US3466162A - Process for control of algae growth using compositions containing diamines and/or derivatives thereof - Google Patents

Description

United States Patent 01 fice 3,466,162 Patented Sept. 9, 1969 3,466,162 PROCESS FOR CONTROL OF ALGAE GROWTH USING COMPOSITIONS CONTAINING DIA- MINES AND/ OR DERIVATIVES THEREOF Urs Gloor, Riehen, and Klaus Bohnen, Dielsdorf, Switzerland, assignors to Hotlmann-La Roche Inc., Nutley, N.J., a corporation of New Jersey No Drawing. Filed Feb. 7, 1967, Ser. No. 614,403 Claims priority, application Switzerland, Feb. 25, 1966, 2,789/ 66 Int. Cl. A01n 9/20 US. Cl. 71--67 10 Claims ABSTRACT OF THE DISCLOSURE Diamines, and acid addition salts thereof, or quaternary products produced therefrom; compositions containing same; and the use of such compounds and compositions for the control of algae.

BRIEF SUMMARY OF THE INVENTION The invention is concerned with compounds which have been found to be highly effective in controlling the growth of algae and with the use of such compounds. The compounds which are employed in the practice of the invention have the formula in which the symbol R represents an aliphatic hydrocarbon residue or a cycloaliphatic-aliphatic hydrocarbon residue containing from 10 to 15 carbon atoms; the symbol R represents hydrogen or a lower alkyl radical; the symbols R represents hydrogen or a lower alkyl radical; the symbol R represents an aliphatic hydrocarbon residue or a cycloaliphatic-aliphatic hydrocarbon residue containing from 10 to 15 carbon atoms; the symbol R represents a straight or branched chain alkylene residue having from 2 to carbon atoms; with the proviso that the residues represented by the symbols R and R taken with the alkylene residue represented by the symbol R provide a total of at least 27 carbon atoms.

Acid addition salts of the Formula I compounds, as well as quaternary products produced therefrom, are also suitable for use in the practice of this invention.

DETAILED DESCRIPTION The present invention provides a means for effectively controlling the growth of algae. The compounds which are used in the practice of the invention have been found to possess a high degree of activity against algae growth, and in use, their effectiveness is long-lasting.

In carrying out this invention, there is employed, as the algae growth controlling agent, at least one diamine having the formula 2 Rs 1 in which the symbol R represents an aliphatic hydrocarbon residue or a cycloaliphtic-aliphatic hydrocarbon residue containing from 10 to carbon atoms; the symbol R represents hydrogen or lower alkyl radical; the symbol R represents hydrogen or a lower alkyl radical; the symbol R represents an aliphatic hydrocarbon residue or a cycloaliphatic-aliphatic hydrocarbon residue containing from 10 to 15 carbon atoms; the symbol R represents a straight or branched chain alkylene residue having from 2 to 10 carbon atoms; with the proviso that the residues represented by the symbols R and R taken with the alkylene residue represented by the symbol R provide a total of at least 27 carbon atoms, or an acid addition salt of, or a quaternary product produced from, a Formula I compound. Where, in subsequent portions of this specification reference is made to the compounds of Formula I, such reference should be construed as including the diamine bases as well as acid addition salts and quaternary compounds produced therefrom.

Compounds of Formula I Whose properties are such as to make them particularly interesting in the practice of this invention are those in which the substituents represented by the symbol R, and R are the same and in which the substituents represented by the symbols R and R are the same.

Preferred classes of compounds which fall within the scope of Formula I are those in which the symbol R and R each represent a 1,5,9-dimethyl-decyl residue, or the corresponding residue unsaturated in the 2,3-, 4,5- and/or 8,9-position; or in which the symbols R and R each represent a 1-methyl-3-(2,6,G-trimethylcyclohexyl)- propyl radical; or in which the symbols R and R each represent a 1 methyl-3-[2,6,6-trimethylcyclohexen-(1)- yl]-propyl residue. Such compounds, preferably have, as

the R and R substituents, a hydrogen atom or an alkyl radical having from 1 to 3 carbon atoms, especially a methyl radical. Moreover, in the case of such compounds, where R represents a straight chain alkylene residue, such residue contains preferably from about 4 to 6 carbon atoms, especially, 6 carbon atom whereas, where R represents a branched chain residue such residue contains, preferably, from about 7 to 10 carbon atoms, especially 9 carbon atoms.

Thus, for example, the present invention embraces the use of diamines having the formula in which the symbol R and R represent a hydrogen atom or a methyl group; and R represents a polymethylene chain, which may be methyl-substituted, having from 2 to 10, and preferably from 6 to 9, carbon atoms, and wherein double bonds indicated by the broken line can be hydrogenated.

Acid addition salts of, and quaternary products derived from, the Formula 1(a) compounds are also suitable for use. Representative of a preferred class of compounds, embraced by Formula 1(a) are those in which the symbol R represents hexamethylene or a trimethyl hexamethylene group, such as, the 2,2-dimethyl-4-methylhexamethylene and the 2-methyl-4,4-dimethyl-hexamethylene radicals. Specific examples of certain Formula 1(a) compounds are as follows:

N,N'-bis( 1,5,9-trimethyldecyl) -1 ,Z-ethyIenediamine N,N-bis-( 1,5,9-trimethyldecyl) -N,N-dimethyl-1,2-

ethylenediamine N,N'-bis-( 1,5 9-trimethyldecyl) -N,N-dimethyl- 1,2-

ethylenediamine bis- (methobromide) N,N-bis-( 1,5,9-trimethyldecyl)-1,6hexanediamine N,N'-bis-(1,5,9-trimethyldecyl)-N,N-dimethyl-1,6-

hexanediamine N,N'-bis-( 1,5,9-trimethyldecyl N,N-dimethyl- 1 ,6-

hexanediamine bismethobromide) N,N-bis-[1,5,9-trimethyldecatrien-(2,4,8)-yl]-1,6-

hexanediamine N,N'-bis-[ 1,5,9-trimethyldecaen- (4) -yl] 1,6-hexanediamine N,N'-bis-( 1,5,9-trimethyldecyl 2,2-dimethyl-4-methyl- 1,6-hexanediamine 3 N,N'-bis-( 1,5,9-trimethyldecyl -2-methyl-4,4-dimethyl- 1,6-hexanediamine.

In one of the preferred embodiments of the invention, a mixture of N,N'-bis-(1,5,9-trimethyldecyl) 2,2-dimethyl-4-methyl-1,6-hexanediamine and N,N' bis-(1,5,9-trimethyldecyl) Z-methyl 4,4-dimethyl 1,6-hexanediamine is used.

Additionally, there can be used in the practice of this invention diamines having the formula in which the symbols R R and R have the same meaning as in Formula I(a).

Acid addition salts of, and quaternary products derived from, the Formula I(b) compounds are also suitable for use in the practice of this invention. As specific examples of compounds encompassed by Formula I(b), the following can be mentioned:

N,N'-bis-{1-methyl-3-[2,6,6-trimethylcyclohexen-( l yl]-propyl}-N,N'-dimethyl-1,5-pentanediamine bis-methobromide N,N-bis(1-methyl-3-[2,6,6-trimethylcyclohexyl]-propyl)-N,N-dimethyl-1,4-butanediamine bis-(methobromide) N,N'-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]- propyl)-N,N'-dimethyl-1,4-butanediamine dihydrochloride N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexen-( l yl]-propyl)-N,N-dimethyl-1,6-hexanediamine bis- (methobromide) N,N'-bis-( l-methyl-3- 2,6,6-trimethylcyclohexyl] -prpyl)-N,N-dimethyl-1,5-pentanediamine bis- (methobromide) N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]- pro pyl) -N,N-dimethyl- 1,6-hexanediamine bis- (methobromide) N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]- propyl)-N,N'-dimethyl-1,Z-ethanediamine bis-(methobromide) N,N-bis-( 1-methyl-3- [2,6,6-trimethylcyclohexyl propyl) -1,2-ethanediamine N,N'-bis-(1-methyl-3 2,6,6-trimethylcyclohexyl] propyl)-N,N'-dimethyl-1,2-ethanediamine N,N-bis-( 1-methyl-3- [2,6,6-trimethylcyclohexyl propyl) -1,6-hexanediamine N,N-bis-( 1-methyl-3- [2,6,6-trimethylcyclohexyl propyl -N,N'-dimethyll ,6-hexanediamine N,N-bis-( 1-methyl-3- [2,6,6-trimethylcyclohexyl] propyl) -2,2-dimethyl-4-methyl-1,6-hexanediamine N,N-bis-( 1-methyl-3 [2,6,G-trimethylcyclohexyl propyl)-2-methy1-4,4-dimethyl-1,6- hexanediamine.

In one of its preferred embodiments, the invention involves the use of a mixture of N,N'-bis-(l-methyl-3- [2,6,6-trimethylcyclohexyl] propyl) 2, dimethyl-4- methyl-1,6-hexanediamine and N,N'-bis (l-methyl)-3 [2,6,6-trimethylcyclohexyl] propyl) 2-methyl 4,4-dimethyl-1,6-hexanediamine.

As indicated heretofore, the present invention contemplates the use of diamine bases of Formulas I, 1(a) and I(b) as well as acid addition salts thereof and quaternary products derived therefrom. Suitable for use are salts of the compounds of Formulas I, 1(a) and I(b) with organic acids, such as, acetic acid; benzoic acid; citric acid; malic acid; maleic acid; salicylic acid; tartaric acid; etc. or with mineral acids, such as, the hydrohalic acids, for example, hydrochloric acid; nitric acid; phosphoric acid; sulfuric acid; etc. Additionally, salts of the compounds with methane sulfonic acid can be used. Furthermore, and as previously indicated, quaternary compounds produced from the compounds of Formulas I, 1(a) and I(b) can be employed. These quaternary compounds are produced, for example, by treating the base with an alkyl halide, such as, methyl bromide, or with an alkyl sulfonate, such as, dimethyl sulfate.

As previously stated, the compounds of Formulas I, and, in certain preferred embodiments of the invention, the compounds of Formulas 1(a) and I(b), are used to prevent or at least retard the growth of algae. At high concentrations, for example, at a level of from about 0.1 to about 10 parts per million parts of the medium to be treated, the compounds described herein act to inhibit algae growth. At lower concentrations, the compounds will retard the growth of algae. The quantity of active ingredient which, in any given case, is added to the medium to be treated will determine, to a great extent, the frequency with which the treatment is repeated. It has been found that inhibition of algae growth, which extends, without further treatment, over a period of several weeks, is achieved when the medium is treated with from about 1 to about 6 parts per million, preferably, from about 2 to about 5 parts per million, of the active ingredient. Where a lower concentration of active ingredient is used, it is advisable to repeat the treatment at regular intervals to compensate for the gradual inactivation of the active ingredient.

Compounds embraced by Formulas I, 1(a) and I(b) are known. Processes for their production are described, for example, in the Journal of Medicinal Chemistry 6, 780 (1963) and US. Patents 3,064,039 and 3,064,052. In general, however, the compounds are produced by the reductive condensation of a diamine having the formula H N-R NH in which the symbol R has the same meaning as in Formula I, with a suitable carbonyl compound.

The manner in which the compounds of Formulas I, 1(a) and I( b) are used in the practice of this invention to prevent and/or inhibit the growth of algae will be readily apparent to persons skilled in the art. For example, the compounds can be formulated as solutions or emulsions and used as such. Alternatively, the compounds can be formulated as emulsifiable concentrates, such concentrates being converted into emulsions prior to use. Additionally, however, the bases of Formulas I, 1(a) and I(b), after having been converted into water-soluble acid addition salts, for example, into an acetate salt, a hydrochloride salt or a sulfate salt, can be incorporated into a permeable vessel, for example, a cloth bag. Such bag can be aflixed to a water hose in such a manner that the water leaving the hose flows through the bag into the tank or pool which is to be protected against algae growth. By proceeding in this manner, the water-soluble salts become dissolved in the water and are distributed throughout the tank or pool by the flow of the water therein. Where it is desired to prevent or inhibit the growth of algae in a swimming pool which is equipped with a rotary filter installation, the compound of Formulas I, I(a) or I(b), or a mixture thereof, in the form of a water-soluble salt, can be introduced onto the filter layer. As the water flows through the filter, the active ingredient becomes dissolved therein.

Where it is desired to provide the compounds of Formulas I, 1(a) and I(b) in the form of emulsifiable concentrates, such concentrates can be produced, for example, by reacting the Formulas I, I(a) or I(b) base with a quantity of acid, for example, acetic acid, slightly in excess of that theoretically required for salt formation and adding such salt to water. In the alternative, an emulsifiable concentrate can be obtained by treating the Formulas I, I(a) or I(b) compounds with a quantity of a suitable emulsifier which is sufficient to emulsify the compound when mixed with water.

For a fuller understanding of the nature and objects of this invention, reference may be had to the following examples which are given merely as further illustrations of the invention and are not to be construed in a limiting sense.

Example 1 In this example, 500 ml. of concentrated (95100%) acetic acid was added to, and stirred in, 9.5 liters of Water. Thereafter, 2.5 kg. of N,N'-bis-(1-methyl-3-[2,6,6 trimethylcyclohexyl] -propyl 1 ,6-hexanediamine was added to the aqueous acetic acid solution. The product, thus obtained, was in the form of a clear concentrate capable of being diluted further with water.

1.0 liter of the concentrate, produced as described in the preceding paragraph, was introduced, with stirring, into a sprinkling can of liters capacity, following which it was diluted to about 10 liters with water. This solution was added to a tank containing about 50 cubic meters of water. Dissolution of the concentrate in the water was facilitated by stirring.

It was found that this treatment effectively inhibited the growth of algae in the tank for a considerable length of time.

Example 2 A concentrate was produced, in the manner described in Example 1 using, with but one exception, the same ingredients and the same quantities thereof as were used in Example 1. In this example, the 2.5 kg. of N,N'-bis- (1-rnethyl-3-[2,6,6 trimethylcyclohexyl] propyl) 1,6- hexanediamine used in Example 1 was replaced with 2.5 kg. of a mixture comprising equal amounts of N,N'-bis- (1,5,9 trimethyldecyl) 2,2 dimethyl 4-methyl-1,6- hexanediamine and N,N-bis-(1,5,9 trimethyldecyl) 2- methyl-4,4-dimethyl-1,6-hexanediamine.

It was found that when 1.0 liter of the concentrate was diluted to 10 liters with water and added to a tank containing about 50 cubic meters of water, the growth of algae therein was inhibited for a significant period of time.

Example 3 A concentrate was produced, in the manner described in Example 1, using, with but one exception, the same ingredients and the same quantities thereof as were employed in Example 1. In producing the concentrate of this example, however, there was used 2.5 kg. of a mixture of equal quantities of N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl] -propyl) 2,2-dimethyl-4-methyl-1,6-hexanediamine and N,N'-bis-(1 methyl-3-[2,6,6-trimethylcyclohexYlJ-propyl) -2-methyl-4,4-methyl-1,6-hexanediamine in place of the 2.5 kg. of N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexylJ-propyl) 1,6-hexanediamine employed in Example 1.

It was found that when 1 liter of such concentrate was diluted with about 10 liters of water and added to a tank containing about 50 cubic meters of water, the growth of algae therein was effectively inhibited for a considerable length of time.

Example 4 In this example, 250 grams of N,N'-bis-(1-methyl-3- [2,6,6 trimethylcyclohexyl]-propyl)-1,6-hexanediamine dihydrochloride was incorporated into a tightly woven cotton sack. This sack was affixed to the water inlet orifice of a tank. The tap was opened and water was allowed to flow in a rapid stream through the cloth sack into the tank. The active ingredient was thus carried into the tank, dissolved in the tank water. The tank was then filled to a capacity of 50 cubic meters of water.

It was found that the growth of algae in the tank was effectively inhibited for a considerable period of time by the treatment described herein.

Example 5 In this example, 250 grams of N,N-bis-( 1,5 ,9-trimethyldecyl) 1,6 hexanediamine dihydrochloride were introduced into a swimming pool, equipped with a rotary pump and filter installation, having the dimensions of 4 meters x 7 meters. The pool was filled with water to the depth of 1.8 meters. The active ingredient was incorporated into. the system by adding it to the circulating water prior to the passage of the water through the filter. The active ingredient became dissolved in the water.

It was observed that the growth of algae was effectively inhibited by incorporating the active ingredient in the system in this manner.

Example 6 In this example, there was used a glass aquarium containing about 10 liters of water. The water in this aquarium, kept in constant motion by the continuous passage of air, was maintained at a temperature within the range of about 20 to about 25 C. This aquarium was lit with a mercury vapor lamp. There was added thereto N,N-bis- (1 methyl 3-[2,6,6-trimethylcyclohexyl]-propyl)-1,6- hexanediamine at a level of 2 parts per million parts of water.

A second aquarium was set up, identical to that described in the preceding paragraph, containing the same active ingredient but at a level of 2.5 parts per million rather than the 2.0 parts per million mentioned heretofore. Furthermore, nine additional glass aquaria were set up to evaluate eight other compounds, identified in the table which follows, at the concentration indicated therein.

On the next day, the eleven aquaria, together with four aquaria of the same kind which did not contain an inhibi-tor against algae growth, were each innoculated with the same quantity of an algae suspension. After a period of about 21 days, the extent of algae growth in each aquarium was ascertained, measured in terms of the of water turbidity. The results obtained in these experiments, together with an identification of the active ingredient and the concentration thereof present, are set forth in the table which follows:

Algal growth Concentration in percent of of compound the water Compound in ppm. turbidity Control (without protectant) 0 60 Do 0 70 Do 0 70 Do 0 60 (1) N,N-bis-(1-methyl-3-[2,6,6-trimethylcyclohexyl]-propyl)-1,6-hexanediamine. 2. 0 0-1 2. 5 0 (2) N,N-bis-(1,5,9trimethy1decyD- 2. 0 02 1,6-hexanediamine. 2. 5 0 (3) N,N-bis-(1,5,9-trimethyldeeyD- 1,2-ethy1enediamine 2. 0 0-20 (4) N,N-bis-(1,5,9-trirnethyldecyl)- N,N-dimethyl-1.2-ethylendiamine. 2. 5 0-20 (5) N,N-bis-(1,5,9-trimethyldecyl)- N,N-dimethy1-l,6-hexanediamine- 2 0 020 (6) N,Nbis-(l-methyl-3-[2.6.6-trimethylcyclohexyl]-propy1)-N,N- dirnethyl-l,4-butane-diamine bis- (methoehloride) 2. 5 020 (7) N ,N-bis- {1-methy1-3-[2,6,6-trirnethylcyclohexen-(1)-yl]-propyl}- N,N-dimethy1-1,6-hexauediamine bis-(methobromide) 2. 5 0-10 (8) N,N'biS-(1-methyl-3[2,6,6-trimethylcyclohexyl1-propyl)-1,2- ethanediamine 2. 5 0-10 (9) N,N-bis(1-methyl-3-[2,6,6-trimethylcyclohexyH-propyl)-N.N- dimethyl-Lfi-hexanediamine 2. 0 [H0 The foregoing results demonstrate that the compounds tested are highly effective in controlling the growth of algae.

We claim:

1. Process for the control of algae growth in an aqueous system which comprises adding to said aqueous system an effective amount of at least one compound selected from the group consisting of (1) N,N'-bis-(1,5,9-trimethyldecyl) 1,6 hexanediamine, N,N-bis-(1,5,9-trimethyldecyl) 1,2 ethylenediamine, N,N'-bis-(1,5,9-trimethyldecyl)-N,N'-dimethyl 1,2 ethylenediamine, N,N-bis- (1,5,9 trimethyldecyl) N,N dimethyl-1,6-hexanediamine, N,N' bis (1 methyl 3-[2,6,6-trimethylcyclm hexyl] propyl) 1,6 hexanediamine, N,N'-bis-(1-methyl 3 [2,6,6-trimethy1cyclohexyl]-propyl)-N,N-dimeth yl 1,4 butanediamine bis-(methochloride), N,N'-bis-{1 methyl 3 [2,6,6 trimethylcyclohexen-(1)-yl]-propyl}- N,N dimethyl 1,6-hexanediamine bis-(methobromide), N,N' bis (1 methyl 3 [2,6,6-trimethylcyclohexy1]- propyl) 1,2 ethanediamine and N,N'-bis-(1-methyl-3- [2,6,6 trimethylcyclohexyl] propyl) N,N-dimethyl- 1,6-hexanediamine; (2) acid addition salts thereof; and (3) a quaternary derived therefrom.

2. The process of claim 1 wherein N,N'-bis-(1,5,9-trimethyldecyl)-1,6-hexanediamine is used as the algae controlling compound.

3. The process of claim 1 wherein N,N'bis-(1,5,9-trimethyldecyl)-1,2-ethylenediami11e is used as the algae controlling compound.

4. The process of claim 1 wherein N,N'-bis-(l,5,9-trimethyldecyl) N,N'-dimethyl-1,6-hexanediamine is used used as the algae controlling compound.

5. The process of claim 1 wherein N,N-bis-(1,5,9-trimethyldecyl) N,N'-dimethyl-1,6-hexanedimaine is used as the algae controlling compound.

6. The process of claim 1 wherein N,N-bis-(1-methyl- 3 [2,6,6 trimethylcyclohexyl] propyl)-1,6-hexanediamine is used as the algae controlling compound.

7. The process of claim 1 wherein N,N-bis-(l-methyl- 3 [2,6,6 trimethylcyclohexyl]-propyl)-N,N-dimethyl- 1,4 butanediamine bis-(methochloride) is used as the algae controlling compound.

8. The process of claim 1 wherein N,N'-bis{1-methyl-3- [2,6,6 trimethylcyclohexen (1) y1]-propy1}-N,N-dimethyl-1,6-hexanediamine bis-(methobromide) is used as the algae controlling compound.

9. The process of claim 1 wherein N,N-bis-(1-methy1- 3 [2,6,6-trimethylcyclohexyl]-pro1py1) -1,2-ethanediamine is used as the algae controlling compound.

10. The process of claim 1 wherein N,N-bis-(1-methyl- 3- [2,6,6-trimethylcyclohexyl] -propyl) -N,N-dimethyl-1,6- hexanediamine is used as the algae controlling compound.

References Cited UNITED STATES PATENTS 3,064,039 11/1962 Goldberg 260-501 3,064,052 11/ 1962 Goldberg 260563 ALBERT T. MEYERS, Primary Examiner D. M. STEPHENS, Assistant Examiner U.S. Cl. X.R. 424325