GB1584429A

GB1584429A - Aquatic herbicides and algicides

Info

Publication number: GB1584429A
Application number: GB3553077A
Authority: GB
Original assignee: Eli Lilly and Co
Current assignee: Eli Lilly and Co
Priority date: 1976-08-31
Filing date: 1977-08-24
Publication date: 1981-02-11
Also published as: BR7705402A; FR2363284A1; DE2738902A1; NL7709421A; JPS5329931A; IT1083904B

Description

(54) AQUATIC HERBICIDES AND ALGICIDES (71) We, ELI LILLY AND COMPANY, a corporation of the State of Indiana, United States of America, having a principal place of business at 307 East McCarty Street, City of Indianapolis, State of Indiana, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention provides a method and compositions for controlling aquatic weeds and algae which comprises the use of a substituted phenoxy(phenylthio)alkylamine in sufficient quantity to kill the weeds.

In the prior art, Lacefield et al., J. Med. Chem. 14, 133 (1971) teach certain biphenylyloxyalkylamines as useful for inhibiting ADP-induced platlet aggregation in vitro. Some of the compounds disclosed in this reference are used in the practice of the present invention.

Another prior art reference is Wright et al., U.S. Patent No. 2,935,439 (May 3, 1960), which teaches the preparation and fungicidal properties of a number of halogen substituted aminoalkanol aryl ethers which are similar to those disclosed herein.

Also in the prior art, Richter et aL, U.S. Patent No. 3,808,257, disclose and claim a series of N - cyanoalkyl - N - cycloalkyl - N - phenoxyalkylamines, alleged to be active as aquatic herbicides.

Still another prior art reference is Richter et al., U.S. Patent No. 3,677,735, wherein is taught and claimed a method of controlling aquatic plant life using substituted phenoxyalkylamines.

This invention provides a novel method and compositions for reducing the vigor of aquatic weeds or algae comprising the use of a compound of the formula

wherein A is hydrogen, bromo, or chloro; B is cyclohexyl, benzyl, or phenyl; X is oxygen or sulfur; m is 0 or 1; when m=0, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=0; R', when taken alone, is hydrogen, C1-C5 alkyl, or -CH2CH2OH; R2, when taken alone, is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -CH2CH2OH, -(C112)3OCH3, I-adamantyl, bentyl, or phenyl; R' and R2, when taken together with the nitrogen atom to which they are attached, form morpholino, 2-methyl-piperidino, 4-(2-hydroxyethyl)piperazino, or pyrrolidino; or the acid addition salts thereof, the composition being in the form of granules, wettable powders or an emulsifiable concentrate.

One embodiment of this invention relates to the use as an aquatic herbicide or algicide of a compound of the formula

wherein A is hydrogen, bromo, or chloro; B is phenyl; X is oxygen or sulfur; m is O or l; when m=O, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=O; R' is hydrogen, C,C5 alkyl, or --CH,CH,OH: R2 is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -CH2CH2OH, or -(CH2)3OCH3; or the acid addition salts thereof.

Another embodiment of this invention relates to the use as an aquatic herbicide or algicide of a compound of the formula

wherein A is hydrogen or chloro; B is phenyl; m is O or 1; when m=O, n+p is 3; and when m=l, n=2 and p=O; R' and R2, taken together with the nitrogen atom to which they are attached, form morpholino, 2-methylpiperidino, 4-(2-hydroxyethyl)piperazino, or pyrrolidino; or the acid addition salts thereof.

Yet another embodiment of this invention relates to the use as an aquatic herbicide or algicide of a compound of the formula

wherein A is hydrogen; B is phenyl; X is oxygen or sulfur; m is O or 1; when m=O, n+p is 3 or 4; and when m=l, n=2, and p=e; RX and R2 are both methyl; or the acid addition salts thereof.

Still another embodiment of this invention relates to the use as an aquatic herbicide or algicide of a compound of the formula

wherein A is hydrogen or chloro; B is phenyl; X is oxygen or sulfur; n+p is 3, 4, or 5; R2 is l-adamantyl; or the acid addition salts thereof.

And another embodiment of this invention relates to the use as an aquatic herbicide or algicide of a compound of the formula

wherein R2 is phenyl or benzyl; or the acid addition salts thereof.

Compounds preferred for use in the compositions and method of this invention are of the formula

wherein m is O or I; when m=O, n+p is 2 to 6; and when m=l, n=p=l, or n=2, and p=O; R1 is hydrogen, C1-C5 alkyl, or -CH3CH2OH; R2 is hydrogen, C1-C5 alkyl, C3 alkenyl, -CH2CH2OH, HCH2)30CH3, or cyclohexyl; or the acid addition salts thereof.

Compounds of choice for use in the compositions and method of this invention are of the formula

wherein m isO or 1; when m=O, n+p is 2, 3, or 4; when m=l, n=2, and p=O; R2 iS C2-C4 alkyl, cyclohexyl, or -(CH2)3OCH3; or the acid addition salts thereof.

In the above formulae, C1-C5 alkyl represents a saturated straight- or branched-chain hydrocarbon radical such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, and neopentyl.

C3 Alkenyl represents allyl or prop-l-enyl.

The acid addition salts are prepared from an acid having sufficient acidity to react with the amino moiety of the compound in question. Such acids include, for example, hydrochloric, hydrobromic, nitric, sulfuric, oxalic, methanesulfonic and p-toluenesulfonic. The preparations are carried out following standard preparative methods well known to those skilled in the art.

The compounds useful in the instant novel method and compositions can be prepared by general procedures well known to the art. One procedure involves the reaction of an aminoalkyl halide with the alkali metal salt of an appropriately substituted phenol in a suitable solvent.

Another procedure involves the reaction of a substituted phenoxyalkyl or phenylthioalkyl halide with an appropriate amine at an elevated temperature. The reaction may be carried out by heating the reactants together in a suitable solvent, for example ethanol, followed by isolation of the desired product via distillation or through formation of an acid addition salt.

The preparation may also be carried out by heating the substituted phenoxyalkyl or phenylthioalkyl halide with an excess of the appropriate amine in a sealed stainless steel reaction vessel. The product is isolated from the reaction product mixture as the free base or as the acid addition salt of the substituted phenoxy(phenylthio)alkylamine.

As will be recognized by those skilled in the art, the intermediate substituted phenols, aminoalkyl halides, and amines necessary for the synthesis of the final products are commerically available or are synthesized by the general methods taught in the literature and familiar to those skilled in the art.

The aminoalkyl halides are readily prepared by allowing an aminoalkanol to react with a halogenating agent, such as thionyl chloride or phosphorus oxybromide in a suitable solvent, and isolating the desired aminoalkyl halide as the hydrohalide salt, as described by Lacefield et al., supra. For example, 3dimethylaminobutanol is dissolved in chloroform, the solution is cooled, saturated with hydrogen chloride, and a solution of thionyl chloride in chloroform is added thereto with stirring and continued cooling. The reaction mixture is allowed to warm to room temperature and to stir overnight, and then refluxed for about two hours. The reaction product mixture is evaporated to dryness and flushed several times with ethanol. The residue is recrystallized from ethanol-ether to yield 3 chloro - N,N,1 - trimethylpropylamine hydrochloride, m.p. 144--1460C.

Another class of intermediates needed are the eo-haloalkoxy substituted phenyl compounds, prepared according to the procedure of Lacefield et al., supra.

Thus, a solution of 5-chloro-2-hydroxybiphenyl, potassium hydroxide, and 1,10dibromodecane in methanol is allowed to reflux overnight. The reaction product mixture is cooled and filtered, and the filtrate concentrated in vacuo to remove solvent. The crude liquid material remaining is dissolved in ether and washed successively with dilute aqueous sodium hydroxide and water until the washings are neutral. The organic layer is dried over a suitable drying agent, filtered, and distilled in vacuo to yield product having a boiling point of about 230235 C./0.1 mm., and identified as 2-( I 0-bromodecyloxy)-5-chlorobiphenyl.

Aminoalkanol compounds used as intermediates are also readily prepared according to well-known literature procedures. Thus, for example, 2methylaminoethanol is synthesized by heating in a sealed pressure reaction vessel a mixture of methylamine and ethylene oxide, in methanol at about 140"C. for about 12 hours. The product is isolated by distilling the reaction product mixture.

Compounds useful in the instant novel compositions and method are prepared by syntheses typified by the fqllowing preparations.

Preparation I I -[3-(5-Chloro-2-biphenylyloxy)propyl]-2-methylpiperidine Hydrochloride A mixture of 20.4 g. (0.10 mole) of 5-chloro-2-hydroxybiphenyl and sodium ethoxide (from 2.3 g. sodium in 150 ml. of absolute ethanol) was prepared, and there was added thereto 21 g. (0.12 mole) of l-(3-chloropropyl)-2-methylpiperidine.

The reaction mixture was refluxed overnight, allowed to cool, and was filtered to remove the precipitated sodium chloride. The filtrate was concentrated in vacuo to leave a residue. The residue was taken up in ether and the ether solution was extracted several times with aqueous 10 percent hydrochloric acid. The combined aqueous acid extracts were cooled, made basic with aqueous sodium hydroxide solution, and the basic mixture extracted with ether. The combined ether extracts were dried over anhydrous sodium sulfate. The drying agent was filtered off and the dry ether filtrate cooled in an ice bath and saturated with an anhydrous hydrogen chloride. The precipitate which formed was filtered off and recrystallized from a mixture of ethanol and ether. There was obtained product having a melting point of about 170--1710C., which product was identified by pKa and elemental analyses as 1 - [3 - (5 - chloro - 2 - biphenylyloxy)propyl] - 2 - methylpiperidine hydrochloride.

Analyses calculated for C2,H26CINO . HCI: Theoretical Found C 66.30 /" 66.01 /" H 7.16 X 7.33% Preparation 2 3-(5-Chloro-2-biphenylyloxy)-N,N,2-trimethyl- Propylamine Hydrobromide In an autoclave equipped with a glass liner, a mixture was prepared of 30 g.

(0.1 mole) of 2 - (3 - chloro - 2 - methylpropoxy) - 5 - chlorobiphenyl, 100 g. (2.2 moles) of anhydrous dimethylamine, and 75 ml. of commerical absolute ethanol.

The autoclave was then sealed and heated to a temperature of about 120"C. for about 8 hours. The autocalve was cooled andopened, and the reaction product mixture removed. The mixture was distilled to remove solvent and excess dimethylamine, and the residue which remained was dissolved in about 500 ml. of dilute aqueous hydrochloric acid. The acidic aqueous solution was washed with ether, made alkaline with aqueous 50 percent sodium hydroxide solution and extracted with ether. The ether extracts were combined and washed with several portions of water. The ether extracts were dried over anhydrous sodium sulfate, the drying agent filtered off, and the solvent removed in vacuo, leaving a residue. The residue was distilled at reduced pressure to yield material having a boiling point of about 155--165"C./0.05 mm. This material was used to prepare the hydrobromide acid addition salt, which salt had a melting point of about 106--109"C. It was identified by elemental analyses as 3 - (5 - chloro - 2 - biphenylyloxy) - N,N,2 trimethylpropylamine hydrobromide.

Analyses calculated for ClBH22ClNO. HBr: Theoretical Found C 56.18% 57.29% H 5.98% 6.27% Preparation 3 N-Adamantyl-5-(5-chloro-2-biphenylyloxy)pentylamine Hydrochloride A mixture of 5 g. of 2 - (5 - bromopentyloxy) - 5 - chlorobiphenyl and 5 g. of l-aminoadamantane was heated at about 135"C. in an oil bath overnight. The reaction mixture was taken up in ether and aqueous 20 percent sodium hydroxide.

The mixture was extracted with ether and the combined ether extracts were then extracted with aqueous 10 percent hydrochloric acid. Crystals separated from the aqueous hydrochloric acid solution, which crystals were filtered off and recrystallized from ethanol. There was obtained 2.5 g. of a colorless solid having a melting point of about 235--236"C. The solid was identified by elemental analyses and NMR spectrum as N - adamantyl - 5 - (5 - chloro - 2 biphenylyloxy)pentylamine hydrochloride.

Analyses calculated for C27H34CINO . HCI: Theoretical Found C 70.42% 70.38% H 7.66% 7.73% Cl 15.40% 15.17% Methods typified by the above description and preparations are used to synthesize all of the compounds used in this invention. Numerous compounds are exemplified below in the section reporting experimental results of tests against aquatic weeds.

The novel method of this invention is practiced by adding the chemicals to the water containing the aquatic weeds or algae. The compounds used in this invention kill or inhibit the growth of aquatic weeds or algae when an herbicidally-effective or algicidally-effective amount of one of the compounds is brought into contact with the weeds or algae. Some aquatic weeds float in or on top of water; others are rooted in the underwater soil. Depending on the type of weed of primary concern in a particular body of water, it may be desirable to supply the compound in a form which sinks or floats.

The method is preferably practiced by adding to the water a sufficient amount of the chemical that a concentration of from 0.5 to 10 parts per million by weight (0.00005% to 0.001%) is obtained, most preferably sufficient chemical to provide a concentration of from 0.5 to 2 parts per million (0.00005% to 0.0002%).

The optimum concentration for any specific control problem varies with the temperature, the species to be controlled, and the shape of the water body to be treated. At higher water temperatures, less chemical is generally required for a given degree of control than is needed at lower temperatures.

In considering the treatment of moving streams for the purpose of destroying flora fixed therein, special account must be taken of the fact that the chemicals will pass over the area to be treated and that the concentration during the contact period is dependent upon the water flow rate, the rate of chemical addition, and the period of addition.

The compounds are added to the water in the form of the novel herbicidal and algicidal compositions of this invention. These compositions are novel because of the presence of the compounds of this invention, which have not previously been known to be useful as pesticides. The inert ingredients of the compositions are similar to other agricultural chemical formulations.

Compositions of this invention contain from 0.1 to 90% of the compound, and are in the forms of granules, wettable powders, emulsifiable concentrates and solutions. Granules are applied by scattering them over the surface of the water.

They may be formulated to sink or float by adjusting the density. In general, granules contain from 0.1% to 10% of the compound, dispersed in or adsorbed on particles of dried earth, stone or sand. Such earths as diatomaceous earth, kaolin, bentonite, montmorillonite, and attapulgite are useful for preparing granules of this invention, and comprise from 90% to 99.9% of the composition.

Wettable powders, emulsifiable concentrates and solutions are particularly useful when the composition containing the compound is desired to float, but may be prepared at a high density so that they sink the compound to the bottom of the water. Usually they are applied by dispersing the composition in a relatively small amount of water and spraying the dispersion over the surface of the water. The concentration of the compound in the preliminary dispersion is not important.

Wettable powders comprise an intimate mixture of the active compound in an inert carrier which is a mixture of a fine inert powder and surfactants. The concentration of the active compound is usually from about 10 percent to about 90 percent by weight. The inert powder is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates.

Effective surfactants, comprising from about 0.5 percent to about 10 percent of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates, and nonionic surfactants such as ethylene oxides adducts of alkyl phenol.

Typical emulsifiable concentrates of the compounds comprise a convenient concentration of the compound, such as from about 50 to about 500 g. per liter of liquid, equivalent to from about 5 percent to about 50 percent, dissolved in an inert carrier which is a mixture of water-immiscible organic solvent and emulsifiers.

Useful organic solvents include the aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from the same types and concentrations of surfactants used for wettable powders.

Solutions of the compounds are essentially similar to emulsifiable concentrates except that no surfactants are used. Solutions can also be prepared in water or aqueous alcohols, in many cases, since many of the compounds are salts with considerable water solubility.

The following formulae illustrate typical exemplary compositions.

Granules Example I Granulated limestone 95% Compound I below 4% Cellulose gum 1% Example 2 Granulated kaolin 90% Compound 2 below 10% Example 3 Silica sand 98% Compound 13 below Polybutenes 1% Example 4 Granulated diatomaceous earth 93% Compound 7 below 7% Wettable Powders Example 5 Compound 3 below 60% Attapulgite 35% Surfactant 5% Example 6 Compound 17 below 80% Kaolin 16% Surfactant 4% Example 7 Compound 24 below 50% Diatomaceous earth 40% Surfactant 10% Example 8 Compound 28 below 90% Purified silicates 6% Surfactant 4% Emulsifiable Concentrates Example 9 Compound 22 below 40% Aromatic naphtha 45% Surfactant 5% Example 10 Compound 15 below 25% Xylene 70% Surfactant 5% Example 11 Compound 48 below 45% Aromatic naphtha 20% 2-Methoxyethanol 30% Surfactant 5% Example 12 Compound 51 below 15% Xylene 80% Surfactant 5% Solutions Example 13 Compound 1 below 30% Water 30% Ethanol 40% Example 14 Compound 3 below 12% Water 88% The novel herbicidal method and compositions are illustrated by the following experiments conducted in the laboratory.

Experiment 1 In a first test, the plants used were coontail Ceratophyllum demersum L.

Florida elodea, Hydrilla verticillata (L.F.); and duckweed, Lemna minor L. The plants were prepared by cutting four-inch terminal sprigs of the coontail and elodea, and selecting approximately enough duckweed to just cover the surface of the water in a 10 ml. beaker (approximately 30 plants). The coontail, elodea and duckweed were then placed in beakers containing 750 ml. of dechlorinated water containing the compounds.

The compounds for this test were formulated in the following manner.

Seventeen mg. of compounds was weighed into a 12 ml. disposable vial. To the vial containing the compound was added 1 ml. of acetone followed by 10 ml. of aqueous 0.1 percent polyoxyethylene sorbitan monooleate. This stock solution was then pipetted into the beakers at volumes of 0.45 ml. and 4.55 ml., to obtain I and 10 ppm. concentration of test compound in 750 ml. of water. Control beakers containing 750 ml. of water together with the solvents used in the formulations were also run. Other concentrations of the test compounds needed for testing were obtained by serial dilution of the I and 10 ppm. concentration solutions.

Observations of the effect of the compounds on the plants were made over a seven-day period. The scale for rating the aquatic herbicidal activity of the compounds was on a basis of 1--5, as follows: I=no effect 2=slight effect 3=moderate effect 4=heavy effect 5=complete kill The compounds tested are listed hereinafter.

1. 2 - (5 - Chloro - 2 - biphenylyloxy) - N,N - dimethylethylamine hydrobromide 2. 3 - (5 - Chloro - 2 - biphenylyloxy} - N,N - dimethyl - propylamine hydrochloride 3. 3 - (2- Cyclohexylphenoxy)- N,N - dimethyl - propylamine hydrochloride 4. 3 - (2 - Biphenylyloxy) - N,N - dimethyl - propylamine hydrochloride 5. 3 - -(2 - Benzyl - 4 - chlorophenoxy) - N,N - dimethylpropylamine hydrochloride 6. 3 - (5 - Chloro - 2 - biphenylyloxy) - N,N,I - trimethyl - propylamine hydrobromide 7. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - ethyl - 1 - methylpropylamine hydrochloride 8. 3 - (2 - Biphenylylthio) - N,N,I - trimethylpropylamine hydrochloride 9. N - (t - Butyl) - 3 - (5 - chloro - 2 - biphenylyloxy) - N - (2 - hydroxyethyl)propylamine hydrochloride 10. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - (2 - hydroxyethyl) - N neopentylpropylamine hydrochloride 11. 3 - (4 - Biphenylyloxy) - N,N,1 - trimethylpropylamine hydrochloride 12. 3 - (2 - Biphenylyloxy) - N,N,I - trimethylpropylamine hydrochloride 13. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - cyclohexylpropylamine hydrochloride 14. N - Adamantyl - 3 - (5 - chloro - 2 - biphenylylthio) - propylamine hydrochloride 15. 3 - (5 - Chloro - 2 - biphenylyloxy) - N,N - diethyl - I - methylpropylamine 16. 3 - (5 - Bromo - 2 - biphenylyloxy) - N,N,I - trimethylpropylamine hydrochloride 17. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - ethylpropylamine hydrochloride 18. 4 - [3 - (5 - Chloro - 2 - biphenylyloxy)propylimorpholine hydrochloride 19. 3 - (5 - Chloro - 2 - biphenylyloxy) - N,N,2 - trimethylpropylamine hydrobromide 20. 3 - (5 - Chloro - 2 - biphenylyloxy) - N,N - diethylpropylamine hydrochloride 21. 4 - (2 - Biphenylyloxy) - N,N - dimethylbutylamine hydrochloride 22. 3 - (5 - Chloro - 2 - biphenylyloxy)propylamine 23. N - Allyl - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine hydrochloride 24. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - isopropylpropylamine hydrochloride 25. N - (n - Butyl) - 3 - (5 - chloro - 2 - biphenylyloxy) - propylamine hydrochloride 26. N - (t - Butyl) - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine hydrochloride 27. 1 - [3 - (5 - Chloro - 2 - biphenylyloxy)propyl] - 2 - methylpiperidine hydrochloride 28. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - (2 - hydroxyethyl)propylamine hydrochloride 29. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - ethyl - N - (2 hydroxyethyl)propylamine hydrochloride 30. 3 - (5 - Chloro - 2 - biphenylyloxy) - N,N - bis(2 hydroxyethyl)propylamine hydrochloride 31. N - Adamantyl - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine hydrochloride 32. 1- [3 - (5 - Chloro - 2- biphenylyloxy)propyll - 4- (2 hydroxyethyl)piperazine dihydrochloride 33. 4- [3 - (3 - Chloro - 2- biphenylyloxy)propyl] - I - (2 - hydroxyethyl)piperazine dihydrochloride 34. N - Adamantyl - 3 - (2 - biphenylthio)propylamine hydrochloride 35. N - Adamantyl - 4 - (2 - biphenylylthio)butylamine hydrochloride 36. 3 - (2 - Biphenylylthio) - N - cyclohexylpropylamine hydrochloride 37. N - Adamantyl - 5 - (5- chloro - 2- biphenylyloxy)pentylamine hydrochloride 38. 4- (5 - Chloro- 2 - biphenylyloxy) - N,N - diethylbutylamine hydrochloride 39. 3 - (2 - Chloro - 5 - biphenylyloxy)- N,N - diethylpropylamine hydrochloride 40. 4 - (5 - Chloro - 2 - biphenylyloxy) - di - n - butylamine hydrochloride 41. 4 - (5 - Chloro - 2 - biphenylyloxy) - N - cyclohexylbutylamine hydrochloride 42. 4 - (5 - Chloro - 2 - biphenylyloxy) - N,N - diisopropylbutylamine hydrochloride 43. 10 - (s?- Chloro - 2 - biphenylyloxy) - N,N - diethyldecylamine hydrochloride 44. 10 - (5 - Chloro - 2 - biphenylyloxy) - N - ethyl - N - (2 - hydroxyethyl)decylamine hydrochloride 45. 3 - (5 - Chloro- 2 - biphenylylthio) - N- cyclohexylpropylamine hydrochloride 46. 10 - (5 - Chloro - 2 - biphenylyloxy) - N,N - dimethyldecylamine hydrochloride 47. 1 - [3 - (5 - Chloro - 2 - biphenylyloxy)propyl]pyrrolidine 48. N - (t - Butyl) - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine 49. N - (n - Butyl) - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine 50. 3- (5- Chloro- 2- biphenylyloxy)- N- phenylpropylamine hydrochloride 51. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - (3 methoxypropyl)propylamine 52. N - Benzyl - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine 53. 4- (5 - Chloro- 2 - biphenylyloxy) - N- ethyl - N- (2 hydroxyethyl)butylamine hydrochloride 54. N - (n - Butyl) - 3 - (5 - chloro - 2 - biphenylyloxy) -N - (2 hydroxyethyl)propylamine hydrochloride 55. 5 - (5 - Chloro - 2 - biphenylyloxy) - N - ethyl - N - (2 - hydroxyethyl)pentylamine hydrochloride 56. 3 - (3 - Chloro - 2 - biphenylyloxy) - N,N,1 - trimethylpropylamine hydrochloride 57. 6 - (5 - Chloro - 2 - biphenylyloxy) - N,N - dimethylhexylamine hydrochloride 58. 3 - (5 - Chloro - 2 - biphenylyloxy) - N - (2 - hydroxyethyl) - N methylpropylamine hydrochloride 59. N - (t - Butyl) - 3 - (2 - chloro - 4- biphenyloxy)propylamine hydrochloride 60. N - (t - Butyl) - 5 - (5 - chloro - 2- biphenylyloxy)pentylamine hydrochloride 61. N - (t - Butyl) - 6 - (5 - chloro - 2 - biphenylyloxy)hexylamine hydrochloride 62. 3 - (2 - Chloro - 5 - biphenylyloxy) - N- cyclohexylpropylamine hydrochloride The results of the test are recorded in Table 1, which follows. In the table, column I identifies the test compound by the number assigned to the compound in the list set forth hereinbefore; column 2, lists the application rate for each compound in parts per million (ppm.); and columns 3, 4 and 5 identify the test plants.

TABLE 1 Appln.

Compound Rate No. ppm. Hydrilla Coontail Duckweed 1 10 5 5 3 1 1 1 2 2 10 5 5 5 3 3 10 5 5 3 1 2 4 10 3 5 2 2 2 5 10 5 5 4 4 5 5 2 4 5 2 .1 2 2 3 0.5 2 4 6 10 5 5 5 4 5 4 5 2 1 2 5 2 2 5 2 7 10 5 5 5 4 5 3 5 2 4 4 4 1 3 4 2 0.5 1 1 2 8 10 2 5 2 1 1 2 9 10 4 5 4 1 3 2 10 10 4 5 1 4 11 10 5 5 5 1 3 1 12 10 5 5 3 4 1 1 13 10 2 5 3 1 5 14 10 5 5 1 3 4 15 10 5 5 5 4 5 5 5 2 4 2 3 1 2 3 0.5 1 1 16 10 5 5 4 1 1 3 17 10 5 5 5 4 5 5 5 2 3 3 4 2 2 4 2 0 TABLE 1 Continued Appln.

Compound Rate No. ppm. Hydrilla Coontail Duckweed 23 10 5 5 4 4 3 4 4 2 1 1 2 1 3 5 2 24 10 5 5 5 4 4 4 5 2 2 4 4 1 3 4 2 0.5 3 1 2 25 10 5 5 4 5 5 5 4 1 4 5 2 0.1 1 4 1 26 10 5 5 5 5 5 5 5 4 4 4 4 2 3 4 3 1 3 4 2 0.5 2 1 1 27 10 5 5 5 5 5 5 4 1 2 4 2 0.1 1 4 3 28 10 5 5 5 4 4 4 5 2 1 1 2 1 4 5 1 29 10 5 5 5 5 5 5 5 1 3 5 2 0.5 2 4 1 30 10 2 5 2 1 4 1 1 31 10 5 5 1 1 1 5 1 32 10 4 5 4 1 1 2 1 33 10 4 5 1 I 1 1 2 34 10 5 5 1 5 5 4 1 35 10 4 5 4 1 3 4 1 36 10 5 5 2 1 1 3 I 37 10 4 5 1 1 I 2 1 38 10 5 5 4 4 3 5 1 2 2 2 1 39 10 5 5 1 1 3 2 1 40 10 5 5 4 4 4 5 1 2 2 3 1 41 10 5 5 3 4 4 5 3 2 5 5 3 1 3 4 2 0.5 3 3 2 TABLE 1 Continued Appln.

Compound Rate No. ppm. Hydrilla Coontail Duckweed 42 10 5 5 4 4 2 4 4 2 1 2 3 1 3 5 I 43 10 3 5 2 1 3 1 1 44 10 4 5 I 1 2 3 I 45 10 5 5 2 1 3 5 I 46 10 4 5 3 4 3 5 I 2 2 2 1 47 10 5 5 4 4 4 51I 2 3 3 48 10 5 5 4 4 5 5 1 2 4 5 2 4 1 4 3 0.5 1 41 49 10 5 5 4 4 5 5 1 2 4 5 2 1 2 4 3 0.5 1 1 1 10 10 3 1 1 1 3 1 1 51 10 5 5 4 4 5 5 2 2 5 5 2 1 3 5 4 0.5 2 4 2 52 10 5 5 4 4 4 51I 2 4 5 2 1 2 5 I 0.5 1 5 1 53' 10 5 5 5 4 1 4 4 2 1 4 2 2 2 51 54 10 5 5 4 1 2 5 2 55 10 5 5 2 5 5 5 4 1 3 5 2 0.1 1 21 56 10 2 4 4 57 10 5 5 4 4 4 3 3 2 1 3 1 2 2 5 3 58 10 5 5 5 1 1 I I 59 10 4 5 4 4 4 4 3 2 3 3 2 60 10 5 5 4 4 5 5 2 2 3 3 2 TABLE 1 Continued Appln.

Compound Rate No. ppm. Hydrilla Coontail Duckweed 61 10 5 5 2 4 4 4 3 2 4 4 3 1 5 5 3 0.5 3 4 2 62 10 5 5 5 4 5 5 3 2 4 4 3 1 3 5 3 0.5 1 1 2 Control 0 0 0 0 Experiment 2 In a second test, the number of plants used in the test was increased to a total of six, and the test was carried out as follows.

Four of the plants to be used in the test, namely Florida elodea, Southern Naiad, Eurasian Milfoil, and Cabomba, were prepared by cutting four-inch terminal stems and burying the lower one inch of each stem in a mixture of sterilized sand-clay loam soil (50:50), in plastic 5-oz. drinking cups. The drinking cups containing the plants thus prepared were placed in l-gallon wide-mouth jars two weeks prior to testing. Each jar was filled with water to the lower edge of the rim, the volume then being equal to approximately 3500 ml. of water. The water used was dechlorinated city water. There were then added to the top of the water in each jar a four-inch length of coontail, Ceratophyllum demersum, and approximately 60 duckweed plants, Lemna minor L. In addition, to promote the good growth of the plants, there was added to the water in each jar three drops of a mixture of 5 ml.

chelated iron solution, 15 ml. water, and 15 ml. of a commerically available liquid fertilizer.

The following plants were used in this test: Florida elodea, Hydrilla verticillata (L.F.) Coontail, Ceratophyllum demersum (L.) Duckweed, Lemna minor L.

Southern Naiad, Nanas quadalupensis (Spreng.) Eurasian milfoil, Myriophyllum specatum L.

Cabomba, Cabomba caroliniana, Gray At the end of two weeks, the jars containing healthy preconditioned plants were selected for testing.

The test compounds were formulated in the following manner. Twenty-seven mg. of compound was weighed into a 12 ml. disposable vial. To the vial containing the compound was added 1 ml. of acetone followed by 10 ml. of aqueous 0.1 percent polyoxyethylene sorbitan monooleate. This stock solution was then pipetted into the jars at volumes of 7.5, 3, 1s.5, and 0.75 ml., to obtain 5, 2, 1, and 0.5 ppm. concentration of test compound in approximately 3500 ml. of water.

Duplicates were run at each concentration of the compound. Controls to which no test compound was added were also run.

Herbicidal activity ratings were made each week for at least three weeks. The herbicidal activity rating was on a basis of 1--5, as was set forth in the description of Experiment 1 above.

The herbicidal activity ratings observed the third week of the experiment are recorded in Table 2, which follows.

TABLE 2 Com- Appln.

pound Rate No. ppm. Hydrilla Coontail Duckweed Naiad Milfoil Cabomba 5 2 5 5 4 5 5 5 3 3 5 3 5 4 4 0.5 3 5 1 3 5 4 7 2 5 5 5 5 5 5 1 5 5 5 3 5 4 0.5 2 3 2 1 5 2 TABLE 2 Continued Com- Appln.

pound Rate No. pom. Hydrilla Coontail Duckweed Naiad Milfoil Cabomba 1.5 2 2 1 1 1 2 2 1 1 I 1 1 2 4 0.5 1 1 1 1 1 2 17 2 5 5 5 5 4 3 1 4 5 5 2 5 2 0.5 1 3 2 2 2 2 24 2 5 5 5 5 5 5 1 4 5 4 3 5 4 0.5 4 5 2 2 5 5 25 5 5 5 5 5 5 5 5 S 5 4 5 5 5 0.1 1 5 2 2 3 I 26 2 5 5 5 5 5 5 1 4 5 5 5 5 4 0.5 3 5 4 2 5 4 27 5 5 5 5 5 5 5 1 4 5 3 5 5 4 0.1 1 4 2 3 2 3 29 5 5 5 5 5 5 5 2 2 5 4 2 5 4 0.1 3 5 2 4 4 2 41 2 5 5 5 4 5 5 1 4 5 4 3 5 5 0.5 4 5 2 3 5 4 48 2 5 5 3 5 5 4 1 3 5 3 3 4 4 0.5 2 5 2 1 4 3 49 2 4 5 4 4 5 4 1 3 5 4 4 5 4 0.5 3 3 1 1 3 51 2 5 5 4 5 5 4 1 5 5 4 5 5 4 0.5 4 5 2 4 5 3 52 2 4 5 1 4 5 4 1 4 5 1 1 4 4 0.5 4 5 1 1 3 3 55 5 5 5 5 5 5 5 1 4 5 3 5 4 3 0.1 1 3 1 2 2 2 61 2 5 5 2 4 5 5 5 S 5 2 5 3 3 0.5 1 5 2 1 2 3 62 2 5 5 3 4 4 2 5 5 5 2 2 4 3 0.5 1 1 1 1 1 3 Controls 0 1 1 1 1 1 1 Experiment 3 Representative compounds were also tested against algae, in a test method which generally followed the herbicide test methods described above. The compounds were tested against representative green, blue-green and red algae of the genera Chlorella, Scenedesmus and Anacystis. The results were as follows.

TABLE 3 Rate of Compound Appln., No. ppm. Chlor. Scene. Anacy.

7 1 1 3 5 10 10 4 3 5 12 10 5 1 5 15 1 1 2 4 17 1 1 4 5 23 10 3 3 5 24 10 2 5 5 27 10 4 3 5 41 10 5 4 5 42 10 4 5 5 WHAT WE CLAIM IS: 1. An herbicidal and algicidal composition comprising an inert carrier and from 0.1% to 90 /" by wt. of a compound of the formula

wherein A is hydrogen, bromo, or chloro; B is cyclohexyl, benzyl, or phenyl; X is oxygen or sulfur; m is 0 or 1; when m=0, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=0; R1, when taken alone, is hydrogen, C1-C5 alkyl, or -CH2CH2OH; R2, when taken alone, is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -CH2CH2OH, -(CH2)3OCH3, l-adamantyl, benzyl, or phenyl; R1 and R2, when taken together with the nitrogen atom to which they are attached, form morpholino, 2-methylpiperidino, 4-(2-hydroxyethyl)piperazino, or pyrrolidino; or acid addition salts thereof, the composition being in the form of granules, wettable powders or an emulsifiable concentrate.

2. An herbicidal and algicidal composition of Claim 1 wherein the compound is of the formula

wherein A is hydrogen, bromo, or chloro; B is phenyl; X is oxygen or sulfur; m is 0 or 1; when m=0, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=O; R1 is hydrogen, C,--C, alkyl, or --CH,CH,OH; R2 is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -CH2CH2OH, or -(CH3)3OCH3; or acid addition salts thereof.

3. An herbicidal and algicidal composition of Claim I wherein the compound is of the formula

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

TABLE 3 Rate of Compound Appln., No. ppm. Chlor. Scene. Anacy.

7 1 1 3 5

10 10 4 3 5

12 10 5 1 5

15 1 1 2 4

17 1 1 4 5

23 10 3 3 5

24 10 2 5 5

27 10 4 3 5

41 10 5 4 5

42 10 4 5 5 WHAT WE CLAIM IS: 1. An herbicidal and algicidal composition comprising an inert carrier and from 0.1% to 90 /" by wt. of a compound of the formula

wherein A is hydrogen, bromo, or chloro; B is cyclohexyl, benzyl, or phenyl; X is oxygen or sulfur; m is 0 or 1; when m=0, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=0; R1, when taken alone, is hydrogen, C1-C5 alkyl, or -CH2CH2OH; R2, when taken alone, is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -CH2CH2OH, -(CH2)3OCH3, l-adamantyl, benzyl, or phenyl; R1 and R2, when taken together with the nitrogen atom to which they are attached, form morpholino, 2-methylpiperidino, 4-(2-hydroxyethyl)piperazino, or pyrrolidino; or acid addition salts thereof, the composition being in the form of granules, wettable powders or an emulsifiable concentrate.
2. An herbicidal and algicidal composition of Claim 1 wherein the compound is of the formula

wherein A is hydrogen, bromo, or chloro; B is phenyl; X is oxygen or sulfur; m is 0 or 1; when m=0, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=O; R1 is hydrogen, C,--C, alkyl, or --CH,CH,OH; R2 is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -CH2CH2OH, or -(CH3)3OCH3; or acid addition salts thereof.
3. An herbicidal and algicidal composition of Claim I wherein the compound is of the formula

wherein A is hydrogen or chloro B is phenyl; mis 0 or 1; when m=O, n+p is 3; and when m=l, n=2, and p=0; R1 and R2 taken together with the nitrogen atom to which they are attached or form morpholino, 2-methylpiperidino, 4-(2-hydroxyethyl)piperazino or pyrrolidino; or the acid addition salts thereof.
4. An herbicidal or algicidal composition of Claim I wherein the compound is of the formula

wherein A is hydrogen; B is phenyl; X is oxygen or sulfur; m is0 or 1; when m=0, n+p is 3 or 4; and when m=l, n=2, and p=O; R1 and R2 are both methyl; or the acid addition salts thereof.
5. An herbicidal or algicidal composition of Claim 1 wherein the compound is of the formula

wherein A is hydrogen or chloro; B is phenyl; X is oxygen or sulfur; n+p is 3, 4, or 5; R2 is l-adamantyl; or the acid addition salts thereof.
6. An herbicidal or algicidal composition of claim I wherein the compound is of the formula

wherein R2 is phenyl or benzyl; or the acid addition salts thereof.
7. An herbicidal and algicidal composition of Claim 2 wherein the compound is of the formula

wherein m is 0 or 1; when m=0, n+p is 2 to 6; and when m=l, n=p=l, or n=2, and p=0; R1 is hydrogen, C1-C5 alkyl, or -CH2CH2OH; R2 is hydrogen, C1-C5 alkyl, C3 alkenyl, --CH,CH,OH, ACH2)3OCH3, or cyclohexyl; or the acid addition salts thereof.
8. An herbicidal and algicidal composition of Claim 7 wherein the compound is of the formula

wherein m is 0 or 1; when m=0, n+p is 2, 3, or 4; when m=l, n=2, and p=0; R2 iS C2-C4 alkyl, cyclohexyl, or ACH2)3OCH3; or the acid addition salts thereof.
9. An herbicidal and algicidal composition of Claim 7 wherein the compound is 3 - (5 - chloro - 2 - biphenylyloxy) - N - ethyl - N - (2 hydroxyethyl)propylamine hydrochloride.
10. An herbicidal and algicidal composition of Claim 8 wherein the compound is 3 - (5 - chloro - 2- biphenylyloxy)- N- ethyl - 1 - methylpropylamine hydrochloride.
11. An herbicidal and algicidal composition of Claim 8 wherein the compound is N - (t - butyl) - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine hydrochloride.
12. An herbicidal and algicidal composition of Claim 8 wherein the compound is 3 - (5 - chloro - 2 - biphenylyloxy) - N - isopropylpropylamine hydrochloride.
13. An herbicidal and algicidal composition of Claim 8 wherein the compound is 4 - (5 - chloro - 2 - biphenylyloxy) - N - cyclohexylbutylamine hydrochloride.
14. An herbicidal and algicidal composition of any of Claims 1--10 which is an emulsifiable concentrate.
15. An herbicidal and algicidal composition of Claim 11 wherein the amount of the compound is from 5% to 50%.
16. An herbicidal and algicidal composition of any of Claims 1--13 which is a wettable powder.
17. An herbicidal and algicidal composition of Claim 16 wherein the amount of the compound is from 10% to 90%.
18. An herbicidal and algicidal composition of any of Claims 1--13 which is a granule.
19. An herbicidal and algicidal composition of Claim 18 wherein the amount of the compound is from 0.1% to 10%.
20. An herbicidal or algicidal method for reducing the vigor of aquatic weeds or algae in water which comprises contacting the weeds or algae with an herbicidally-effective or algicidally-effective amount of a composition comprising a compound of the formula

wherein A is hydrogen, bromo, or chloro; B is cyclohexyl, benzyl, or phenyl; X is oxygen or sulfur; m is 0 or 1; when m=0, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=0; R', when taken alone, is hydrogen, C1-C5 alkyl, or -CH2CH2OH; R2, when taken alone, is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -QH2ClI2OH, -(CH2)3OCH3, l-adamantyl, benzyl, or phenyl; R' and R2, when taken together with the nitrogen atom to which they are attached, form morpholino, 2-methylpiperidino, 4-(2-hydroxyethyl)piperazino, or pyrrolidino; and or acid addition salts thereof.
21. An herbicidal or algicidal method of Claim 20 wherein the composition comprises a compound of the formula

wherein A is hydrogen, bromo, or chloro; B is phenyl; X is oxygen or sulfur; m isO or 1; when m=0, n+p is 2 to 10; and when m=l, n=p=l, or n=2, p=0; R' is hydrogen, C1-C5 alkyl, or ---CH,CH,OH; R2 is hydrogen, C1-C5 alkyl, C3 alkenyl, cyclohexyl, -CM2CH2OH, or -(CH2)3OCH3; or acid addition salts thereof.
22. An herbicidal or algicidal method of Claim 20 wherein the composition comprises a compound of the formula

wherein A is hydrogen; B is phenyl; X is oxygen or sulfur; m isO or 1; when m=0, n+p is 3 or 4; and when m=l, n=2, and p=0; R' and R2 are both methyl; or the acid addition salts thereof.
23. An herbicidal or algicidal method of Claim 21 wherein the composition comprises a compound of the formula

wherein m isO or 1; when m=0, n+p is 2 to 6; and when m=l, n=p=l, or n=2, and p=0; R' is hydrogen, C1-C5 alkyl, or -CH2CH2OH; R2 is hydrogen, C1-C5 alkyl, C3 alkenyl, -CH2CH2OH, -(C112)3OCH3, or cyclohexyl; or the acid addition salts thereof.
24. An herbicidal or algicidal method of Claim 23 wherein the composition comprises a compound of the formula

wherein m isO or 1; when m=0, n+p is 2, 3, or 4; when m=l, n=2, and p=0; R2 iS C2-C4 alkyl, cyclohexyl, or -(CH2)3OCH3; or the acid addition salts thereof.
25. An herbicidal or algicidal method of any of Claims 2024 wherein the composition supplies to the water from 0.5 ppm. to 10 ppm. by wt. of the compound.
26. An herbicidal or algicidal method of Claim 25 wherein the composition supplies to the water from 0.5 ppm. to 2 ppm. of the compound.
27. An herbicidal or algicidal method of Claim 25 or 26 wherein the compound is 3 - (5 - chloro - 2- biphenyloxy) - N - ethyl - 1 - methylpropylamine hydrochloride.
28. An herbicidal or algicidal method of Claim 25 or 26 wherein the compound is N - (t - butyl) - 3 - (5 - chloro - 2 - biphenylyloxy)propylamine hydrochloride.
29. An herbicidal or algicidal method of Claim 25 or 26 wherein the compound is 3 - (5 - chloro - 2 - biphenylyloxy) - N - isopropylpropylamine hydrochloride.
30. An herbicidal or algicidal method of Claim 25 or 26 wherein the compound is 3 - (5 - chloro - 2 - biphenylyloxy)- N - ethyl - N- (2 hydroxyethyl)propylamine hydrochloride.
31. An herbicidal or algicidal method of Claim 25 or 26 wherein the compound is 4 - (5 - chloro - 2 - biphenylyloxy) - N - cyclohexylbutylamine hydrochloride.
32. An herbicidal and algicidal composition as claimed in Claim I substantially as hereinbefore described with particular reference to any one of the Examples.
33. An herbicidal or algicidal method as claimed in Claim 20 substantially as hereinbefore'described with particular reference to any one of the Examples.