DE2330454B2 - 4-tert-butylcyclohexylaminoalkanes, processes for their production and microbicidal preparations - Google Patents

Description

The invention relates to 4-tert-butylclohexylaminolilkenes the general formula

CIl ₃
H, C -C- 'H> ONLY

CH,

in which R denotes an alkyl radical having S to 12 carbon atoms, and processes for their preparation and microbicidal preparations containing these compounds.

In the context of the present invention, microbides are understood to mean the property of a compound or a preparation containing this compound, gram-positive and gram-negative bacteria, skin and Molds, yeasts. Kill viruses or algae.

When applying microbial active compounds, it is desirable to have a wide range to have a wide variety of substances available in order to avoid the development of resistance. A selective effective wedge is also desirable.

The new compounds can be prepared by reacting 4-tert-bulylcyclohexylamine in a manner known per se with the corresponding ^N- alkyl halide in a molar ratio of 1: 1 to 5: 1 at temperatures from KK) to 150 ° C. Usually -.in the reaclone mixture abd, stylized.

Fs can be binary, in the presence of a 1 lalogcnwasscrsli'ffakzeptoi ν preferably alkali metals krdalkali sulphide. / Li work. Fin special However, the addition of a hydrogen halide acceptor may be unnecessary if with one large excess of amine the reaction is carried out, since the amine rlann acts as an acid acceptor. The reaction takes place at temperatures from 100 to about 150 ° C., the lower limit being the temperature is given by the fact that the reaction is carried out in economic times and the upper limit must not be exceeded because the

ίο reaction proceeds quickly enough and by-products can arise at higher temperatures :; , - .. Preferably, the temperature range of 130: 140 C. The desired product of the process is separated by distillation from the reaction mixture. If the alkyl radical is an octyl radical, the boiling point of the desired compound is 155 to 160 ° C. at a pressure of 0.6 torr. If 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 having 8 to 12 carbon atoms, mixtures of alkyl radicals can also be used which _{contain on average C 8} to C ₁₂ radicals and can be straight-chain or branched, but in which the proportion of C ₈ - to Cii alkyl components should be as high as possible.

The new compounds are not soluble in water. It is therefore necessary to make the connections either applies to a filler with a high specific surface area in order to obtain dust or she. if you want to use them in an aqueous medium, use them together with a solubilizer. Examples of such solubilizers are the products of the addition of ethylene oxide to hydrophobic ones Compounds with active hydrogen alom, for example addition products of ethylene oxide of tridecyl alcohol. You can also use cation-active solubilizers, such as dodecyldimethylbenzylammonium chloride, use, usually you choose, based on the active ingredient, about the same amount Solubilizers.

The connection produced according to the invention can be assembled in the usual way, i. h., the dissolved or solubilized compound can be used together with other microbial compounds and with other additives, such as odorous substances or colorants. The connection can too can be dissolved in fluorinated chlorinated hydrocarbons and used in aerosol form. 1 Kirch the addition of the solubilizing agent when using an aqueous solution is simultaneously the The cleaning power of the solutions is enhanced, especially when used as a solubilizing agent non-ionogenic surfactants are used.

In the following examples, the inventive Explained in relation to each other. The effective wedge is then shown in tabular form of the preparations produced according to the invention are shown. The test for microbicides was carried out after ile guidelines of the German Society for Hygiene and microbiology e. V., Gustav Fischer Verlag, Stuttgart. 1959. In the tables, ; Germ growth, no germ growth.

Examples I and 2 describe the preparation of the new compounds according to the invention.

c> 5 Examples 3 to U illustrate the production of preparations using these compounds. This is followed by tables to demonstrate the superior microbial effects.

example 1
4-lert.-ButyIcydohexylaminooctan

in a 4-1 four-necked flask equipped with a K PG stirrer (= Küppers precision glass stirrer), dropping funnel. Thermometer and reflux condenser, 12 mol ^ tert.-ButylcycIohexylamin and 4.8 mol Submitted NaOH. 3 mol of n-octyl bromide are slowly added to this mixture and the mixture is then heated 1 hour at about 135C. Then it is decanted from the inorganic residue while still hot and subjects the decanted liquid to a fractionated distillation. After a course of 4-tert-Butylcyclohexylamine «ehen at 155 to 160 ° C. and 0.6 torr 608 g.

Elemental analysis for C ₁₈ Hj-N (molecular weight 268):
Calculated ... C 80.9, H 13.9. N 5.2%:
found C "80.5, H 13.7. N 5.2%.

e ι s ρ j e J 2

Production of 4-tert-butylcyclohexylaminododecane

To 12 moles of 4-tert-butylcyclohexylamine. 4.S mol NaOH and 10 ml H ₂ O in a 4-1 four-necked flask. equipped with KPG stirrer. Adding funnel, thermometer and reflux condenser, 3 moles of dodecyl bromide are added in small portions and then heated to 140 ° C. for 1 hour. Thereafter, the inorganic residue is decanted hot from the inorganic residue and the decanted liquid is subjected to fractional distillation. After 4-tert-butylcycloli.wylamine has passed over between 175 and 177 ° C. at 0.1 Torr 77 (ig -l-tert-butylcyclohexylamiiododecane).

Elementary analysis for C ₂₂ H ₄₅ N (molecular weight 324):

Calculated ... C 81.6. H 13.9. N 4.5 wt .- ",,:
found .... C 81.3, H 14.1. N. 1.4 wt. "".

Example 3

H) parts by weight 4 - terl. - Butylcyclohexylaminooctane. 10 parts by weight of an addiction principle of 12 moles of ethylene oxide in 1 mole of isotridccyl 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 so a yellow-colored, clear solution that dissolves with water can be easily diluted.

at

spat

Example 5

10 parts by weight of 4 - tert. - Butylcyclohexylaminododecane, 10 parts by weight of an adduct of 12 moles of ethylene oxide with 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 of a solution that is 80%

C ₁₂ H ₂₅ -N-CH ₂ -? CH ₃

Cl

and contains 20% ethanol, as well as 10 parts by weight of acetic acid and 70 parts by weight of water are under

2; Stirring homogenized at about 50 ° C.

The forischriuiiche 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, the pH of the solution containing 0.1 percent by weight of active ingredient is indicated in each case.

Table 1

pH value: 7.0.

40 cones / cit in minutes

ι "" ι 1: ^ς ίο: o w

10 parts by weight of 4 - tert. - Butylcyclohexylaminooctane. 10 parts by weight of a solution. the SO "«

CII.,

C ₁₂ Il ₂₅ -N CH, - ·· - '

and 20 ".. contains ethanol and 10 crew members Acetic acid and 70 parts by weight of water are homogenized with stirring at about 40 ° C. One succeeded! so / u a yellow, clear solution that dissolves with water mix in all proportions.

45 S. aureus E. coli 55 1'. vuigaris (JO 1. nienta- 0.1 - - - »Rophvles
65 0.05 t H- + - - 0.01 t 4- H- + 0.005 i- H- + + so 0.001 4 - I- H- 0.1 - - 0.05 ⁴ H- 0.01 * 1 ; f \ 0.005 ^y -, + ■ t- H- 0.001 - i + 0.1 - 0.05 0.01 1 4 H- 4th 0.005 t H- 0.001 t '- t 0.1 ₄ y 0.05
0.01 * ί 4 0.005 ι , -4- - 0.001: 4th 4-

Table 2
pH value: 6.7.

Test lamb
S. aureus

Table 4

E. coli

P. vulszaris

M. gypscum

Table 3
pH value: 5.0.

Tribe

concentration

0.1

0.05

0.01

0.005

0.001

0.1

0.05

0.01

0.005

0.001

0.1

0.05

0.01

0.005

0.001

0.1

0.05

0.01

0.005

0.001

Effective time in minutes I 2 5 10 2 (1

4- 4-

4- _ - - - -

4-4-4-

4-4-4-

Con / entrution

I "1.1

effect / eii in Mimileii 1 2 5 11) 20 pH value: 5.1

TeslsUimm concentration effect line in minutes

tration

l »il I 2 5 10 20

S. aureus 0.1

0.05 0.01 0.005

0.001

P. vulgaris 0.1

0.05 0.01 0.005 0.001

P. aeruginosa 0.1

0.05 0.01

0.005 0.001

4-

4-4-4 4-

4-

H-

4- 4-

4- +

4-

P. expansum OJ 0.05 0.01 0.005 0.001

H- f +

H- 4 - (-

+ - 4 4-

S. aurcus 0.1

0.05 0.01 0.005 0.001

E. coli 0.1

0.05 0.01 0.005 0.001

E. aeruginosa 0.1 0.05 0.01 0.005 0.001

C. albicans 0.1 0.05 0.01 0.005 0.001

+ 4-

4 4-

4th

■ f 4-

4-

4 4-

4 4 +

+ ■ 4- 4- 4-4 -4 4- 4- 4- The following experiment serves as a comparison experiment.

The mode of action of hexachlorophene as a disinfectant is described in the book »Sterilization. Disinfection, Conservation, chemotherapy «by WaIlhäußer and Schmidt, Georg Thierne Verlag, Stuttgart. 1967, p. 193.

A mixture of equal parts by weight of hexachlorophene and a Transfer product of 12MoI ethylene oxide with Tridecyl alcohol used. The stated concentrations relate to the hexachlorophene content. The pH of the aqueous solution is 7.7.

Te ^ istamm Kon / .cn- l.inffektunus / cit in minutes

ti'atini!

l "") I 2 5 Kl 20

S. aureus 0.1 4- - - -

0.05 4 - - -

0.01 4 t + H-

0.005 i -) I I

continuation
Tesl tribe

E. coli 1.0

0.5

P. aeruginosa 2.0 1.0 0.5

C. albicans 5.0 2.5 1.0

Concentration exposure time in minutes (ration

10

30th

Test lamb

P. expansum

Concentration line of action in minutes

5.0 2.5 1.0

10 20

The table shows the superiority of the invention Compounds for their microbicidal activity.

The other compounds covered by the protection request have similar effects.

50952C

879

Claims (3)

Patent claims: 1. 4-tert-Butylcyclohexylaminoalkanes of the general formula NHR in which R is an alkyl radical with 8 to 12 carbon atoms means. 2. Process for the preparation of the compounds according to Claim 1, characterized in that 4-tert-butylcyclohexyiamine is reacted in a manner known per se with the corresponding alkyl halide in a molar ratio of 1: 1 to 5: J at temperatures of 100 to 150 ° C and that Process product is distilled off from the reaction mixture in a customary manner. 3. Microbicidal preparation, characterized by a content of a compound according to claim 1 in addition to a carrier that contains the usual additives or fillers.