DE2330454C3 - 4-tert-butylcyclohexylaminoalkanes, processes for their production and microbicidal preparations - Google Patents

Description

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

35

CH,

H, C-C

NHR

40

CH ₃

in which R denotes an alkyl radical having 8 to 12 carbon atoms, and processes for their preparation and microbicidal preparations containing these compounds.

Microbicides in the context of the present invention are understood to mean the property of a compound or a preparation containing this compound, gram-positive and gram-negative bacteria, skin and Kill mold, yeast, viruses or algae.

When applying microbicidal compounds, it is desirable to have a wide range to have a wide variety of substances available in order to avoid the formation of resistance. Selective effectiveness is also desirable.

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

It can be useful in the presence of a hydrogen halide acceptor, preferably alkali or Alkaline earth hydroxide to work. A special addition of a hydrogen halide acceptor is unnecessary however, if necessary, if the reaction is carried out with a large excess of amine as the amine then acts as an acid acceptor.

The reaction proceeds at temperatures of from 100 to about 15O ⁰ C, the lower limit of 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 reaction proceeds rapidly enough at higher temperatures By-products can arise. The temperature range from 130 to 140 C. is preferred.

The desired process product is separated off from the reaction mixture by distillation. 1st 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 group is a dodecyl group. the boiling point at 155 to 177 ° C is 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 C _I2 -alkyl component 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 if you want to use them in an aqueous medium, use them together with a solubilizer. Examples of such solubilizers are the addition products of ethylene oxide with hydrophobic ones Compounds with an active hydrogen atom, 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 substance, about the same amount Solubilizing agents.

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 microbicidal 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. By adding the solubilizing agent when using an aqueous solution, the The cleaning power of the solutions is enhanced, especially when used as a solubilizing agent non-ionic surfactants are used.

In the following examples, the connection genius according to the invention is first explained. Afterward the effectiveness of the preparations produced according to the invention is shown in tabular form shown. The test for microbicides was carried out according to the guidelines of the German Society for Hygiene and microbiology e. V., Gustav Fischer Verlag, Stuttgart, 1959. In the tables, means + Germ growth, - no germ growth.

In Examples ί and 2, the preparation of the new compounds according to the invention is described. Examples 3 to 6 show the preparation of preparations using these compounds explained. This is followed by tables showing the superior microbicidal effect.

example 1 ^ tert-Butylcyclohexyiaminooctane

A 4-1 four-necked flask equipped with a KPG stirrer (= Küppers precision glass stirrer), dropping funnel, thermometer and reflux condenser is charged with ρ mol ^ tert-butylcyclohexylamine and 4.8 mol NaOH. 3 mol of n-octyl bromide are slowly added to this mixture and then heated for 1 hour to about 135 ° C. The inorganic residue is then decanted while still hot and the decanted liquid is subjected to fractional distillation 155 to 160 C and 0.6 torr 608 g above.
Elemental analysis for C ₁₈ H ₃₇ N (molecular weight 268):

Calculated ... C 80.9, H 13.9, N 5.2%;

found .... C 80.5, H 13.7, N 5.2%.

Example 2

Production 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 4-1 four-necked flask equipped with a KPG stirrer, dropping funnel. Thermometer and reflux condenser, 3 mol of dodecyl bromide are added in small portions and then heated to 140 ^° C. for 1 hour. Then the inorganic residue is 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-butylcyclohexylaminododecane are transferred.

Elemental analysis door C ₂₂ H ₄₅ N (molecular weight 324):

Calculated ... C 81.6, H 13.9, N 4.5 wt%; found .

IO

Example 5

10 parts by weight 4 - tert. - Butylcyclohexylaminodod ^ can 10 parts by weight of an addition product of 12 moles of ethylene oxide and 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 80 / o

CH ₃

i
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

Stirring homogenized at about 50 ° C.

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 percent by weight active ingredient Solution given.

35

Table 1

C8Ü ', H 14J * N4 ^ 4% by weight.

Example 3

40

10 parts by weight 4-liter. - Butylcyclohexylaminooctane, 10 parts by weight of an addition product of 12 moles of ethylene oxide with 1 mole 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. with stirring and heating.} This gives a yellow, clear solution which can be easily diluted with water.

Example 4

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

Cl

C ₁₂ H ₂₅ -N-CH ₂

CH ₃

55

60

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

pH value: 7.0. I. Conc l-.invsirkunj; szeit 2 5 in minutes 20th 30th Agree tration 4- __ - - - (%) I. 4th - - 10 - - 0.1 4- + + - - - S. aureus 0.05 4- 4- + - 4- + 0.01 - 4- 4- 4- 4- 4- 0.005 - - 4- - - 0.001 4- - - 4- - - 0.1 + + + - 4- 4- Ii. coli 0.05 + 4- + - 4- 4- 0.01 - + 4- 4- 4- 4th 0.005 - - 4- - - 0.001 + - 4- - - 0.1 4- 4- 4- - 4- 4th P. vulgaris 0.05 4- 4- 4- - + 4th 0.01 4th 4th 4- + + 4th 0.005 4- - - 4- - - 0.001 4- - - 4- - - 0.1 f 4- + - - - T. menta- 0.05 + 4- 4- - - - grophylcs 0.01 4- 4- - + - 0.005 - 0.001 +

Concen- I: inuir _n ungs / cit concentration in minutes

(%) 1 2 5 IO 20

- - - - - -

Table 2
pH value: 6.7.

Tesl tribe

S. aurei's 0.1

0.05 _0: 01 0.005 0.001

E. coli 0.1

0.05 0.01 0.005 0.001

P. vulgaris 0.1

0.05 0.01 0.005 0.001

M.gypseum 0.1 0.05 0.01 0.005 0.001

Table 3
pH value: 5.0.

Test lamb concentration in minutes

!ration

-f table 4
pH: 5.1

Teslsiamm
S. aureus

~~ 2o P. vulaaris

25th

P. acruginosa

30th

35

P. expansum

Kun / en fcinpolitunö / eii !ration

(%) 1 2

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

I 2 5 10 20 0.1

0.05

0.01

0.005

0.001

in minutes IO 20 M)

S. aureus 0.1 - - - - - - 0.05 + - - - - - 0.01 + + + + - - 0.005 + + + + + + 0.001 4- + 4- 4- 4- 4- E. coli 0.1 - - - - _ - 0.05 + - - - - - 0.01 + + + -f 4- 4- 0.005 + + + + 4- + 0.001 4- 4- 4- 4- + + E. acruginosa 0.1 - - - - - - 0.05 - - - - - - 0.01 -f 4- 4- + + + 0.005 4- 4- 4- + ₊ 0.001 4- + + + 4- 4- C. albicans 0.1 _ _ _ 0.05 - - _ _ - - 0.01 + + - - - - 0.005 + + + + - - 0.001 _{+ +} + -I- -I-

The following experiment serves as a comparative experiment.

The mode of action of hexachlorophene as a disinfectant is described in the book »Sterilization, Disinfection, Conservation, Chemotherapy «by Wa 11-h ä u ß e r and Schmidt, Georg Thieme Verlag. Stuttgart, 1967, p. 193.

A mixture of equal parts by weight of hexachlorophene and a Reaction product of 12 moles of ethylene oxide with tridecyl alcohol is used. The specified concentrations relate to the content of chlorophore. The pH of the aqueous solution is 7.7.

Teslsiamm Concentration / cil in minutes

tration

(%) I 2 5 10 20

S. aureus 0.1

0.05 0.01

continuation

Test strain

E. coli O ¹

0.5

P. aeruginosa 2.0 1.0 0.5

C. albicans 5.0

2.5 1.0

Concentration exposure time in minutes

10 20

Test strain

P. expansum

- to

15th

concentration

5.0 2.5 1.0

Exposure time in minutes, 2 5 10 20

The table shows the superiority of the invention Compounds related to their microbicidal «

Effectiveness.

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

Claims (3)

Patent claims: 1. 4-tert-ButylcycIohexylaminoalkane of the general formula H, C-C- (H> -NHR IO in which R denotes an alkyl radical having 8 to 12 carbon atoms. 2. Process for the preparation of the compounds according to claim 1, characterized in that 4-tert-butylcyclohexylamine is reacted in a manner known per se 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 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.