked in.

The 5,5-disubstituted hydantoin compounds are preferred, especially the 5,5-dimethylhydantoins. However, other disubstituted salts can also be used for the abovementioned salts
Compounds can be used, for example 5-methyl-5-ethyl-hydantoin, 5,5-diphenylhydantoin, 5-methyl-5-phenylhydantoin and 5,5-pentamethylene-hydantoin.

The invention thus comprises a large number of quaternaries
Ammonium salts of hydantoins and their manufacture. It is obvious to a person skilled in the art that derivatives not expressly described here can easily be converted in an analogous manner
can be produced. It is only necessary to select suitable starting materials and, if necessary, to adjust the reaction conditions accordingly. The specific

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It is not necessary to write down and list all of the quaternary ammonium salts encompassed by the invention.

The compounds of the general formulas (I), (III) and (IV) can easily be prepared by adding 1 mol of acrylonitrile to the selected hydantoin, which can be unsubstituted or mono- or disubstituted in the 5-position, for Example for 5,5-dimethylhydantoin, whereupon the corresponding Receives mononitrile. The reaction is carried out in a closed reaction vessel, for example in a stirred autoclave an aqueous solvent in the presence of a catalytically effective amount of, for example, about 0.5 to 1.5% by weight of the Starting hydantoin of a 45 to 50% aqueous KOH or NaOH solution carried out at a temperature of about 70 to 101 ° C. It runs according to the following equation:

^R 3? 3

C = OR ₄ C

HNNH cat. ^ HN NCH ₂ CH ₂ CN

\ / CH ₀ = CHCN \ '

S. ² <ü (V)

The nitrile (V) produced in this way is treated with hydrogen

2
a pressure of 28 to 42 kg / cm at a temperature of about 100 to 125 ° C in the presence of a suitable catalyst, for example Raney nickel, to the corresponding monoamine (VI)

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hydrogenated. The reaction proceeds according to the following equation:

H N

NCH ₂ CH ₂ CN

(V)

^{2 H} 2 _v

} H N

Ni-Kat. \ /

The obtained monoamine (VI) is then using Formaldehyde and formic acid are methylated to the corresponding mono-tert-amine (VII). This implementation proceeds according to the following Equation:

R-

N Y *

(VI)

2CH ₂ O

CH ₂ CH ₂ CH ₂ NH ₂

JO

Other useful mono-tert-amines can be made by stepwise Alkylation of the monoamine (VI) can be produced. For example, you can use the N-methyl-N-benzyl-tert-amine (VIIa) prepare by adding first methyl chloride and then benzyl chloride to the amine (VI). This alkylation proceeds according to the following Equation in front of you:

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H N

C =

N-

1. CH ₃ Cl NaOH

2. C ₆ H ₅ CH ₂ Cl NaOH

-C-

-C: N-

CH,

(CH ₂ ) 3-M

CH,

(VI)

(Vila)

Compounds in which R _n . and / or R, = -CH " . can be prepared in a similar manner by adding corresponding alkyl halides CH "..X, where X and ρ have the meanings given. The reaction of the tertiary amine of the general formula (VII) or (VIIa) with a suitable alkyl halide, for example dodecyl bromide with the general formula CH " ₊₁ X, preferably in the presence of an effective amount of, for example, less than 1% of an alkali metal hydroxide as a catalyst and a solvent gives the desired quaternary ammonium salt (VIII) according to the following

Equation:

R, R-.

NCH ₂ CH ₂ CH ₂ N-CH ₃ -

^C P ^H 2P ₊ 1 ^X

H-

Benzene or toluene as a solvent

[CH ₂ CH ₂ CH ₂ N-CH ₃

CH.

(VII)

(VIII)

The bis-quaternary ammonium compounds of the general formulas (I) and (II) can easily be prepared by

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that 2 moles of acrylonitrile are added to the selected hydantoin which is not substituted or mono- or disubstituted in the 5-position can be like 5,5-dimethylhydantoin there. You get the corresponding dinitrile (IX). The reaction is carried out in a closed reaction vessel, for example in a stirred autoclave in the presence of a catalytically effective amount of, for example, about 0.5 to 1.5% by weight of the starting hydantoin a 45 to 50% aqueous KOH or NaOH solution at a temperature of about 70 to 135 ° C. She runs according to the following equation:

R-

Γ C-

0 ■ H

Cat.

Il 0

2 CH ₂ = CHCN

-) MCCH ₂ CH ₂ N,

NCH ₂ CH ₂ CN

(IX)

The dinitrile (IX) obtained in this way is treated with water

substance under a pressure of 3 5 to 42 kg / cm at a temperature of about 100 to 125 C in the presence of a suitable Catalyst, for example Raney nickel, hydrogenated to the corresponding diamine (X) according to the following equation:

NCCH ₂ CH ₂ N

NCH ₂ CH ₂ CN

^ H ₂ NCH ₂ CH ₂ CH ₂ N
Ni cat. \

Il 0

(IX)

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NCH ₂ CH ₂ CH ₂ NH ₂ (X)

The diamine (X) is then combined with formaldehyde and formic acid methylated to the corresponding di-tert-amine (XI). The methylation runs according to the following equation:

4CH ₂ O

H, NCH, CH, CH, N tO, CH CH NH ¹ - > CH ₃ -NCH ₂ CH CH ₃ N N CH CH CH N-CH ₃

² \ / * ■ * ■ <■ ^l HCOOH \ I

N tO, CH CH NH> CH ₃ NCH ₂ CH CH ₃ NN

\ / * ■ * ■ <■ ^l HCOOH \ /

Il

(XI)

Other useful di-tert-amines can be made by stepwise Alkylation of the diamine (IX) can be produced. For example, one can N-methyl-N-benzyl-di-tert-amine by stepwise Add methyl chloride and benzyl chloride to diamine (IX) using the following equation:

R ₄ CC ^ 0 1.2CH ₃ Cl CH ₃ R ₄ CC = O CH ₃ I I NaOH I III _V - <CH ₂ , ₃ - 'I, «,,, -«, --__, H _t CH _2> 3—. _N - (C " ₂ , ₃ -K

NaOH f ² C CH ₂

Compounds in which R_ and / or R _ß = -CH " * can be prepared in a similar manner by the gradual addition of suitable alkyl halides C H_ ^ X, where X and ρ have the meanings given.

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The implementation of the di-tert-amine (X) or (Xa) with a corresponding one Alkyl halide, for example lauryl bromide of the general formula C H ".X, which is preferably in the presence an effective amount of, for example, less than 1% of the alkali metal hydroxide catalyst and a solvent is carried out, gives the desired bis-quaternary ammonium salt (XI) according to the following equation:

R <—- *

2CH, ^, X C

© | P

CH

.NCH ₂ CH ₂ CH ₂ N NCH ₂ CH ₂ CH ₂ N-CH ₃ CH ₃ -NCH ₂ CH ₂ CH ₂ N NCH ₂ CH ₂ CH ₂ N-CH ₃ X

CH ₃ \ / CH ₃ benzene or CH _3. , Ch ₃

0 toluene as °

(X) solvent (xi)

It is known that commercially available alkyl halides of the general formula C H_ ..X are present as mixtures can vary, for example in terms of chain length. These mixtures are equally suitable for the one according to the invention Processes like the purified alkyl halides. For example, a suitable alkyl halide includes a mixture from predominantly octadecyl halide together with hexadecyl halide and / or tetradecyl halide. Connections that were prepared with such mixtures, therefore, alkyl groups with chain length varying in the desired range can be used contain.

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The implementation of the mono-quaternary ammonium salt (VIII) in Aqueous alkaline solution with formaldehyde gives the desired monomethylol-mono-quaternary ammonium salt (XII) following equation:

© Γ r \ ^CH i ° I ® ' F)

H NN CH ₂ CH ₂ CH ₂ -N CHj Χ ^ϋ i-> HIGH ₂ NN CHjCHjCHj— N CH ₃ X ^

^CH 3 I ^CH 3

ο ο

(VIII) ( ^χΙΙ >

Compounds of the general formula (I) and (IV) in which R. represents the β-hydroxyethyl group can be used in the same way Way by adding ethylene oxide to the selected monoquaternary ammonium compounds.

The addition of the first mole of acrylonitrile to hydantoins, the ring nitrogen atoms of which are not substituted, in alkaline Medium, leads to a reaction at the nitrogen atom in the 3-position. For the preparation of compounds which have the mono-quaternary ammonium substituent on the ring nitrogen atom in the 1-position

and a -CH ₀ OH substituent (n = 2-4) on the ring nitrogen 2n

have atom in 3-position, it is therefore necessary to add the corresponding alkylene oxide before adding the acrylonitrile. If R ₀ is supposed to represent the methylol group (that

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if η = 1), the nitrogen atom in the 3-position must be protected with a group which is inert towards the acrylonitrile before the acrylonitrile is added. After the acrylonitrile has been added, the protective group is removed again. For example, the nitrogen atom in the 3-position can be provided with a —CH — Cl substituent by reacting the selected 1,3-unsubstituted hydantoin with formaldehyde and thionyl chloride. After the addition of the acrylonitrile to the nitrogen atom in the 1-position, the -CH ₂ C1-substituent is removed by hydrolysis, so that the corresponding 1-monoquaternary hydantoin salt is obtained, which upon further treatment with formaldehyde in an aqueous solution, the 1-mono- quaternary ammonium 3-methylolhydantoin salt results.

The starting hydantoins for the preparation of the compounds (I), (II), (III) and (IV) are known.

For the preparation of compounds with a mono-quaternary Ainmoniumsubstituenten on the nitrogen atom in the 1-position and Hydrogen on the nitrogen atom in the 3-position is from the For the reasons given above, it is also necessary to add a protective group to the 3-position before adding the acrylonitrile provided, which is inert to the acrylonitrile. The protecting group is then also removed again. To the Example can be given as above by treating with

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Formaldehyde and thionyl chloride form the nitrogen atom in 3-Stellunq with a -CH-Cl -substituent which follows the addition of the acrylonitrile in the 3-position is removed again by hydrolysis.

The invention also encompasses bactericidal and funcicidally effective Compositions that are an effective component of a quaternary The ammonium salt of hydantoins of the general formulas (II), (III) or (IV) contain. These compositions show a broad spectrum of activity both against bacteria and against Funqi, so that if both types of infection exist, they can be combated with a single composition.

The compounds according to the invention also provide, as already mentioned, are antistatic, surface-active or wetting agents and are therefore suitable for incorporation into deodorants, soaps, Cosmetics and antiseptic lotions qeeiqnet to keep infections to fight against unwanted bacteria and / or funqi or to prevent. They can also be used to treat and prevent unwanted bactericidal and fungicidal infections from Wounds used in humans and animals are made by cutting them applies to the wound in the form of wound cleansers.

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Another intended use of the compounds according to the invention consists in their encore? to aqueous organic mixtures, such as emulsified cutting oils, latices, paints and the like, to an infestation with bacteria or Fungi as described in U.S. Patent 3,228,829 to fight or prevent.

Contain the bactericidally and / or fungicidally active compositions with a broad spectrum of activity according to the invention in addition to the active compounds (II), (III) or (IV), inert solid or liquid diluents or carriers. In general the compounds (III) or (IV) are effective when they are used in an amount of from about 0.025 to about 10% and in particular from about 0.0025 to about 0.1% by weight in aqueous-organic Mixtures as described in U.S. Patent 3,228,829, cited above, are incorporated. The connections of the general formula (II) are effective when they are in an amount of about 0.00007 to about 10% and in particular of from about 0.00007 to about 0.1%.

The bactericidally and / or fungicidally active compositions can be produced in the form of liquids or solids will. The active compounds can, for example, be incorporated directly into cosmetic preparations. she can also be in solutions, suspensions or antiseptic Formulations to be included.

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The compounds (II), (III) and (IV) can also be incorporated into gel, cream, lotion or powder formulations.

When the composition of the invention as a liquid is present, it preferably contains a surfactant to disperse the active compound in the to effect aqueous solutions. The solutions can be used as sprays, for example.

If the bactericidally and / or fungicidally active compositions are to be used as antiseptics, the carrier must of course be inert and non-toxic. The antiseptics can be in the form of gels, creams, lotions, and suspensions Powders are present which can be prepared in a conventional manner by incorporating the active ingredient into the appropriate carrier materials see US Pat. No. 2,886,487.

As already stated, the bactericidally and / or fungicidally active compositions can be used as sprays in the form of aerosols are used in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane under pressure be kept in a container.

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Compositions to be used in the form of aqueous dispersions or emulsions are usually in the form of concentrates with a high proportion of the active ingredient or ingredients before their application be diluted with water. These concentrates must be able to be stored for long periods of time and after storage be dilutable with water to give aqueous preparations which remain homogeneous for a relatively long period of time.

The fungicidally active compositions according to the invention In addition to the hydantoin salt, one can of course also use one or contain several other biologically active compounds.

The following examples illustrate the invention.

example 1 Production of mono-quaternary ammonium salt

Into a 22 liter flask equipped with a mechanical stirrer, thermometer and reflux condenser, there were 3203 g (25 mol) of 5,5-dimethylhydantoin and 500O ml Given water. When heated to 73 C, complete dissolution of the dimethylhydantoin occurred. Then 664 g (12.5 mol) Acrylonitrile and 24 g of 50% strength aqueous NaOH were added as a catalyst. Reflux occurred and was continued until the temperature had reached 100 ° C. Then the heat

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supply interrupted and when the temperature has fallen to about 7 3 C. was, 663 g (12.5 mol) of acrylonitrile were added. After the temperature reached 100 to 101 C, was the supply of heat was interrupted, cooled from the outside until the temperature had fallen to 3 1 C and the cooled reaction solution was seeded with a monoconitrile crystal. The mononitrile crystallized out of solution. It was filtered off and air dried. F = 97.5-99.5 ° C (literature 98-101 ° C); Yield 3.24.5 g (71.6%).

370.4 cj (2 moles) of the mononitrile was added along with 41.2 g Put Raney nickel and 500 ml of toluene in a 2 liter Parr pressure vessel. The reaction system was with hydrogen

flushed through and then an ammonia partial pressure of 4.92 kg / cm upset. The pressure was then brought to 35.2 kg / cm 2 with hydrogen and the temperature to 117 ° C increased and the hydrogen uptake noted, whereby the Pressure consistently held at 28.1 to 42.2 kg / cm. After the hydrogen uptake had ended, the reaction vessel was cooled and the Filtered toluene solution to remove the nickel catalyst. On standing, white crystallized from the toluene filtrate or very light blue crystals made from pure monoamine. F = 79-81 ° C (literature about 70 ° C); Yield 90-95%.

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A modified one was used to prepare the mono-tertiary amine Eschweiler-Clarke reaction applied. In a 1-liter flask fitted with a condenser, stirrer, and thermometer 17 5.6 g (0.943 mole) of the monoamine and 153.9 g of 37% aqueous formaldehyde were added. After this Cooling to 25 ° C., 109.5 g of 90% strength formic acid were added, which led to vigorous evolution of gas. After 5 minutes a further 109.5 g of 90% formic acid were added. This mixture was heated to 105 ° C and refluxed for 6 hours held. After cooling, the pH of the solution was brought to 7.21 with 50% aqueous NaOH. The neutralized Solution was concentrated to a gummy solid on a rotary evaporator. Isopropyl alcohol was added to this, which dissolved the desired mono-tert-amine, and the sodium formate formed as a by-product was filtered off and discarded. The filtrate obtained in this way was concentrated on a rotary evaporator. It made a greenish raw one mono-tert-amine. The distillation of the crude amine under reduced pressure resulted in pure, light yellow, clear, light viscous mono-tert-amine: bp = 143-148 ° C / 250, u; yield 100 ml (52.6%).

In a 500 ml flask equipped with a stirrer, a condenser and a thermometer, 4 3.0 g (0.2 mol)

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of the mono-tertiary amine, 71.4 g (0.28 mol) bromododecane and 250 ml Given benzene. Some quaternary salt precipitated out of the solution almost immediately. The mixture was stirred up 85 C and mixed with a drop of 50% aqueous NaOH as a catalyst. The mixture was used for 8 hours Heated to reflux, whereupon a cloudy, viscous solution was obtained. A viscous semi-solid formed on cooling and standing Precipitation. Upon treating the mixture with diethyl ether, the mono-quaternary salt separated out as a waxy whiter Solid which was filtered off, washed with solvent and dried in a vacuum oven. The connection obtained had the following structure and properties:

CH ₃

CH ₃ CC ^ = O

HN, N (CH ₂ J ₃ N CH ₃ Br ^

CH ₃

Il ο

(Villa)

N, N-dimethyl-N-dodecyl-quaternary-ammonium bromide of 3- (3'-aminopropyl) -5,5-dimethylhydantoin (Villa)

Physical properties :

F = 90-93 ° C

Appearance: waxy, white solid

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Analysis: Found: C 57.02 H 9.56 N 9.02

Dr 17.44

Theory: C 57.13 H 9.59 N 9.09 Br 17.28

Example 2 Production of mono-methylol-mono-quaternary ammonium salt (XIIa)

14.8 g (0.032 mol) of the monoquaternary bromide according to Example 1 and 25 ml of water were placed in a small flask. At the Stirring dissolved all of the salt. Then the pH was adjusted to 8.2 with aqueous NaOH. This solution was 2.85 g (0.033 mol) of 37% aqueous formaldehyde were added. After mixing thoroughly, the solution was left Stand for 24 hours. Obtained by concentration on a rotary evaporator and subsequent drying under high vacuum one the solid white quaternary salt of the following structure:

CH ₃

CH ₃ c C = OC ₁₂ H ₂₅

ff)

HOCH., NN ( ⁰¹ Va ^{N CH} 3 ^Br

(XIIa)

Analysis: Found: C 56.02 H 9.22 N 8.40

Br 15.97

Theory: C 56.09 H 9.41 N 8.53 Br 16.22

F = 135-138 ° C; Yield 9.5g (60%).

8098 1 5/0654

Example 3 Production of mono-methylol-mono-benzy1-quaternary salt (XIII)

In a 500 ml flask equipped with a condenser, a stirrer and a thermometer, 43.3 g (0.2O mol) of the mono-tert-AmLn according to Example 1, 36.2 g (0.28 mol) of benzyl chloride and added 250 ml of benzene. The mixture was stirred vigorously and refluxed for three hours. It was part A white precipitate separated out, which was collected by filtration, washed with solvent and placed in a vacuum oven was dried. If desired, the quaternary monobenzyl chloride can be obtained from an isopropyl alcohol / diethyl ether / water mixture be recrystallized, whereupon 50 g (73.5%) of a white solid with a melting point of 243-244 ° C. are obtained.

It has the following structure:

CH.,

CH.

CH.

N (CH.), N-CH.

2 ' 3

Analysis:

found:

Theory:

C 59.95 Cl 10.28

C 6O, O8 Cl 10.43

H 7.63 N 12.46 H 7.71 N 12.36

8098 1 5/0654

To a 250 ml flask was 40.11 g (0.118 mol) of the quaternary Added monobenzyl chloride and 150 ml of distilled water. Then the pH of the solution was adjusted with aqueous NaOH adjusted to 8.1. This solution was mixed with 9.5 g of 37% aqueous formaldehyde and then three Stirred for hours. When evaporating the solution on a rotary evaporator you got the following connection:

CH-

CH.

HIGH.

-C-

-N

CH,

, N (CH ₂ ) ₃ N CH ₃

Cl

CH.

(XIII)

Analysis: Found: C 55.87 H 7.89 N 11.02

Cl 9.36

Theory: C 58.45 H 7.63 N 11.36

Cl 9.53

The quaternary ammonium salts obtained according to Examples 1 to 3 are all water-soluble.

Example 4 Production of di-quaternary ammonium salt (XIa)

In a 12 liter flask fitted with a mechanical stirrer, thermometer and reflux condenser,

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there were 5253 g (41 moles) of 5,5-dimethylhydantoin and 2176 g Given (41 moles) of acrylonitrile. The slurry was taking Stirring heated to 55 ° C. and mixed with 82 g of 50% strength aqueous NaOH as a catalyst. Then continued heating until the temperature had reached 70 ° C. An exothermic reaction occurred which was so strong that external cooling took place had to. After the exothermic reaction ceased, the now homogeneous amber-colored viscous solution became cooled to about 68 ° C and treated with 1114 g (21 mol) of further acrylonitrile. A strong exotherm occurred again Reaction, so that it had to be cooled again from the outside. After the temperature had dropped to about 70 C, were finally 1061 g (20 mol) of acrylonitrile were added. This raised the temperature to around 124C. It was not cooled from the outside. The temperature slowly fell to about 80 ° C, whereupon the viscous greenish-amber colored Pour raw dinitrile into 8 liters of warm water with stirring. Gradual crystallization occurred. The cleaned Dinitrile was filtered off and air dried. F = 98-1OO ° C (literature 98-99 ° C); Appearance: White dust; Yield 94.1%.

To a 1 liter Parr pressure vessel was added 468.5 g (2 moles) Given dinitrile, 40 g Raney nickel and 500 ml toluene. To

809815/0 6 5

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After purging the reaction system with hydrogen, an Aj-Timonia partial pressure of 6.7 kg / cm was brought up. then the pressure of the system was brought to 35.2 kg / cm with hydrogen. The temperature was increased to 117 C and then recorded the hydrogen uptake. One stopped

increased the pressure to 28.1 to 42.2 kg / cm and supplied hydrogen as needed. After hydrogen absorption has ended the reaction vessel was cooled and the toluene solution, now containing crude diamine and catalyst, became Removal of the nickel catalyst filtered. The resulting light blue solution was concentrated on a rotary evaporator. Crude diamine was obtained in a yield of 450 g (93%); Total Amine Value (TAV) = 4 33/463 = 93.4%; glc (BSA derivative) = 94.6%.

The crude diamine was distilled under reduced pressure to give water-white, somewhat viscous, pure diamine; Bp - 161 ° C / 35 u; TAV = 458.3 / 463 = 98.9%; glc (BSA derivative) = 99%.

A modified Eschweiler-Clarke reaction was used to prepare the di-tertiary amine. In a 1 liter flask, equipped with a mechanical stirrer, condenser, and thermometer, became 97.1 g (0.4 mol) of diamine and 169.34 g of 37% aqueous formaldehyde are added. It kicked

8098 15/0654

an exothermic reaction occurred and the resulting solution became noticeably gelatinous. After the solution has cooled to 40 ° C 241.5 g of 90 ° 6% formic acid were carefully added. Gas evolution occurred. The reaction solution was heated to moderate reflux with stirring Was maintained for 6 to 8 hours. After cooling, the crude reaction product was on a rotary evaporator narrowed to half of its original volume. Then 200 ml of 25% strength aqueous NaOH were added. The further concentration on the rotary evaporator gave a greenish viscous liquid, which from the desired crude di-tert-amine, together with precipitated sodium formate. The sodium formate was filtered off with Washed isopropyl alcohol and discarded. The isopropanol wash liquid was combined with the filtrate and concentrated on the rotary evaporator. The obtained raw Di-tertiary amine was distilled under reduced pressure. Clear, colorless, somewhat viscous, pure was obtained di-tert-amine; Bp = 137 ° C / 90, u; TAV = 364/376 = 96.8%; Yield 80 ml (67%).

Into a 500 ml flask equipped with a mechanical stirrer, thermometer and condenser were 27.5 g (0.092 mole) di-tertiary amine, 64.3 g (0.26 mole) bromododecane and 2 added 50 ml of benzene. One heated to return

809815/0 65A

flow and after several hours a drop became 50% aqueous NaOH added as a catalyst. The further reflux treatment gave a voluminous white precipitate. The di-quaternary salt was filtered off with solvent washed and dried in a vacuum oven. A white, slightly waxy, very hygroscopic one was obtained Solid of the following structure:

Θ I Il Θ I Θ

CH, N (CH,), NN (CH ₂ ), ^{Ν CH} 3 ^Br

CH ₃

(XIa)

bis-N, N-dimethyl-N-dodecyl-quaternary ammonium bromide of 1,3-Di- (3'-aminopropyl) -5,5-dimethylhydantoin (XIa)

Physical properties :

MW = 796.92

F = 174-176 ° C

Appearance: off-white solid

IR spectrum (KBr) = 3.4; 3.49; 5.65; 5.85; 6.8; 6.98;

7.27; 7.4 and 12.9, u

Analysis: Found: C 58.49 H 9.96 N 7.31

Br 20.41

Theory: C 58.78 H 10.12 N 7.03 Br 2O, O5

809815/0654

If desired, the quaternary salt can be recrystallized from a mixture of isopropyl alcohol and ether:
F = 176-177.5 ° C.

Example 5 Production of the quaternary di-octadecyl bromide (XIb)

29.80 g (0.1 mol) of the di-tert-amine according to Example 4, 66.7 g (0.2 mol ) Bromooctadecane, 100 ml of benzene and 1 drop of 50% aqueous NaOH given as a catalyst. The mixture was refluxed for about 8 hours. The solvent was removed on a rotary evaporator leaving a viscous mass. 100 ml of toluene were added to the viscous mass. The mixture was then refluxed for a further 4 hours. After standing for a few days, the reaction mixture became gelatinous. Addition of diethyl ether to the mixture gave a white, sticky solid which was filtered off, washed with solvent and dried in a vacuum oven. The cjuaternary
Di-octadecyl salt should be of acceptable purity at this stage, but further bromooctadecane can be reacted with the salt if necessary to ensure complete quaternization to form a white, waxy solid compound with a melting point of 150C and having the following structure:

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Θ ^CH f

^C 18 ^H 37

CH,

CH ₃

Analysis:

found:

Theory:

CH-,

N '

Il
ο

C 62.43 Br 16.92

C 63.46 Br 16.59

(CH,)

2'3

CH,

CH ₃

(XIb)

H 10.27 N 6.45

H 10.86 N 5.80

Example 6 Production of the quaternary dimethyl iodide (XIc)

In a flask was 14.95 g (0.05 mol) of the di-tertiary amine according to Example 4 and given a total of 25 ml (0.39 mol) of methyl iodide. A strong exothermic reaction occurred, which quickly resulted in the formation of a white solid. This was slurried in ethyl alcohol, filtered off, with ethyl alcohol washed and dried in a vacuum oven. The essentially pure quaternary dimethyl iodide was obtained

as a creamy white solid with a melting point of 256.5-259 ° C (decomposition); Yield 22.5g (77.2%). This one has the

following structure:

Γ ·

■ N -
CH,

• (CH,)

2'J

-3

C C ■

ι ι

(CH,)

2'3

-N -

CH,

-CH,

(XIc)

Analysis:

found:

Theory:

C 34.84 I 43.62

C 35.06 I 43.58

H 6.02 H 6.23

N 9.88 N 9.61

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Example 7 Production of the quaternary dibenzyl chloride (XIV)

In a 500 ml flask fitted with a mechanical stirrer and a condenser, 27.5 cj (0.092 mol) of the di-tert-amine according to Example 1, 34.85 g (0.26 mol) Benzyl chloride and 250 ml of benzene. After careful The solution was left to mix, whereupon a white precipitate separated out. By heating for 15 minutes considerably more precipitate was formed at reflux. The di-quaternary salt was filtered off with solvent washed and air dried. It had the following structure:

_{0 θ} ρ ^CH 3 ί "ΐ ~" ° θ Γ ²

^C1 CH ₃ N (CH ₂ I ₃ HN (CH ₂ ) 3 _Ν CH _{3 ς]}

Θ I \ / I

Cl CH C _CH

³ Il ³ (XIV)

F = 129-132 ° C

Appearance: white solid

Ana Lysis: found: C 62.8O Il 7.7.9, N 9.89

Cl 12.81

Theory: C 6 3, 15 II 8, O4 N 1O, 16

Cl 12.85

8098 1 5/0 6 5

The salts prepared in Examples 5, 6 and 7 have no bactericidal and / or fungicidal activity, even if they can be used in amounts of 1000 ppm. The quaternary ammonium salts of Examples 4-7 are water soluble and result with AgNO., a positive reaction to halogen.

Example 8 Production of mono-quaternary ammonium salt (XV)

In a 22 liter flask equipped with a stirrer, a reflux condenser and a thermometer, 3203 g (25 mol) of dimethylhydantoin and 5000 ml of water were placed. When the temperature was raised to 73 ° C., the dimethylhydantoin was completely dissolved. Then 664 g (12.5 mol) of acrylonitrile and 24 g of 50% strength aqueous NaOH were added as a catalyst. The solution was heated to reflux and refluxed until the temperature reached about 100 ° C. The heat was then discontinued and when the temperature had dropped to 73 ° C., an additional 663 g (12.5 moles) of acrylonitrile was added. The mixture was then refluxed again. After the temperature reaches 100 to 101 ⁰ C, the heat supply was discontinued, had cooled from the outside until the temperature reaches about 31 ° C, and seeded, the cooled reaction solution with an Mononitrilkristall. The mononitrile crystallized from the solution. It was filtered off and air dried. F = 97.5-99.5 ° C

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27-353

(Literature 98-10 ° C); glc (TMS derivative) = 99%; yield 3.245 g (71.6%).

Into a 2 liter Parr pressure reaction vessel was 370.4 g (2 moles) Added mononitrile, 41.2 g of Raney nickel and 500 ml of toluene.

The reaction system was flushed with hydrogen,

then an ammonia partial pressure of 4.92 kg / cm was applied. Then was with hydrogen to a pressure of 35.2 kg / cm. The temperature was increased to 117 ° C. and the hydrogen uptake was recorded, whereby the

2 Pressure constantly maintained at 28.1 to 42.2 kg / cm. After finished The reaction vessel was cooled and hydrogen uptake the toluene solution is filtered to remove the nickel catalyst. On standing, the toluene filtrate crystallized white or very light blue pure monoamine. F = 79-81 C (literature about 70 ° C); Total amine value (TAV) = 297.9 / 300 = 98.4%; Yield 90-95%.

A modified one was used for the preparation of the mono-tertiary amine Eschweiler-Clarke reaction applied. In a 1 liter flask fitted with a condenser, stirrer and thermometer 175.6 g (0.943 mole) of monoamine and 153.9 g of 37% aqueous formaldehyde were added. To After cooling to 25 ° C., 109.5 g of 90% strength formic acid were added, whereupon vigorous evolution of gas began.

80981 5/065

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After 5 minutes, a further 109.5 g of 90% formic acid were added added. The mixture was heated to 105 ° C. and refluxed for 6 hours. After cooling, the pH was the solution was adjusted to 7.21 with 50% strength aqueous NaOH. The neutralized solution was concentrated to a gummy solid on a rotary evaporator. the Addition of isopropyl alcohol to the solid dissolved the desired mono-tertiary amine. That formed as a by-product Sodium formate was filtered off and then discarded. Concentration of the filtrate on a rotary evaporator gave greenish crude mono-tertiary amine. The distillation of the crude amine under reduced pressure resulted in pure, light yellow, clear, slightly viscous mono-tert.-amine; Bp = 143-148 ° C / 250, u; glc (BSA derivative) = 99+%; Yield 100 ml (52.6%).

To a 500 ml flask equipped with a stirrer, condenser, and thermometer was added 43.0 g (0.2 mol) mono-tertiary amine, 71.4 g (0.28 mol) bromododecane and 250 ml Given benzene. Some quaternary salt precipitated out of solution almost immediately. The mixture was stirred heated to 85 C, mixed with a drop of 50% aqueous NaOH as a catalyst. Then 8 hours was under Held at reflux, whereupon a cloudy viscous solution was obtained. When cooling and standing, a viscous one fell out of her

8098 1 5/0654

semi-solid precipitate. Treatment of the mixture with diethyl ether turned it into a waxy white solid quaternary Monododecyl bromide which was filtered off, washed with solvent and dried in a vacuum oven. F = 85-88 C. The halogen test with AgNO-. was positive. yield 50 g (54%) of a very hygroscopic compound of the formula: CH.,

CH

^C 12 ^H 25

■ Ν

- (CH ₂ ) J-

Analysis:

0
found:

Theory:

C 57.02 Br 17.44

C 57.13 Br 17.28

M CH-

CH ₃

H 9.56 N 9.02 H 9.59 N 9.09

(XV)

IR spectrum (solid film) = 3.17; 3.42; 3.5; 5.67;
5.85; 6.81; 6.92; 7.04; 7.35; 7.87; 9.39 and 12.99

Example 9

Production of quaternary monobenzyl salt (XVI)

In a 500 ml flask, which was equipped with a condenser, a stirrer and a thermometer, 43.3 g (0.20 mol) of mono-tertiary amine according to Example 8, 36.2 g (0.28 mol)
Benr: yl chloride and 250 ml of benzene added. The mix was

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27U353

stirred vigorously and refluxed for 3 hours. A white precipitate formed which was filtered off with Solvent washed and dried in a vacuum oven. If desired, the quaternary monobenzyl chloride can be used from a mixture of isopropanol, ethyl ether and water to give 50 g (73.5%) of a white solid be recrystallized with a melting point of 243-244 ° C. It had the following structure:

CH, C C = O I

³ · CH.

HNN (CH ₀ ) - ^ N CH- _,

\ / I

It ^CH 3 (XVI)

Analysis: Found: C 59.95 H 7.63 N 12.46

Cl 10.28

Theory: C 60.08 H 7.71 N 12.36 Cl 10.43

The compounds of Examples 2 and 4 to 8 were compared for their activity in the procedure described below Bacteria and Fungi studied and with a known commercially available compound with broad bactericidal and fungicidal spectrum of activity compared.

809815/0654

27U353

The compounds to be tested were dissolved in sterile distilled water in an amount of 10,000 ppm. With Serial dilutions of these basic solutions were prepared in suitable culture media, which were then carried out with cultures of microorganisms have been inoculated and incubated. The experiments with bacteria were carried out in BBL Trypticase soybean broth, which was incubated for 48 hours at 35 C. The tests carried out with Aspergillus niger were carried out in Difco Sabouraud dextrose broth incubated at 26 ° C for 5 days.

Staphylococcus aureus 6538, Pseudomonas aeruginosa 9027 and Aspergillus niger 16404 were used for the test cultures. The compounds of Examples 5 to 7 were found to be inactive even at concentrations of 1000 ppm. the The results obtained are shown in Table 1 below.

0 9 815/0654

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concentration Table 1 and results 0 9027 Asporgillus in ppm Test culture eudomonas 0
0 niger 16404 link 1000 Staphylococcus psi aureus 6538 aeruginosa 0 0 of the example 900
800 0 0 0
0 Compound XIIa 700 0
0 0 0 Example 2 600 0 ■ f 0 500 0 + 0 400 0 + 0 300 0 + 0 200 0 - 0 100 0 0 50 0 • f 25th 0 0

12.5 6.25 3.12

Compound XIa Example 4

100

50

25th

12.5 6.25 3.12 1.56 0.78 0.39 0.19

0 0 0 0 0 0 0 0

Compound XV
Example 8

1000 900 800 700 600 500 400 300 200 100 50 25th

12.5 6.25 3.12 1.56

0 0 0 0 0 0 0 0 0 0 0 0

Comparison substance

1000 900 800 700 600 500 400 300 200 100

0 0 0 0 0 0 0 0 0

- not examined

+ Growth

O no growth

Comparison substance: Dowicil 2OO, 1- (3-chloroallyl) -3,5,7-triaza-1-azoniaadamantane chloride (Manufacturer Dow Chemical Company, see US Pat. No. 3,228,829)

1 5/0654

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The minimum concentrations of Ilemm are in the following Table 2 listed.

Test culture

Table 2 Minimum inhibitory concentration, ppm

Example Example Example Dowicil 2 4 8 2OO

Staph. Aureus 6538

Asperg, niger 16404

25th

Pseudo, aerugin.

9027 500

100

0.78

12.5

3.12

25th

600

300

200

900

800

sch: kö

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Claims (18)

UEXKÜLL & STOLBERG BESELERSTRASSE 4 2OOO HAMBURG 52 F- ¹ AVEN Attorneys DR. JD. FRHR. by UEXKÜLL OR. ULRICH GRAF STOLBERG DIPL-ING. JÜRGEN SUCHANTKE Glyco Chemicals, Inc. 51 Weaver Street,
Greenwich, Conn./V.St.A . (Prio: October 4, 1976 US 729 342, US 729 343 and US 729 344 - 14399) Hamburg, September 28, 1977 Hydantoin derivatives, process for their preparation and their use Claims Quaternary ammonium salts of hydantoins with the general formula in which R. and R_ are identical or different and are hydrogen, lower alkyl groups with 1 to 6 carbon atoms, -C H-OH or
η 2η 809815/0654 274A353 Θ | ⁷ Θ ₂ ) JNR ₅ ^{Χ R} 6 mean, where at least one of the substituents and R _{2 has} the meaning NO ₂₅₆ X ^R 5 has, R ₃ and R. are identical or different and represent hydrogen, alkyl groups with 1 to 6 carbon atoms, phenyl groups or together a cycloaliphatic group with 4 or 5 carbon atoms, R ₅ , R ₆ and R_ are identical or different and denote benzyl groups or -C H_ .., X is a physiologically acceptable anion, η is an integer from 1 to 4 and ρ is an integer from 1 to 24. 2. Compounds according to claim 1, characterized in that R ₁ and R _{2 are} identical or different and - (CH ₂ ) 3 N ^R 5 mean. 6098 15/0654 3. Compounds according to claim 1, characterized in that when R ₁ = -CH »OH, R ~ is the meaning ^R 7 ^R 5 «7 has, and if R ₁ = _ _(CH ) _ _n _ ^R 5 is, R ₂ = -C _n H _2n OH. 4. Compounds according to claim 1, characterized in that one of the substituents R ₁ and R "is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and the other is the meaning - (CH ₂ ) 3 N ₅ ^R 6 Has. 5. Compounds according to claim 1, characterized in that R and R. are methyl groups. 809815/0664 6. Compounds according to claim 1, characterized in that R ₅ and R, are identical or different and are lower alkyl groups with 1 to 6 carbon atoms and R ₇ = -CH ".., where ρ is an integer from 8 to 24 . 7. Compounds according to claim 6, characterized in that X is the bromide ion, R, - and R _{fi are} methyl groups and ρ is an integer from 12 to 18. 8. Compounds according to claim 3, characterized in that they have the formula ^C 12 ^H 25 ° h ~ ^C C = O CH —N— (CH,), - N N R \ _c / fl CH ₃ CH- C C- == 0 C H ³ II | 12 ^H 25 where Rg = -C H_OH and Z is a physiologically acceptable one Is anion and η has the meaning given. 809615/0664 9. A compound according to claim 8 having the formula: CH ₃ CH ₃ CC = O I © _H0CH ν N (CH.), N CH. ^C 12 ^H 25 \ p / CH. Br 10. A compound according to claim 8 having the formula: CH. CH. HIGH. C- -N C: N- CH. (CH ₀ ), N CH ₁ Cl ^λ 2'3 CH. 11. A compound according to claim 2 having the formula: Br ^w CH. ^C 18 ^H 37 CH. (CH ₂ ) -N - CH. Γ ³ -C C- -N N- ^C 18 ^H 37 ■ N CH. 809815/0654 27U353 12. A compound according to claim 2 having the formula: CH 3 CtI / ■■ / - ■ <· ■> CH. ^ CH, N- CH- I I -N JN- • N CH, I CH. 13. A compound according to claim 2 having the formula CH-, CH, C- CH. Cl ^ CH ₀ N- CH. ■ N N- -N CH ₃ CH, 14. A compound according to claim 2 having the formula: CH, Z ^w CH. -N— CH- CH - (CH ₂ J ₃ - ^C 12 ^H 25 , N- - (CH ₂ ) -N CH, Z CH. where Z is a physiologically acceptable anion, especially the bromide ion. 809816/0664 15. A compound according to claim 4 having the formula: CH, C = 0 Z ^ CH - Ν— (CH -) - NN CH. ^or he ^CH 3 Il CH. CH - ^ C CH ^ NN (CH ₂ J ₃ N CH ₃ Z V / CH, where Z is a physiologically acceptable anion. 16. A compound according to claim 1 having the formula CH -N -C = N- ^C 12 ^H 25 N CH, Br CH. 17. Fungicidal and bactericidal agents, characterized in that that there is one or more active ingredients 809815/0654 Compounds according to claims 1 to 16 as well as conventional carriers and auxiliaries. 18. fungicidal and bactericidal agent according to claim 17, characterized in that it is in the form of a soap bar, a cosmetic preparation or a wound treatment agent is present. 809815/0664