DE2457257A1 - ALCOXYLATED N-ALKYL DERIVATIVES OF PROPYLENEDIAMINE - Google Patents

Description

7457257

Th. Goldschmidt AG, Essen

Alkoxylated N-alkyl derivatives of propylenediamine

The invention relates to alkoxylated N-alkyl derivatives of propylenediamine and microbicidal preparations, marked by an effective content of such compounds.

The advancing technology of food production, be it in dairies, breweries, meat and sausage factories, but also requires the necessary disinfection in hospitals, bathing establishments and slaughterhouses the provision of highly effective compounds, which if possible not only against bacteria alone, but against Bacteria, fungi and yeast are equally effective and not only have an inhibitory, but also a killing effect. Through the formation of resistant strains and natural selection, it is necessary to constantly provide new funds, which outperform or complement some of the tried and tested older products. The technical Progress made by finding new and effective

ν'ί.ΙΓ

ties do not necessarily have to be in
that these compounds are better in their absolute effectiveness than the compounds of the prior art. Their mere provision enables existing disinfectants to be exchanged and thus reduces the formation of resistant strains. This alone can be a significant one
be technical progress.

The invention relates to new compounds of the general formula

.R ²

R ¹ HSiR ² (CH ₀ ) N:

where R is the cyclohexyl radical and R is a straight-chain alkyl

2
rest with 12 to 16 carbon atoms, R is a water

4 4

Substance radical or the group CH ₂ CHR OH, where R is a

Is hydrogen or methyl, and at least 1 R radical

4th
has the meaning of a CH “CHR OH group. It is under

having 12 to 16 carbon atoms to be understood the term straight chain alkyl group, a mixture of alkyl groups of different chain length which on average ki- C ₁₂ ^s Cg
Contain carbon atoms. Such mixtures of alkyl groups can be derived from naturally occurring fats

The compounds according to the invention can be obtained by reacting ethylene oxide or propylene oxide with compounds of the

6 ü υ 8 2 II 1 0 5 9

general formula

R ² ^ -NH (CH ₉ ), Νζ - ^: II

\ 3

in a molar ratio of 1: 1 to 2: 1 and the reaction mixture is heated to reflux for 10 to 25 hours. the The reaction can be carried out in the presence of a polar solvent. As polar solvents are suitable especially lower alcohols and their mixtures with water. A mixture of water and ethanol is particularly suitable in a volume ratio of 1: 1. '

If only 1 mol of alkylene oxide is added to compound II, creates a compound of the formula

R ¹ -N ~ (CH ₀ ), N <or R ¹ -NH -. (CH ₀ ).-N I \ 3

1 λ ^ R

CH ₂ CHR OH ■■ "'■.' ■ - ■■■ .-.: ..- ■■:. ■

The chromatogram ^shows': that only one single connection arose not determine · -ist.- Which of the two possible connections arise on ^1, can sich'ohne unreasonable analytical AuEwand. ■ "-""·

When the compound of the formula II is reacted with 2 mol alkylene oxide creates a uniform compound of the formula

Π U 9 Η 7 Λ / 1 0 5 §- ■■ ..

.CH ₂ CHR ⁴ OH

RN- (CH ₉ ), N '

ι 4 ^N R

^ OH

which can easily be proven by the fact that there are no longer any NH groups.

The new compounds are highly effective against bacteria, Fungi and yeasts and can therefore be referred to as microbicidal compounds.

The new compounds obtainable according to the invention are like this Well soluble in water that you can easily prepare 10 weight percent aqueous stock solutions, which in any Way can be diluted to use concentrations. . . . .-._..-.-

The products can be assembled in the usual way. This means dissolving in the desired solvents, Setting a certain pH value, preferably with organic acids such as acetic acid, possibly the Coloring and / or perfuming the preparation. The compounds can also be dissolved in low-boiling solvents and market them in aerosol form. Another type of aerosol preparation consists in dissolving the active substance in a solvent and forcing nitrogen onto the solutions in aerosol bottles.

6U3824 / 1ÜS9 ''

Wetting agents and cleaning agents, such as the addition products of ethylene oxide, can be added to the microbicidal preparations Compounds with acidic hydrogen, in particular with alcohols with a chain length of 8 to 14 carbon atoms, or quaternary ammonium compounds such as cetylpyridinium chloride are mixed in.

In the following examples, the preparation of the invention Compounds, the production of the microbicidal preparations therefrom and the microbicidal properties of these preparations 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, 1972. In the means Tables + germ growth, - no germ growth.

Θ U a 8 2 4/1 β 5

example 1

a) Implementation of S-n-dodecylamino-l-cyclohexylaminopropane with ethylene oxide in a molar ratio of 1: 1

To 1 mol of 3-n-dodecylamino-1-cyclohexylaminopropane, dissolved in 1000 ml of 60% ethanol, 1 mol of ethylene oxide cooled to 0 ° C. is slowly added under nitrogen and then left Boil under reflux for 20 hours. In the following distillation, 2 fractions are isolated:

1. 188 g 1,1-cyclohexyl, ß-hydroxyethylamino-3-n-dodecylaminopropane or l-cyclohexylamino-3,3-ß-hydroxyethyln-dodecylaminopropane;

Bp 190 to 196 ° C at 0.01 torr.

Elemental analysis for CH ₄₈ N ₃ O:

calculated: C 73.8%; H 14.0%; N 7.6%; 0 4.6% found: C 74.7%; H 13.0%; N 7.6%; 0 4.6%

2. 86 g 1,1-cyclohexyl, ß-hydroxyethylamino-3,3-n-dodecyl, ß-hydroxyethylaminopropane;

Bp 215-218 ° C at 0.01 torr.

Elemental analysis for C-rHroNpO-:

calculated: C, 72.8 I; H 12.7 I; N 6.8%; 0 7.7% found: C 73.2%; H 12.6%; N 6.9%; 0 7.4%

10S9

b) Production of the microbicidal preparations

To produce preparation 1, 0.1% by weight of the fraction was dissolved in water and made up with acetic acid adjusted to a pH of 7.6.

To produce preparation 2, the fraction 0.1% by weight dissolved in water and adjusted to a pE value of 6.0 'with acetic acid.

c) Testing of the microbicidal effectiveness of the preparation. 1

Test strain concentration exposure time in minutes in% 12 5 10 20 30

S. aureus 0.1 ___

0.01 ■ - - - ■ - ■■ - -

P. vulgaris 0.1. ■ · - -. -. . .-r: ■ - ■ .- '.' .. -

0, Oi ^{i; 1} ■■ '- ^a -' ^: - · "'-" ■ - - ·

0.001

P. expansüm ο vl · ' 0 , 05 ■ 1 - * * ■ -. ■: ■ '0 /Oil ■: ■; · - ■ ° , 005 0 , 001

• 0 υ a 8 2 4 / τ 0 S 9

Preparation 2

Test strain concentration exposure time in min,

in% 1 2 5 10 20 30

S. aureus 0.1 ______

0.005 + + + ---

E. coli 0.1 --- r ~ - - - -

0.001 + 4-4- 4- 4- 4-

C. albicans 0.1 - '- - - - - -

0.005 4-4-4-

M. gypseum .0,1 ,; -, 4-.; ■ + ·. ■■, ■ ..-: ■ - · -; - * .- ■

0.01 4- 4- -

S 9

Example 2

a) Implementation of S-n-dodecylamino-1-cyclohexylaminopropane with propylene oxide in a molar ratio of 1: 1

To 1 mole of S-n-dodecylamino-1-cyclohexylaminopropane, dissolved in 1000 ml of n-propanol, moles of propylene oxide cooled to 0 C are slowly added under nitrogen and then left Boil under reflux for hours. In the subsequent distillation, 2 fractions are isolated:

1. 23 5 g 1,1-cyclohexyl, β-hydroxy-n-propyl-amino-3-ndodecylaminopropane or 1-cyclohexylamino-3,3-3-hydroxyn-propy 1-n-dodecy laminopropane;

Bp 195 to 201 ° C at 0.05 torr.

Elemental analysis for C ₃₄ H ₅₀ N ₂ O:

calculated: C 75.5 I; H 13.1 I; N 7.2%; 0 4.2% found: C 74.6%; H 13.1%; N 7.2%; 0 4.4%

2. 79 g 1,1-cyclohexyl, 3-hydroxy-n-propylamino-3,3-3-hydroxy-n-propy1-n-dodecylaminopropane; Bp 228-233 ° C at 0.05 torr.

Elemental analysis for C ^ ₇ H ₁ -, N ₃ O-:

calculated: C 73.7%; H 12.7%; N 6.4%; 0 7.2% found: C 73.0%; H 12.2%; N 7.0%; 0 6.9%

9824 / ΙΟ S9

b) Production of the microbicidal preparations

To produce preparation 1, 0.1% by weight of the fraction was dissolved in water and made up with acetic acid adjusted to a pH of 7.4.

To produce preparation 2, 0.1% by weight of the fraction was dissolved in water and made up with acetic acid adjusted to a pH of 6.2.

c) Testing for microbicidal effectiveness Preparation 1

Test strain concentration exposure time in min,

in% 1 2 5 10 20

S. aureus 0.1 ___ __ _

0.01 + - -

0.005 +++

E. coli 0.1 ______

0.05 - - -

C. albicans 0.1 ______

0.05 - - -

0.01 - - -

0.005 _ _ -

0.001 + - -

P. expansum 0.1 ______

0.05 - - -

0.01 + - ■ -

0.005 + + -

0.001 + + + + +

Preparation 2

Test strain

Concentration in%

Exposure time in minutes 1 2 '5 10 20 30

S. aureus

0.05 0.01 0.005 0.001

E. coli

0.1

0.05

0.01

0.005

0.001

Example 3

a) Implementation of S-n-hexadecylamino-1-cyclohexylaminopropane with ethylene oxide in a violet ratio of 1: 1

1.5 mol of Sn-hexadecylamino-1-cyclohexylaminopropane are dissolved in 1300 ml of 60% ethanol. Under nitrogen is slowly leaves 1.5 moles to 0 ⁰ C gekünltes ethylene oxide to-. .. drip »Then - it is allowed to boil under reflux for 20 hours. The following fractions are obtained in the subsequent distillation: ¹ ^.

f VO 5.9.

1. 118 g 1,1-cyclohexylvβ-hydroxyethylamino-3-n-hexadecylaminopropane or l-cyclohexyl-3,3-ß-hydroxyethyln-hexadecylinopropane;

Bp 234-237 ° C at 0.05 torr.

Elemental analysis for C ₀ -H ₁ - .. N ₀ O:

27 56 / -

calculated: C, 76.4 I; H 13.2%; N 6.6%; 0 3.8% found: C 76.4%; H 13.1. %; N 6.9%; 0 3.4%

2. 55 g of 3,3-n-hexadecyl, 3-hydroxyethylamino-l, 1-cyclohexyl, ß-hydroxyethylaminopropane;

B.p. 255 to 260 ° C at 0.05 torr.

Elemental analysis for C29 ^H 6O ^N 2 ^ 2 ^:

calculated: C 74.3%; H 12.9%; N 6.0%; 0 6.8% ■ found: 'C "' 74.6"%; H '13, 0%; N 6.5%; Ö 6.2%

b) Production of the microbicidal preparations

For the production of preparation 1, fraction 1 0.1% by weight dissolved in water and adjusted to a pH of 5.0 with acetic acid. . ;

To produce preparation 2, fraction 2 was dissolved to 0.1% by weight in water and made up with acetic acid adjusted to a pH of 4.9.

6 U 90 24 / 1069-

c) Testing for microbicidal effectiveness Preparation 1

Test strain concentration exposure time in min,

in% 1 2 5 10 20

S. aureas 0.1 ______

0.05 - - -

0.01. + - -

0.005 + - -

0.001 +++

E. coli 0.1 ______

0.005 + + + + +

0.001 ++ ■ + _ + - + +

C. albicans 0.1 ______

0.05 _ _ -

0.01 - - -

0.005 + - -

0.001 + + -

M. gypseum 0.1 ++ ----

0.05 + + -

0.01 + ■ + ----

0.005 + + -

0.001 + + -

6U38 24/10 59

? 4 5 7 2 5 7

Preparation 2

Test strain concentration exposure time in min,

in% 1 2 5 10 20 30

S. aureus 0.1 ______

0.005 + + -

E. coli 0.1 + ____-

0.05 + ■ + +

P. aeruginosa 0.1 ______

Claims (2)

Claims 1. Compounds' of the general formula. R-NR ² (CH ₂ ) ₃ N < where R is the cyclohexyl radical and R is a straight chain Is an alkyl radical having 12 to 16 carbon atoms, R is one 4 - ■ <- Is hydrogen radical or the group CH ₂ CHR OH, where 4th
R is a hydrogen or methyl radical, and at least k R ² residue the meaning of a. CH ^ CHR ⁴ OH group, obtainable by mixing; Ethylene oxide or propylene oxide with compounds of the general formula; - ,, -, ^ ■ -, -. R ¹ -NH (CH ₂ ) ₃ N { II \ _R 3 - ■ · - " in a molar ratio of 1: 1 to 2: 1 and heating the reaction mixture to reflux temperature for 10 to 25 hours, preferably in the presence of a polar solvent. 2. Microbicidal preparations, characterized by an effective content of compounds of claim 1. 9824 / ιαε-9