US3717579A - Biocidal preparation - Google Patents
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- US3717579A US3717579A US00078246A US3717579DA US3717579A US 3717579 A US3717579 A US 3717579A US 00078246 A US00078246 A US 00078246A US 3717579D A US3717579D A US 3717579DA US 3717579 A US3717579 A US 3717579A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/40—Monoamines or polyamines; Salts thereof
Definitions
- BIOCIDAL PREPARATION [75] Inventors: Eberhard Batman, 43 Essen- Bredeney; Ulrich Holtschmidt, Es-
- R is alkyl with 8 to 18 carbon atoms
- carbon chain may be interrupted by O, -NI-I, or
- R is hydrogen, -CH or Cl-I CH OH
- R is hydrogen or CH CI-I,OH, (CH CH NR),
- R and R have the above meaning, and R is one of the groups -oHQo00H, CH3(
- R is alkyl with eight to 18 carbon atoms or the group wherein X is chlorine or bromine.
- X is chlorine or bromine.
- Surface active amines corresponding to and being embraced by formula I are, for example, laurylamine, N,N- bis -hydroxyethyllaurylamine, N-hydi'oxyethyllaurylamine, N,N-dimethyllaurylamine, N-laurylethylenediamine, N-lauryl-diethylenetriamine, N- laurylpropylenediarnine, N-lauryl-N', N -dimethy1- propylenediamine and N-lauryldipropylenetriamine, as well as the analogous compounds which instead of lauryl contain octyl, decyl, tetradecyl, hexadecyl or octadecyl. Particularly economical are often times mixtures of such homologues as they, for example, are formed in the production of surface active amines from natural fatty acids, such as, for example, coconut fatty acids.
- N-laurylaminoacetic acid N-laurylethylenediaminoacetic acid, N-lauryldiethylenetriaminoacetic acid, N-laurylpropylenediaminoacetic acid, N-lauryL diethylenetriamino-a-propionic acid and N-laurylpropylenediamino-B-butyric acid, as well as the homologue compounds wherein the lauryl group is replaced by octyl, decyl, tetradecyl, hexadecyl or octadecyl and their mixtures, for example, mixtures havin g alkyl which is derived from a coconut fatty acid.
- the compounds of formula I and II may, in accordance with the invention, preferably be employed in the form of their mixtures. Such mixtures are, for example, obtained if compounds of formula I are reacted with chloroacetic acid, a-chloropropionic acid or crotonic acid in a mole ratio of l:l. However, it is also feasible to employ the compounds of the formulas l and ll individually, to wit, not in mixture, for the purpose of preparing the inventive preparations or mixtures which then additionally contain the 2-alkylamino- 6-aminopyridines. However, in such event, it should be observed that not all the compounds of formula I are sufficiently water soluble at pH values of 7.
- surface active amines of sufficient water solubility at the indicated pH, should be used, such as, for example, N-hydroxyethyllaurylamine, lauryldiethylenetriamine, laurylpropylenediamine, lauryldipropylene-triamine and N- lauryl-N',N'-dimethylpropylenediamine.
- the weight ratio of the substances of formula I and/or [1 to the substances of formula III should in the inventive mixtures or preparations be between about l and l 3.
- a preferred ratio is between about 3 1 and l :2.
- inventive preparations or mixtures is accomplished in technically exceedingly simple manner, by simply mixing the individual components per se or by mixing them in the form. of their aqueous or alcoholic solutions at temperatures between about 20 to l00C.
- aqueous or alcoholic solutions at temperatures between about 20 to l00C.
- solvents are eminently suitable for the indicated purpose: n-propylalcohol, isopropylalcohol, ethylglycol, ethyleneglycol, propyleneglycol (1,2), dioxane and glycoland dimethylether.
- non-ionogenic tensides may be incorporated into the mixtures or preparations.
- inventive mixtures or preparations may be produced in solid form, as pastes or in dissolved or dispersed form.
- inert carrier materials such as thickeners, inorganic salts, such as alkali metal phosphates, alkali metal silicates, alkali metal borates or urea, as well as aroma imparting compounds, is of course feasible and does not affect the scope of this invention.
- inventive preparations or mixtures may be used as disinfectants and preservatives in food processing plants, breweries, animal breeding establishments and hospitals. They are also effective algecides, fungicides and virucides.
- EXAMPLE 1 50 parts by weight of 2-octylamino-6-aminopyridine are dissolved in 100 ccm of alcohol while heating to 50C. 200 parts by weight of an aqueous solution of 25 percent concentration are then added which solution contains as active component the reaction product of a mixture of 1 mole of N-lauryldiethylenetriamine and 2 mole of N-laurylpropylenediamine with 2 mole of chloroacetic acid. The pH value of the system thus ob tained was adjusted to 4.5 by adding acetic acid. A clear foaming preparation was obtained containing about 28 percent of active ingredient. The preparation could be diluted with water in any desired ratio.
- EXAMPLE 2 10 parts by weight of 2-octylamino-6-aminopyridine are dissolved in a mixture of 30 parts by weight of npropanol and 10 parts by weight of glacial acetic acid. 50 parts by weight of a 20 percent aqueous solution containing as active ingredient the reaction product of 2 mole of N-laurylpropylenediamine and 1 mole of chloroacetic acid are then added. A clear, foaming solution is obtained which can be diluted with water in any desired ratio and which contains about 20 percent of active ingredient.
- EXAMPLE 3 20 parts by weight of N-lauryl-N,N'-dimethylpropylenediamine, 10 parts by weight of 2-laurylamino-fi-aminopyridine, 30 parts by weight of glacial acetic acid and 40 parts of water were worked into a homogenous preparation under heating to C.
- the preparation contains 30 percent of active ingredient and can be diluted with water in any desired ratio.
- the preparation exhibits pronounced fungicidal activity.
- EXAMPLE 4 50 parts by weight of N,N-bis-hydroxyethyllaurylamine, 20 parts by weight of Z-chlorobenzylaminoo-aminopyridine, 30 parts by weight of concentrated hydrochloric acid, and 40 parts by weight of ethylglycol are homogenized under heating to 50C.
- the resulting solution contains 50% of active ingredient and can be diluted with water.
- EXAMPLE 5 100 parts by weight of N-coconutalkylpropylenediaminoacetic acid and 40 parts by weight of 2- decylamino-6-aminopyridine were dissolved in 300 parts by weight of propyleneglycol (1,2) under slight heating.
- the N-coconutalkylpropylenediaminoacetic acid was obtained by reaction of 1 mole of N-coconutpropylenediamine with 1 mole of chloroacetic acid.
- the chain length distribution in the coconutpropylenediamine was as follows:
- EXAMPLE 6 In a manner analogous to that of Example 5, a preparation was manufactured which instead of N- coconutalkylpropylenediaminoacetic acid contained N-coconutalkylpropylenediamino-abutyric acid. The latter was synthesized by reaction of N-coconutpropylenediamine with crotonic acid.
- the preparation consists of 1 part by weight of the reaction product of a mixture of 2 mole of C I-I NH (CI-I NH and 1 mole of C I-I NI-I(CH NII(CI-I NI-I with 2 mole of chloroacetic acid and 1 part by weight of This preparation is being designated as preparation A.
- the pH of the 0.1 percent solution calculated on the total amount of active ingredient was adjusted to a value of 5.
- the bacteriological activity of the reaction product of a mixture of 2 mole ofC I-I NI-I(CH,) NH and 1 mOle 0f CI2HZ5NH (CH2)2 NH(CH2)2 NH2 with 2 mole of chloroacetic acid was examined (hereinafter referred to as preparation B).
- the pH of the solution containing 0.1 percent of active ingredient was adjusted to a value of 5. This was effected with acetic acid.
- preparation C The bacteriological activity of a dispersion of 2-Octylamino-6-aminopyridine was tested (hereinafter referred to as preparation C).
- the pH value of the 1 percent dispersion was adjusted to a value of 4.3 with acetic acid.
- the preparation consists of 1 part by weight of the reaction product of 2 mole of C, H NH-(CH NR with 1 mole of chloroacetic acid and 1 part by weight of OEHYINH NH:
- This preparation is indicated as preparation D.
- TEST SERIES V than the comparison or con
- This test series examines the eye irritation caused by the inventive preparations and by the individual components thereof.
- Proteus vulgaris and 118 through 12 Escherichia coli V (a) The inventive preparation corresponded to preparation A, contained, however, 0.5 percent of active ingredient. The pl-l-value of this solution was 5.
- V (b) The comparison preparation corresponded to I preparation B, contained, however, 0.5 percent of active ingredient.
- the pH-value of the solution was 5.
- a synergistic biocidal mixture consisting essentially of a. a compound of the formula wherein R is alkyl with eight to 18 carbon atoms, R is hydrogen, Cl-l or CH Cl-l Ol-l, and R is hydrogen, CH CH OH, (CH CH NR (CH CH NR ),,,R (CH CH CH NR ),,.R m having a value of l or 2, CH COOI-l,
- R is alkyl of eight to 18 carbon atoms or the group wherein X is chlorine or bromine, the weight ratio a b being about between 5 l to l 3.
- a biocidal preparation essentially consisting of a biocidally effective amount of the synergistic mixture of claim 1 and an inert carrier.
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Abstract
A synergistic, biocidally active mixture comprises surface active amines and/or aminoacids and 2-alkyl-amino-6aminopyridines.
Description
United States Patent [1 1 Hoimann et al.
[ 51 Feb. 20, 1973 [54] BIOCIDAL PREPARATION [75] Inventors: Eberhard Batman, 43 Essen- Bredeney; Ulrich Holtschmidt, Es-
sen, both of Germany [73] Assignee: Th Goldschmidt A.G., Essen, Germany [22} Filed: Oct. 5, 1970 [2]] Appl. N0.: 78,246
UNITED STATES PATENTS 2,963,486 l2/l960 Mizzoni ..260/296 2,080,517 5/1937 Tisza ..260/296 3,225,04l 12/1965 Johnson ..260/247.5 3,290,040 8/1965 Lange et al ..260/296 FOREIGN PATENTS OR APPLICATIONS 963,907 7/1964 Great Britain 692,022 5/1953 Great Britain 932,012 8/l955 Germany Primary Examiner-Leon D. Rosdol Assistant Examiner-P. E. Willis Attorney-Toren & McGeady 5 7 ABSTRACT A synergistic, biocidally active mixture comprises surface active amines and/or aminoacids and 2-alkylamino-6-aminopyridines.
5 Claims, No Drawings BIOCIDAL PREPARATION CROSS REFERENCE TO PRIOR DISCLOSURE This invention corresponds to Disclosure Document 000737, deposited on Oct. 21, 1969.
FIELD OF INVENTION BACKGROUND INFORMATION AND PRIOR ART A recently filed U.S. patent application Ser. No. 51,396, which is based on German Pat. application No. P 19 33 504.7, as well as U.S. Pat. application Ser. No. 10,280, filed Feb. 10, 1970 now U.S. Pat. No. 3,647,808, based on German application No. P 19 08 078.5, disclose synergistic mixtures which contain 2-alkylamino-6-aminopyridines as bacteriologically active component. The second component suggested in the applications referred to consists of quaternary ammonium compounds or betaines.
These previously disclosed mixtures or preparations made therefrom exhibit excellent bacteriological characteristics, characteristics which are also pronounced in the presence of soaps, protein or lipoids. However, the cleaning action and foam forming properties of preparations which contain quaternary ammonium compounds and 2-alkyIarnino-6- aminopyridines are not always satisfactory, particularly if strongly soiled materials are to be cleaned. For this reason additional ingredients, such as, for example, non-ionogenic tensides have to be incorporated into the preparations so as to improve the cleaning and foaming actions.
In respect to preparations which contain betaines, it will be appreciated that mixtures of 2-alkylamino-6- amino-pyridines and betaines are relatively expensive. This is so because the betaines which in themselves are relatively inexpensive and which are used in the mixture as solubilizing agent, do not themselves possess any bacteriological activity. For this reason, higher concentrations of active component have to be used which thus renders the preparation relatively expensrve.
SUMMARY OF THE INVENTION It is a primary object of the invention to overcome the drawbacks of the known synergistic mixtures and preparations and to provide a biocidally active mixture which has superior cleaning and foam producing characteristics, is relatively inexpensive and exhibits excellent biocidal or bacteriological properties.
Generally, it is an object of the invention to improve on the art of synergistic mixtures and preparations exhibiting biocidal activity.
Briefly, and in accordance with this invention, it has surprisingly been found that the above indicated objects are superiorly obtained and the drawbacks referred to are effectively overcome by synergistic mixtures which comprise surface active amines and/or aminoacids as well as 2-alkylamino-6-aminopyridines. Such mixtures, contrary to the individual components taken alone, exhibit superior biocidal activity and excellent cleaning action over a wide pH range. Further, the inventive mixtures or preparations have satisfactory compatibility in respect to skin and mucous membranes and are substantially insensitive in respect to protein, lipoids and anionic detergents. Moreover, the inventive mixtures are exceedingly economical both in respect to manufacture and use.
Concerning the surface active amines, compounds of the following formula I yield excellent results:
In this formula, R is alkyl with 8 to 18 carbon atoms, in
which the carbon chain may be interrupted by O, -NI-I, or
R is hydrogen, -CH or Cl-I CH OH, and
R is hydrogen or CH CI-I,OH, (CH CH NR),
(CI-I CI-I,NR),,,R or (CH CH CH NR ),,,R, wherein m has a value of l or 2.
If a surface active aminoacid is used, compounds of the general formula II are recommended:
wherein R and R have the above meaning, and R is one of the groups -oHQo00H, CH3(|3HCOOH, onac lirouaooou,
As 2-alkylamino-6-aminopyridines, compounds of the general formula III are used:
III
wherein R is alkyl with eight to 18 carbon atoms or the group wherein X is chlorine or bromine. The preparation of compounds of formula III is disclosed in U.S. Pat. No. 3,647,808, column 2.
Surface active amines corresponding to and being embraced by formula I are, for example, laurylamine, N,N- bis -hydroxyethyllaurylamine, N-hydi'oxyethyllaurylamine, N,N-dimethyllaurylamine, N-laurylethylenediamine, N-lauryl-diethylenetriamine, N- laurylpropylenediarnine, N-lauryl-N', N -dimethy1- propylenediamine and N-lauryldipropylenetriamine, as well as the analogous compounds which instead of lauryl contain octyl, decyl, tetradecyl, hexadecyl or octadecyl. Particularly economical are often times mixtures of such homologues as they, for example, are formed in the production of surface active amines from natural fatty acids, such as, for example, coconut fatty acids.
Surface active aminoacids which can successfully be used for the purposes of this invention and are embraced by the formula ll, are, for example, N-laurylaminoacetic acid, N-laurylethylenediaminoacetic acid, N-lauryldiethylenetriaminoacetic acid, N-laurylpropylenediaminoacetic acid, N-lauryL diethylenetriamino-a-propionic acid and N-laurylpropylenediamino-B-butyric acid, as well as the homologue compounds wherein the lauryl group is replaced by octyl, decyl, tetradecyl, hexadecyl or octadecyl and their mixtures, for example, mixtures havin g alkyl which is derived from a coconut fatty acid.
The compounds of formula I and II may, in accordance with the invention, preferably be employed in the form of their mixtures. Such mixtures are, for example, obtained if compounds of formula I are reacted with chloroacetic acid, a-chloropropionic acid or crotonic acid in a mole ratio of l:l. However, it is also feasible to employ the compounds of the formulas l and ll individually, to wit, not in mixture, for the purpose of preparing the inventive preparations or mixtures which then additionally contain the 2-alkylamino- 6-aminopyridines. However, in such event, it should be observed that not all the compounds of formula I are sufficiently water soluble at pH values of 7. Accordingly, if the compounds of formula I are used without formula II compounds, surface active amines of sufficient water solubility at the indicated pH, should be used, such as, for example, N-hydroxyethyllaurylamine, lauryldiethylenetriamine, laurylpropylenediamine, lauryldipropylene-triamine and N- lauryl-N',N'-dimethylpropylenediamine.
Reverting now to the compounds corresponding to formula III, the following examples embraced by this formula are suitable: 2-octylamino-6-aminopyridine, 2- decylaminoJi-aminopyridine, 2-laurylamino-6- aminopyridine, 2-myristylamino-6-aminopyridine, 2- stearylamino--aminopyridine, 2-pchlorobenzylamino-6-aminopyridine 2-0- chlorobenzylamino-o-aminopyridine.
The weight ratio of the substances of formula I and/or [1 to the substances of formula III should in the inventive mixtures or preparations be between about l and l 3. A preferred ratio is between about 3 1 and l :2.
The manufacture of the inventive preparations or mixtures is accomplished in technically exceedingly simple manner, by simply mixing the individual components per se or by mixing them in the form. of their aqueous or alcoholic solutions at temperatures between about 20 to l00C. In addition to water and ethylalcohol, the following solvents are eminently suitable for the indicated purpose: n-propylalcohol, isopropylalcohol, ethylglycol, ethyleneglycol, propyleneglycol (1,2), dioxane and glycoland dimethylether. If desired, non-ionogenic tensides may be incorporated into the mixtures or preparations. The inventive mixtures or preparations may be produced in solid form, as pastes or in dissolved or dispersed form. The addition of inert carrier materials, such as thickeners, inorganic salts, such as alkali metal phosphates, alkali metal silicates, alkali metal borates or urea, as well as aroma imparting compounds, is of course feasible and does not affect the scope of this invention.
The inventive preparations or mixtures may be used as disinfectants and preservatives in food processing plants, breweries, animal breeding establishments and hospitals. They are also effective algecides, fungicides and virucides.
The invention will now be described by several examples, it being understood that these examples are given by way of illustration and not by way of limitation, and that many changes may be effected without affecting in any way the scope and spirit of this invention as recited in the appended claims.
The following examples describe the preparation of the inventive mixtures:
EXAMPLE 1 50 parts by weight of 2-octylamino-6-aminopyridine are dissolved in 100 ccm of alcohol while heating to 50C. 200 parts by weight of an aqueous solution of 25 percent concentration are then added which solution contains as active component the reaction product of a mixture of 1 mole of N-lauryldiethylenetriamine and 2 mole of N-laurylpropylenediamine with 2 mole of chloroacetic acid. The pH value of the system thus ob tained was adjusted to 4.5 by adding acetic acid. A clear foaming preparation was obtained containing about 28 percent of active ingredient. The preparation could be diluted with water in any desired ratio.
EXAMPLE 2 10 parts by weight of 2-octylamino-6-aminopyridine are dissolved in a mixture of 30 parts by weight of npropanol and 10 parts by weight of glacial acetic acid. 50 parts by weight of a 20 percent aqueous solution containing as active ingredient the reaction product of 2 mole of N-laurylpropylenediamine and 1 mole of chloroacetic acid are then added. A clear, foaming solution is obtained which can be diluted with water in any desired ratio and which contains about 20 percent of active ingredient.
EXAMPLE 3 20 parts by weight of N-lauryl-N,N'-dimethylpropylenediamine, 10 parts by weight of 2-laurylamino-fi-aminopyridine, 30 parts by weight of glacial acetic acid and 40 parts of water were worked into a homogenous preparation under heating to C. The preparation contains 30 percent of active ingredient and can be diluted with water in any desired ratio. The preparation exhibits pronounced fungicidal activity.
EXAMPLE 4 50 parts by weight of N,N-bis-hydroxyethyllaurylamine, 20 parts by weight of Z-chlorobenzylaminoo-aminopyridine, 30 parts by weight of concentrated hydrochloric acid, and 40 parts by weight of ethylglycol are homogenized under heating to 50C. The resulting solution contains 50% of active ingredient and can be diluted with water.
EXAMPLE 5 100 parts by weight of N-coconutalkylpropylenediaminoacetic acid and 40 parts by weight of 2- decylamino-6-aminopyridine were dissolved in 300 parts by weight of propyleneglycol (1,2) under slight heating. The N-coconutalkylpropylenediaminoacetic acid was obtained by reaction of 1 mole of N-coconutpropylenediamine with 1 mole of chloroacetic acid. The chain length distribution in the coconutpropylenediamine was as follows:
C 1.3 C 4.5 C 61.2% C 30.3 C 2.0% C 0.7
After addition of 120 parts by weight of acetic acid of 30 percent concentration, a clear foaming solution containing 25 percent of active ingredient was obtained.
EXAMPLE 6 In a manner analogous to that of Example 5, a preparation was manufactured which instead of N- coconutalkylpropylenediaminoacetic acid contained N-coconutalkylpropylenediamino-abutyric acid. The latter was synthesized by reaction of N-coconutpropylenediamine with crotonic acid.
In order to demonstrate the synergistic effect of the inventive preparations, the bacteriological activity that the individual components of the mixtures.
The bacteriological tests were performed according to the Richtlinien der deutschen Gesellschaft fuer I-Iygiene und Mikrobiologie (guidelines of the German association for hygiene and microbiology).
TEST SERIES I I a) Testing of the inventive preparation corresponding to Example 1:
The preparation consists of 1 part by weight of the reaction product of a mixture of 2 mole of C I-I NH (CI-I NH and 1 mole of C I-I NI-I(CH NII(CI-I NI-I with 2 mole of chloroacetic acid and 1 part by weight of This preparation is being designated as preparation A.
The pH of the 0.1 percent solution calculated on the total amount of active ingredient was adjusted to a value of 5.
Species Concentration Action time in minutes of active substance in% l 2 5 lo 20 30 Staphylococcus aureus 0.05 0.01 0.005
Pseudomonas 0.l
aeruginosa Proteus 0.1
vulgaris Escherichia coli no bacteria growth bacteria growth I (b) Control test with mixture outside the scope of this invention:
The bacteriological activity of the reaction product ofa mixture of 2 mole ofC I-I NI-I(CH,) NH and 1 mOle 0f CI2HZ5NH (CH2)2 NH(CH2)2 NH2 with 2 mole of chloroacetic acid was examined (hereinafter referred to as preparation B). The pH of the solution containing 0.1 percent of active ingredient was adjusted to a value of 5. This was effected with acetic acid.
Species Concentration Action time in minutes of active substance in% l 2 5 10 20 30 Staphylo- 0 l coccus 0.05 aureus 0.01
Pseudomonas 0.1
aeruginosa 0.05 0.01 0.005 0.001
Proteus 0.1 vulgaris 0.05 0.01 0.005 0.001
Escherichia 0.1 coli 005+ I Control test with preparation outside the scope of this invention:
The bacteriological activity of a dispersion of 2-Octylamino-6-aminopyridine was tested (hereinafter referred to as preparation C).
The pH value of the 1 percent dispersion was adjusted to a value of 4.3 with acetic acid.
Species Concentration Action time in minutes of active substance in% l 2 5 2O 30 Staphylo- 0.1 coccus 0.05 aureus 0.01 0.005
Pseudomonas 0.1
aeruginosa 0.05
Proteus 8.1- vulgaris 0.05 0.01 0.005
Escherichia 0.1
coli 0.05
Comparison of the values of Tables Ia through 1c indicates clearly the superiority of the inventive synergistic mixture (preparation A) as compared to the individual components (preparations B and C).
TEST SERIES II II (a) Test of an inventive preparation corresponding to Example 2:
The preparation consists of 1 part by weight of the reaction product of 2 mole of C, H NH-(CH NR with 1 mole of chloroacetic acid and 1 part by weight of OEHYINH NH:
This preparation is indicated as preparation D.
The pH of an aqueous solution containing 0.1% of active ingredient was adjusted was adjusted with acetic acid to a value of5.
Pseudomonas aeruginosa Proteus vulgaris Escherichia coli Species Concentration Action time in minutes of active substance in% l 2 5 10 2O 30 Staphylo- 0.1 coccus 0.05
aureus 0.01 0.005 0.001
Pseudomonas 0.1
aeruginosa 0.05 0.01
Proteus 0.1 vulgaris 0.05 0.005 0.001
Escherichia 0.1 coli 0.05 0.01 0.005 -i 0.001
The comparison of the values of Tables 11 (a) and 11 (b) indicates clearly the superiority of the inventive mixture as compared to the characteristics of the individual components.
TEST SERIES ill in this test series, the bacteriological activity of the inventive preparations A and D, as well as of the control preparations B and E is tested in the presence of 20 percent by weight of bovine (cattle) serum. The tests were also performed pursuant to the Richtlinien der deutschen Gesellshaft fuer Hygiene und Mikrobiologie.
l IV (a) Bacteriological activity of the inventive preparations A and D in the presence of 0.1percent by weight of soft soap.
D Concentration Action time Action time of active subin minutes in minutes stancein% 125 30125 10 20 Species Staphylococcus aureus Pseudomonas aeruginosa Proteus vulgaris Species Staphylo coccus au reus Pseudomon as aeruginosa Escherichia coli Proteus vulgaris by weight Action time in minutes 1251020301251020 30 IV (b) Bacteriological activity of the control Concentration Action time of active subin minutes stance in% preparations B and E in the presence of 0.1%
of soft soap. III (b) Bacteriological activity of the control preparations B and E in the presence of 20 percent by weight of Species bovine serum.
Staphylo- Concentration Action time Action time coccus of active sub- Escherichia coli Species l 1 5 .J 0000000000 m n a mu m o c 8 2m u ea e e u g i fer. Ol Cl u e u o aPa Pv E0 0 4 0 2 0 m m m2 .m 0 3 2 S mm n5 m2 .m .m m
51 m a 000 h D.
c mom SCa A comparison of Tables IV (a) and W (b) clearly indicates that the inventive preparations are rendered considerably less inactive b Pseudomonas aeruginosa y the presence of soft soap trol preparations.
TEST SERIES V than the comparison or con This test series examines the eye irritation caused by the inventive preparations and by the individual components thereof. The eye irritation test according to J.ll. Draize and E.A. Kelley as described in Drug and Cosmetic Industry, volume 71 (1952) pages 36 and 37 0, was used for this purpose.
Proteus vulgaris and 118 through 12 Escherichia coli V (a) The inventive preparation corresponded to preparation A, contained, however, 0.5 percent of active ingredient. The pl-l-value of this solution was 5.
rabbit no.
average value 1st day A und TEST SERIES IV In this test series, the bacteriological activity of the inventive preparations A and B as well as the control preparations B and E is tested in the presence of 0.1 percent by weight of soft soap. The Richtlinien der deutschen Gesellschaft fuer Hygiene Mikrobiologie were observed.
V (b) The comparison preparation corresponded to I preparation B, contained, however, 0.5 percent of active ingredient. The pH-value of the solution was 5.
2nd day A 1 1 2 2 l B l 1 2 l l C 1 1 l 1 l 3X2=6 3X2=6 5 2=l0 4X2=8 31X2=6 7.2
3rd day A l 1 l 1 1 B 0 0 l l 0 C 0 l l 0 0 2Xl=2 2X2= 3X2=6 2X2fl 2Xl=2 3.6
4th day A 0 1 1 1 0 B 0 0 l 0 0 B 0 O 0 0 0 O 2X1=2 2X2=4 1 2=2 0 1.6
7th day A O O 0 0 0 B 0 0 0 0 0 C 0 O 0 0 0 0 V (c) The inventive preparation corresponded to the preparation D, contained however 0.5 percent of active ingredient. The pH value of the solution was 5.
2nd day A l 1 l l 1 B l 1 O l 1 C O 1 1 0 O 2X2=4 3X2=6 2XZ=4 2 2=4 2X2=4 3rd day A 0 l 0 l 0 B 0 O 0 O 0 C 0 0 0 O 0 4th day A 0 0 0 0 0 B O 0 0 0 O C 0 0 0 0 0 0 V (d) The comparison preparation corresponded to preparation E, contained however 0.5 percent of active ingredient. The pH-value of the solution amounted to rabbit no. 1 2 3 4 5 average value 1st day A 3 2 2 3 2 B 2 2 2 2 2 C 2 l 2 2 l 7X2=14 5X2=l0 6X2=12 7X2=14 5X2=l0 2nd day A 2 2 2 2 i B 2 l 1 l l C 1 1 1 1 l 5X2=l0 4X2=8 4 2=8 4X2=83X2=6 8 3rd day A 1 1 1 1 l B 1 1 O 1 0 C l 0 1 0 0 3X2=6 2X2=4 2X2=4 2X2=41 2=2 4 4th day A l l l l 0 B 1 O O 0 O C 0 0 0 0 0 2X2=4 1 2= 1X2=2 1X2=2 O 2 7th day A 0 0 0 0 0 B 0 0 0 0 0 C 0 O 0 0 O O The average value whose numerical value is a measure for the irritation effect is significantly lower in the inventive preparations A and D than in the comparison preparations B and E. It follows that the inventive preparations cause considerably less irritation effect than the control preparations.
What is claimed is:
1. A synergistic biocidal mixture consisting essentially of a. a compound of the formula wherein R is alkyl with eight to 18 carbon atoms, R is hydrogen, Cl-l or CH Cl-l Ol-l, and R is hydrogen, CH CH OH, (CH CH NR (CH CH NR ),,,R (CH CH CH NR ),,.R m having a value of l or 2, CH COOI-l,
| l CH CHCOOH, CHgCHCHzCOOH,
wherein R is alkyl of eight to 18 carbon atoms or the group wherein X is chlorine or bromine, the weight ratio a b being about between 5 l to l 3.
2. A mixture as claimed in claim 1, wherein the weight ratio of a b is between about 3 1 to l 2.
3. A biocidal preparation essentially consisting of a biocidally effective amount of the synergistic mixture of claim 1 and an inert carrier.
4. A preparation as claimed in claim 3, wherein said inert carrier is water, a lower alkanol, a lower alkyleneglycol, dioxane or glycoldimethylether.
5. A preparation as claimed in claim 3, wherein the concentration of the active ingredient is between about 0.001 and 0.5 percent.
Patent No. 3,717,579 Dated February 20, 1973 Inventor) Eberhard IIofmann and Ulrich Holtschmidt Itis certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In the heading of the patent insert:
-- [30] Foreign Application Priority Data I October 10, 1969 Germany........P 19 51 156.9-41-- Signed and sealed this 3rd day of July 1973.
' (SEAL) Attest:
EDWARD M.FLETCHER,JR. Rene T egtmeyer Attesting Officer I Acting Commissioner of Patents FORM PO-105O (10-69) USCOMM-DC 60376-P69 t u.s sovznumsm' PRINTING OFFICE: I989 0-366-314.
Claims (4)
1. A synergistic biocidal mixture consisting essentially of a. a compound of the formula wherein R1 is alkyl with eight to 18 carbon atoms, R2 is hydrogen, -CH3 or -CH2CH2OH, and R3 is hydrogen, -CH2CH2OH, -(CH2CH2NR2), -(CH2CH2NR2)mR2, -(CH2CH2CH2NR2)mR2, m having a value of 1 or 2, -CH2COOH, -CH2CH2NHCH2COOH, -CH2CH2NHCH2CH2NHCH2COOH or -CH2CH2CH2NHCH2COOH, and b. 2-alkylamino-6-aminopyridines of the formula: wherein R5 is alkyl of eight to 18 carbon atoms or the group wherein X is chlorine or bromine, the weight ratio a : b being about between 5 : 1 to 1 : 3.
2. A mixture as claimed in claim 1, wherein the weight ratio of a : b is between about 3 : 1 to 1 : 2.
3. A biocidal preparation essentially consisting of a biocidally effective amount of the synergistic mixture of claim 1 and an inert carrier.
4. A preparation as claimed in claim 3, wherein said inert carrier is water, a lower alkanol, a lower alkyleneglycol, dioxane or glycoldimethylether.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7824670A | 1970-10-05 | 1970-10-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3717579A true US3717579A (en) | 1973-02-20 |
Family
ID=22142840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00078246A Expired - Lifetime US3717579A (en) | 1970-10-05 | 1970-10-05 | Biocidal preparation |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3717579A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976587A (en) * | 1975-02-12 | 1976-08-24 | Millmaster Onyx Corporation | Amino derivatives of tetrasubstituted benzene compounds |
| EP0333143A2 (en) * | 1988-03-18 | 1989-09-20 | Lonza Ag | Medicinal soaps |
| US4964892A (en) * | 1988-12-22 | 1990-10-23 | Rohm And Haas Company | Synergistic microbicidal combinations containing 2-N-octyl-3-isothiazolone and certain commercial biocides |
| US5041457A (en) * | 1989-03-10 | 1991-08-20 | Rohm And Haas Company | Synergistic microbicidal combinations containing 2-n-octyl-3-isothiazolone and certain commercial biocides |
| US5131939A (en) * | 1988-12-22 | 1992-07-21 | Rohm And Haas Company | Synergistic microbicidal combinations containing 2-n-octyl-3-isothiazolone and certain commercial biocides |
| WO1995000613A1 (en) * | 1993-06-28 | 1995-01-05 | Henkel-Ecolab Gmbh & Co. Ohg | Cleaning and disinfecting agent |
| FR2742993A1 (en) * | 1996-01-03 | 1997-07-04 | Brun Michel | Deodoriser for indoor use, for rapid destruction of bacteria |
| US20050004112A1 (en) * | 2003-04-25 | 2005-01-06 | Player Mark R. | C-fms kinase inhibitors |
| US20050113566A1 (en) * | 2003-04-25 | 2005-05-26 | Player Mark R. | Inhibitors of C-FMS kinase |
| US20050131022A1 (en) * | 2003-04-25 | 2005-06-16 | Player Mark R. | C-fms kinase inhibitors |
| US20050271781A1 (en) * | 2003-03-05 | 2005-12-08 | Burwell Steve R | Antimicrobial solutions and process related thereto |
| US20070082820A1 (en) * | 2002-12-02 | 2007-04-12 | Fred Busch | Composition and Method for Treating Plant Fungal Disease |
| US7790724B2 (en) | 2003-04-25 | 2010-09-07 | Janssen Pharmaceutica N.V. | c-fms kinase inhibitors |
| US20100298386A1 (en) * | 2007-10-03 | 2010-11-25 | Burwell Steven R | Compositions and methods for treating mastitis |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2080517A (en) * | 1931-11-05 | 1937-05-18 | Pyridium Corp | Medicinal preparations including aminopyridine salts and methods of preparing and utilizing the same |
| GB692022A (en) * | 1949-01-27 | 1953-05-27 | Goldschmidt Ag Th | Improved body cleansing agents |
| DE932012C (en) * | 1952-02-07 | 1955-08-22 | Yair Dr Sprinzak | Process for the preparation of secondary benzylarylamines and secondary heterocyclic benzylamines |
| US2963486A (en) * | 1958-04-23 | 1960-12-06 | Ciba Pharmacentical Products I | Certain bis-(alkylaminomethyl)-pyridines |
| GB963907A (en) * | 1959-11-12 | 1964-07-15 | Nicholas Milkos Molnar | Compositions including a phenolic component and a polyamine component |
| US3225041A (en) * | 1962-12-12 | 1965-12-21 | Dow Chemical Co | Process for producing 2,6-diamino pyridines |
| US3290040A (en) * | 1964-04-06 | 1966-12-06 | Robert M Kerr | Clamp |
-
1970
- 1970-10-05 US US00078246A patent/US3717579A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2080517A (en) * | 1931-11-05 | 1937-05-18 | Pyridium Corp | Medicinal preparations including aminopyridine salts and methods of preparing and utilizing the same |
| GB692022A (en) * | 1949-01-27 | 1953-05-27 | Goldschmidt Ag Th | Improved body cleansing agents |
| DE932012C (en) * | 1952-02-07 | 1955-08-22 | Yair Dr Sprinzak | Process for the preparation of secondary benzylarylamines and secondary heterocyclic benzylamines |
| US2963486A (en) * | 1958-04-23 | 1960-12-06 | Ciba Pharmacentical Products I | Certain bis-(alkylaminomethyl)-pyridines |
| GB963907A (en) * | 1959-11-12 | 1964-07-15 | Nicholas Milkos Molnar | Compositions including a phenolic component and a polyamine component |
| US3225041A (en) * | 1962-12-12 | 1965-12-21 | Dow Chemical Co | Process for producing 2,6-diamino pyridines |
| US3290040A (en) * | 1964-04-06 | 1966-12-06 | Robert M Kerr | Clamp |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976587A (en) * | 1975-02-12 | 1976-08-24 | Millmaster Onyx Corporation | Amino derivatives of tetrasubstituted benzene compounds |
| EP0333143A2 (en) * | 1988-03-18 | 1989-09-20 | Lonza Ag | Medicinal soaps |
| EP0333143A3 (en) * | 1988-03-18 | 1990-03-28 | Lonza Ag | Medicinal soaps |
| US4964892A (en) * | 1988-12-22 | 1990-10-23 | Rohm And Haas Company | Synergistic microbicidal combinations containing 2-N-octyl-3-isothiazolone and certain commercial biocides |
| US5131939A (en) * | 1988-12-22 | 1992-07-21 | Rohm And Haas Company | Synergistic microbicidal combinations containing 2-n-octyl-3-isothiazolone and certain commercial biocides |
| US5041457A (en) * | 1989-03-10 | 1991-08-20 | Rohm And Haas Company | Synergistic microbicidal combinations containing 2-n-octyl-3-isothiazolone and certain commercial biocides |
| WO1995000613A1 (en) * | 1993-06-28 | 1995-01-05 | Henkel-Ecolab Gmbh & Co. Ohg | Cleaning and disinfecting agent |
| FR2708278A1 (en) * | 1993-06-28 | 1995-02-03 | Paragerm Snc | Cleansing and disinfecting composition for hospital environment. |
| TR27796A (en) * | 1993-06-28 | 1995-08-29 | Henkel Ecolab Gmbh & Co Ohg | Cleaning and disinfection agents. |
| FR2742993A1 (en) * | 1996-01-03 | 1997-07-04 | Brun Michel | Deodoriser for indoor use, for rapid destruction of bacteria |
| US20070082820A1 (en) * | 2002-12-02 | 2007-04-12 | Fred Busch | Composition and Method for Treating Plant Fungal Disease |
| US20090192165A1 (en) * | 2003-03-05 | 2009-07-30 | Burwell Steve R | Antimicrobial solutions and process related thereto |
| US20050271781A1 (en) * | 2003-03-05 | 2005-12-08 | Burwell Steve R | Antimicrobial solutions and process related thereto |
| US20060110506A1 (en) * | 2003-03-05 | 2006-05-25 | Burwell Steve R | Antimicrobial solutions and process related thereto |
| US8075936B2 (en) | 2003-03-05 | 2011-12-13 | Byocoat Enterprises, Inc. | Antimicrobial solutions and process related thereto |
| US8080269B2 (en) | 2003-03-05 | 2011-12-20 | Byocoat Enterprises, Inc. | Antimicrobial solutions and process related thereto |
| US8586115B2 (en) | 2003-03-05 | 2013-11-19 | Byocoat Enterprises, Inc. | Antimicrobial solutions and process related thereto |
| US20050131022A1 (en) * | 2003-04-25 | 2005-06-16 | Player Mark R. | C-fms kinase inhibitors |
| US20050113566A1 (en) * | 2003-04-25 | 2005-05-26 | Player Mark R. | Inhibitors of C-FMS kinase |
| US7427683B2 (en) * | 2003-04-25 | 2008-09-23 | Ortho-Mcneil Pharmaceutical, Inc. | c-fms kinase inhibitors |
| US7429603B2 (en) * | 2003-04-25 | 2008-09-30 | 3-Dimensional Pharmaceuticals, Inc. | C-fms kinase inhibitors |
| US20050004112A1 (en) * | 2003-04-25 | 2005-01-06 | Player Mark R. | C-fms kinase inhibitors |
| US7790724B2 (en) | 2003-04-25 | 2010-09-07 | Janssen Pharmaceutica N.V. | c-fms kinase inhibitors |
| US20100298386A1 (en) * | 2007-10-03 | 2010-11-25 | Burwell Steven R | Compositions and methods for treating mastitis |
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