DE2330454A1 - Microbicidal 4-tert. butylcyclohexylamino alkanes - prp. by reacting 4-tert.butylcyclohexylamine with alkylhalides, used with solubilising agent in customary prepns. - Google Patents

Abstract

Title cpds. are of formula (I): (where R = 8-12C alkyl; are prepd. by reacting 4-tert. butylcyclohexylamine (II) with a corresp. alkyl-halide at pref. 130-140 degrees C in a mole ratio of 1-5:1 in the presence of an acid-acceptor or excess (II). (I) may be used against a broad spectrum of Gram-pos. and Gram-neg. bacteria, fungi, yeasts etc.

Description

TH. GOLDSCHMIDT AG, Essen

New microbicidal compounds

The invention relates as new compounds to 4-tert-butylcyclohexylaminoalkane, wherein the alkyl group is a hydrocarbon group having 8-12 carbon atoms, and methods for the preparation of these compounds and preparations containing these compounds, which by microbicidal activity are excellent.

Microbicides are understood in the sense of the present compounds the property of a compound or a preparation containing this compound, gram-positive and kill gram-negative bacteria, skin and mold, yeast, viruses or algae. With the variety of these Living beings it is understandable that the effectiveness does not exist against all of the aforementioned living beings is, but that with good action against some of these organisms it had an excellent effect on Organisms can show. That means that the

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Understandably, this does not affect all microorganisms is equal to. However, finding new substances with microbicidal properties is always an asset the technology of microbicides, as by changing the active compounds and by using new ones Products reduce the resistance of the microorganisms, not even the ability of the organisms to develop resistance will. In addition, as mentioned above, it is particularly effective in selective areas.

The new compounds can be prepared by reacting 4-tert-butylcyclohexylamine with the corresponding Reacts alkyl halide in a molar ratio of 1: 1 to 5: 1 at temperatures of 100 to 150 ° C and the process product distilled off from the reaction mixture.

It may be expedient, in the presence of an alkali metal or alkaline earth metal Halogenwatsserstoffakzeptors _f is preferably to work. A special addition of a hydrogen halide acceptor may, however, be unnecessary if the reaction is carried out with a large excess of amine, since the amine then acts as an acid acceptor.

The reaction takes place at temperatures from 100 to about 150 ^° C., the lower limit of the temperature being given thereby

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is that the reaction can be carried out in economic times and the upper limit cannot be exceeded must, since the reaction takes place quickly enough and by-products can arise at higher temperatures. Is preferred the temperature range from 130 to 140 C.

The desired process product is expediently obtained by distillation separated from the reaction mixture. Is the alkyl radical an octyl radical, the boiling point of the desired compound is 155 to 160 ° C. at a pressure of 0.6 torr. is the alkyl radical is a dodecyl radical, the boiling point is 155 to 177 ° C at 0.1 Torr.

It is understandable to the person skilled in the art that, instead of the pure alkyl radicals with 8-12 carbon atoms, mixtures of alkyl radicals can also be used, which on average _{contain C ß} - to C _ radicals and can be straight-chain or branched, but in which the proportion the C _g - to C - alkyl component should be as high as possible.

The new compounds are not soluble in water. It is therefore necessary that you connect the connections to either one Filler with a high specific surface area is applied in order to get to dust or to remove them, if they are in water

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Wants to apply medium, together with a solubilizer apply. Examples of such solubilizers are the addition products of ethylene oxide with hydrophobic compounds with an active hydrogen atom, for example addition products of ethylene oxide to tridecyl alcohol. You can also use cation-active solubilizers, such as dodecyldimethylbenzylammonium chloride, use, usually you choose, based on the active substance, about the same amount Solubilizing agents.

The compound produced according to the invention can be used in a conventional manner Way, i.e. the dissolved or solubilized compound can be used together with other microbicidal compounds and can be provided with other additives such as odorous substances or dyes. The connection can also be in fluorinated chlorinated hydrocarbons are dissolved and used in aerosol form. By adding the Solubilizing agent when using an aqueous solution, the cleaning power of the solutions is increased at the same time, in particular when nonionic surfactants are used as solubilizing agents.

In the following examples, first of all, what is according to the invention Mixture of compounds explained. Then the effectiveness of the inventively her-

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Prepared preparations shown. The test for microbicides was carried out according to the guidelines of the German Society for ' Hygiene und Mikrobiologie e.V., Gustav Fischer Verlag, Stuttgart, 1959. In the tables + germ growth, - no germ growth.

In Examples 1 and 2, the preparation of the invention new connections described. Examples 3-6 use the preparation of formulations these connections explained. This is followed by tables to demonstrate the microbicidal effect.

example 1

Preparation of 4-tert-butylcyclohexylamlnooctane 12 mol of 4-tert-butylcyclohexylamine and 4.8 mol of NaOH are placed in a 4 liter four-necked flask equipped with a KPG stirrer, dropping funnel, thermometer and reflux condenser. 3 mol of n-octyl bromide are slowly added to this mixture and then heated to about 135 ° C. for one hour. Then the inorganic residue is decanted while still hot and the decanted liquid is subjected to fractional distillation. After a lapse of 4-tert-butylcyclohexylamine proceed at 155 to 160 ⁰ C and 0.6 torr 608 g over.

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Elemental analysis for C.gH -N (molecular weight 268):

calculated found

C 80.9% by weight C 80.5% by weight

H 13/9% by weight H 13.7% by weight

H 5.2% by weight N 5.2% by weight

Example 2

Preparation of 4-tert-butylcyclohexylaminododecane to 12 mol of 4-tert-butylcyclohexylamine, 4.8 mol of NaOH and 10 ml of H ₂ O in a 4 liter four-necked flask equipped with a KPG stirrer, dropping funnel, thermometer and reflux condenser are added 3 mol dodecyl bromide in small portions and then heated to 140 ° C. for one hour. The inorganic residue is then decanted while still hot and the decanted liquid is subjected to fractional distillation. After 4-tert-butylcyclohexylamine has passed over between 175 and 177 ° C. at 0.1 Torr, 776 g of 4-tert-butylcyclohexylamxnododecane are transferred.

Elemental ^{analysis for C} 22 ^H 45 ^N ( ^Mo lg ewlcnt 324):

calculated found

C 81.6% by weight C 81.3% by weight

H 13.9% by weight H 14.1% by weight

N 4.5% by weight N 4.4% by weight

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'■ · ■■. . · ■■ ·. Example 3 : ..:. ·.:. ■ .. ■ ·· .. · ■ .. ■;. ■; ■■ - ■■■ ··., '·

10 parts by weight of 4-tert-butylcyciohexylamine-octane, 10 parts by weight of an addition product of 12 mol of ethylene oxide with 1 mol of isotridecyl alcohol, 10 parts by weight of acetic acid, 20% isopropanol and 50 parts by weight of water are homogenized to about 40 ° C. while stirring and heating. You get such a yellow-colored, clear solution that can be easily diluted with water.

Example 4

10 parts by weight of 4-tert-butylcyclohexylaminoocatn, 10 parts by weight a solution that is 80%.

Cl

and 20% Xthanol contains, as well as 10 parts by weight of acetic acid and 70 parts by weight of water are homogenized with stirring at about 40 ⁰ C. This leads to a yellow, clear solution which can be mixed with water in any proportion.

Example 5

10 parts by weight of 4-tert-butylcyclohexylaminododecane, 10 parts by weight of an addition product of 12 moles of ethylene oxide

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of 1 mole of isotridecyl alcohol, 10 parts by weight of acetic acid and 70 parts by weight of water are homogenized at 40 ° C. with stirring. A clear solution which can be diluted with water is obtained in this way.

Example 6

10 parts by weight of 4-tert-butylcyclohexylaminododecane, 10 parts by weight a solution that is 80%

CH.

egg

and contains 20% ethanol, and 10 parts by weight acetic acid and 70 parts by weight of water are homogenized at about 50 ° C. with stirring.

The progressive effect of the substances according to the invention can be seen from the following tables, Table 1 with the preparation! of Example 3, Table 2 with the preparation of Example 4, Table 3 with the preparation of Example 5 and Table 4 with the preparation of Example 6 has been worked out. At the top of the table is the pH of the 0.1% by weight of the active ingredient Solution given.

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Tabel

pH value: 7.0

Test strain

Concentration in% exposure time in min. 1 2 5 10 20 30

S. aureus

0.1

0.05 0.01 0.005 0.001

E. coli

O, O5 0.01 O, OO5 0.001

P. vulgaris

0.1

0.05

0.01

O, OO5

0.001

T. mentagrophytes O, l

0.05 0.01 0.005 0.001

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2331) 454

Tabel

pH value: 6.7

Test StaHna

concentration

'■■ in% ^:

Exposure time in minutes, 12 5 10 20 30

S, aureus

0.1 ^: 0.05

"O / oil ^a 0.005 0.001

E. coli

0.1 O, O5 O, oil ' 0.05 0.001

P. vulgaris

O _f l

0.05

0.01

0.005

0.001

M. gypseum

0.1
0.05 O, Ol O, OO5 0.001

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- T table 3 Exposure time 2 5 IO 2Ο ϊ-: ■■: - ■; ■! \ pH value: 5.0 - - - ■ - ■ - ■ - 1 - - - - in min. Teststanffia · ■■ - - --- ■ E. aeruginosa concentration - ■ - - - - 3α - - - ■ - E. coli in % 4 · 4 · 4- 4- - S. aureus 0.1 * 4- 4- 4- 4- - .. O, O5 + " * · ■ + ■ 4- - - - - ■ - · ■ Ο, ΟΙ - - - - 4- .. C. albicans 0, OQ5 - - - - - -0.001 4- - Ο, Ι ! ■ ^r i 4- 4- 4 · + - 0, OS + 4- 4- 4- 4- 4- 0.01 4- + 4-. ·, 4- Ο, ΟΟ5 - - - - - - - - ... 4r - 0.001 - 4- 4- 4- 4- - Ο, Ι ν 4- 4- 4 · + - 0.05 4 · 4- ♦ ■■■ * ■ Ο, ΟΙ 4- - - - - + 0.005 - - - - - 0.001 - 4- ■ - - - - ' 0.1 4- ') + ⁺ - _ 0.05 ■ + 4- + - + - ■ - Ο, ΟΙ - 0.005 Θ, ΟΟΙ · ■

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Tabel

pH: 5.1

Test strain

Concentration in% exposure time in min. 1 2 5 10 20 30

S. aureus

0.1

0.05

0.01

0.005

0.001

ι., "

P. vulgaris

0.1

0.05

0.01

0.005

0.001 t ί

P. aeruginosa

0.1
0.05 0.01 0.005 0.001

P. expansum

0.1

0.05

0.01

0.005

0.001

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The following experiment serves as a comparative experiment:

The mode of action of hexachlorophene as a disinfectant is described in the book "Sterilization, Disinfection, Preservation, Chemotherapy "by Wallhäusser and Schmidt, Georg Thieme Verlag, Stuttgart, 1967, p. 193, described.

A mixture of equal parts by weight was used as a comparison substance Hexachlorophene and a conversion product of 12 moles of ethylene oxide with tridecyl alcohol are used. The specified Concentrations refer to the hexachlorophene content. The pH of the aqueous solution is 7.7.

Test strain concentration exposure time in min.

in% 1 2 5 10 20

S. aureus 0.1 + _____

0.05 + - - -

E. coli 1.0 + + + + + -

P. aeruginosa 2.0 ______

C. albicans 5.0 + + + + + +

P. expansum 5.0 + + + + + +

The table shows the superiority of the compound according to the invention with regard to its microbicidal activity.

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Claims (4)

Claims 1. New compounds of the general formula CH., -CM H) -NH-R, R - alkyl radical with 8-12 carbon atoms. 2. A process for the preparation of the compounds of claim 1, characterized in that 4-tert-butylcyclohexylamine is reacted with the corresponding alkyl halide in a molar ratio of 1: 1 to 5: 1 at temperatures of 100 to 150 ° C and the process product from the reaction mixture distilled off '. 3. The method according to claim 2, characterized in that in particular at low molar ratios in Presence of a hydrogen halide acceptor works. 4. Microbicidal preparation, characterized by an effective content of compounds of claim 1 in a carrier which can contain conventional additives, fillers and the like. 409883/1387