WO2004101500A1 - Algicidal compound - Google Patents

Algicidal compound Download PDF

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Publication number
WO2004101500A1
WO2004101500A1 PCT/EP2004/005023 EP2004005023W WO2004101500A1 WO 2004101500 A1 WO2004101500 A1 WO 2004101500A1 EP 2004005023 W EP2004005023 W EP 2004005023W WO 2004101500 A1 WO2004101500 A1 WO 2004101500A1
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Prior art keywords
compound
algicidal
test
algae
ethoxyphenyl
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PCT/EP2004/005023
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French (fr)
Inventor
Yves Bessard
Michael LÜTZELER
Gérard ROMEDER
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Lonza Ag
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Publication of WO2004101500A1 publication Critical patent/WO2004101500A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C07C255/43—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms the carbon skeleton being further substituted by singly-bound oxygen atoms
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids

Definitions

  • the present invention relates to compounds that are useful as algicids.
  • Algicidal compounds are of use in industrial waters, for the sanitation of swimming pools and the like. Ideally, in the concentrations employed, they should be harmless for man and animal.
  • Marine algae are simple plants and as such are better protected against toxic influences than animal organisms, in particular complexly organized multicellular organisms of the animal kingdom. Plants do have a large central vacuole which allows of quick removal of toxic compounds from cytosol. Algae are continously exposed to surrounding liquid phase harboring all kind of solutes; their metabolism and cellular physiology evolved to withstand toxic compounds, therefore. In contrast, animal organisms, except simple unicellular protozoa, have evolved either tissue barriers functioning as diffusional barriers or additionally draw advantage from the air/liquid barrier. Algae are therefore much more robust to toxic influences.
  • a suitable compound according to the present invention is a compound of the formula I
  • Rl, R2 individually are C1-C4 aliphatic hydrocarbon or, taken together, are cycloalkane.
  • suitable hydrocarbon are e.g. alkyl, alkynyl or alkenyl.
  • 'Cycloalkane' refers to a R1-(CH2) X -R2 structural moiety; given the presence of the nitrogen atom in the cyclic structure thus formed, examples of type I compounds wherein R1,R2 are cycloalkane are e.g. 2-piperidino- 3 2-pyrrolizidino- or 2-pyrrolidino-2-(p- ethoxyphenyl)-acetonitrile.
  • the R1,R2 residues individually are methyl, ethyl, n-propyl or iso-propyl and may be the same or different. More preferably, R1,R2 are methyl or ethyl. Most preferably, R1,R2 are ethyl.
  • Compounds of formula I comprise a chiral carbon atom denoted in the formula (*). Further preferred, the compound of formula I is the L-enantiomer thereof. The L- enantiomer of formula I is more potent in its algicidal effect. It is equally possible though, to employ the racemic compound or a mixture having any other quantitative ratio of the two enantiomeric forms for use as an algicide. More preferably, the compound I is the L- enantiomer with R1,R2 being methyl, ethyl, n-propyl or iso-propyl. Most preferably, the compound of formula I is L-2-(p-ethoxyphenyl)-2-N,N'-diethylamino-acetonitrile.
  • Compound I may be synthesized by methods well-known in the art, namely Strecker synthesis suitably employed for synthesis of ⁇ -aryl- ⁇ -amino-nitriles as described in e.g. Suginome eta 1., Chemical Communications (of the Royal Society), 2002, 13:1392-1393. Since the established synthetical methods usually result in racemic compound, separation of enantiomers can be achieved by well-established enantioselective separation methodology, for example by preparative HPLC enantioselective chromatography emplyoing a chiral column material or separation in the presence of a soluble chiral auxiliary.
  • isolation of the pure L-enantiomer from racemic compound I as usually obtained by unselective chemical synthesis may be achieved e.g. by the method of Sokolie ⁇ , T. et al., Separation of racemic drugs on chiral resorcinarene-bonded HPLC columns, Pharmazie 2002, 57:589-590.
  • suitable HPLC stationary phases are in particular chiral cyclodextrin separation columns such as e.g. ChiraDex ® or ChiraDex Gamma ® (VWR it., UK) or chiral, microcrystalline cellulose-triacetate HPLC columns (VWR Int., UK), the latter being particularly suited for preparative chiral HPLC.
  • chiral separation matrices always the mobile solvent system needs to be selected based on polarity and the elution conditions carefully optimized for the specific separation problem as is well known to the skilled person.
  • algicidal is understood as to mean to have at least cytostatic, preferably a cytotoxic effect on growth and survival of microalgae. Details of suitable testing method can be found in the experimental section.
  • This method allows to determine the qualitative algicidal efficacy of biocides against the freshwater algae Chlorella vulgaris (green spherical algae), compare ISO 7218/Microbiology: General guidance for microbiological examinations and test method DIN 38412 from the German Institute for Standardization, 'Testing Testtechnisch mit Wasserorganismen (group L) ' .
  • Aqueous nutrient solutions with different concentrations of the products to be tested, inoculated with the selected alga, are placed on a shaker under specified conditions.
  • the algicidal efficacy is determined visually by controlling the growth or the absence of growth of the test algae.
  • Chlorella vulgaris Bejerinck green spherical algae, 5 - 10 ⁇
  • test strain can be freely obtained from the Algae collection, Physiological Plant Institute of University G ⁇ ttingen (SAG), Germany, Strain N° 211-ll b ( C. vulgaris Bejerinck) or is publically available from the American Type Culture Collection (ATCC), P.O.Box 1549, Manassas, VA 20108 /USA under accession number ATCC 13482. ATCC is an official national culture depository.
  • test strains may be enlarged. If other algae were used than the described, their cultivation, media and incubation temperature might need to be adjusted. Changes must be indicated in the report.
  • the reference alga is suspended in an adequate nutrient solution regarding enhancement (100-ml sterile Erlenmeyer flask or Pyrex bottle filled with 25 ml nutrient solution). This culture is incubated for 2 weeks at room temperature on a mini shaker, continuous lighting (2000 - 3000 LUX) under following conditions:
  • the algal suspension should have attained a concentration of approx. 2.5x10 7 cells /ml.
  • Cell counting can be performed e.g. by means of a counting chamber as is routine in the art.
  • the iron - EDTA complex solution should be only sterilized by a filtration procedure.
  • the other solutions should be sterilized in an autoclave at 121 °C.
  • the algicidal product or formulation should be diluted with an adequately sterilized nutrient solution down to the required test concentrations (ppm range usually).
  • the pH-value is not adjusted. In the proper concentration range, a dilution series of several different concentrations is tested. The lower the effective concentration threshold at which still some algicidal activity can be observed, the more potent the compound proves to be in the test.
  • the assessment is based on the qualitative absence or presence of algae growth in the nutrient solution.
  • the following scheme presents the evaluation of the algicidal effect of materials with regard to algae growth in the nutrient solution:
  • an algicidal compound is considered to have a good perfomance if effective in the ⁇ 100 ppm range, ideally in the ⁇ 20 ppm range.
  • Analytically pure (>98% w/w pure) DL-2-(p-ethoxyphenyl)-2-N,N'-diethylamino- acetonitrile as obtained from example A showed algicidal effect in dilutions below a 100 or 20 ppm, with some dependency on the solubilizing method and apparently on enrichment of the L-enantiomer as tested after chiral chromato graphic processing of the racemic mixture .
  • This data refers to about neutral pH of solution in the presence of a surfactant and/or using a suitable DMSO/water 1 : 1 system for initial solubilization of the test substance .
  • the aromatic aminonitrile compound according to the present invention is, due to its simple structure, biodegradable.
  • the amino- function does not give rise to exotic, harmful degradation products.
  • the 4- ethoxy-substituent at the aromatic core proved to be important for potency of algicidal effect and long term biodegradability in free waters.
  • a sodium bisulfite solution (40%, 68.3 g, 262 mmol, 1.05 eq) was added to a mixture of 4-ethoxybenzaldehyde (37.5 g, 250 mmol, 1 eq.) in 335 ml water in about 15 min.
  • the pH was raised to pH 7.0 by adding a 30% NaOH solution.
  • diethylamine 27.4g, 375 mmol, 1.5 eq
  • NaCN (12.9 g, 262 mmol, 1.05 eq, in 50 ml water
  • the reaction mixture is then cooled to 20°C and separated into two phases.
  • the water phase is extracted with toluene (2x100 ml) and combined with the organic phases.
  • the title compound is obtained as a yellow-orange oil (bp»100°C) comprising up to 10% impurity from the unreacted aldehyde educt (GC area analysis).
  • Stoechiometric yield is 85% at this stage.
  • Glucopon 600 CS UP 3 g orange oil product (*) obtained from example C were dissolved in water in the presence of the nonionic surfactant Glucopon 600 CS UP.
  • Glucopon 600 CS UP is a C 12 _ 14 Alkyl poly glycoside (Cognis/Henkel, Germany). Screening showed that a 1 : 1 ratio of the title compound aminonitrile and Glucopon 600 CS UP was feasible. The aqueous test dilutions were clear (only 250 and 500 ppm solutions showed a slight opaque behaviour). Product concentrations referred to are normalized to the weight ratio of pure title compound as comprised in the crude product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

A new algicidal compound is devised.

Description

ALGICIDAL COMPOUND
The present invention relates to compounds that are useful as algicids.
Algicidal compounds are of use in industrial waters, for the sanitation of swimming pools and the like. Ideally, in the concentrations employed, they should be harmless for man and animal.
Marine algae are simple plants and as such are better protected against toxic influences than animal organisms, in particular complexly organized multicellular organisms of the animal kingdom. Plants do have a large central vacuole which allows of quick removal of toxic compounds from cytosol. Algae are continously exposed to surrounding liquid phase harboring all kind of solutes; their metabolism and cellular physiology evolved to withstand toxic compounds, therefore. In contrast, animal organisms, except simple unicellular protozoa, have evolved either tissue barriers functioning as diffusional barriers or additionally draw advantage from the air/liquid barrier. Algae are therefore much more robust to toxic influences.
In the past, copper or aluminium sulfate proved to be efficient algicides in dosages of about 1-50 g/100 1 water. These amounts are comparatively huge, though; further, raising ionic strength of solutions treated in such way is not always desireable for certain applications.
An algicide that is harmless to man in the amounts used, is non-ionic and requires lower dosing in general would be desirable.
It is an object of the present invention to devise another algicidal agent. This object is solved by the compounds of formula I as set forth in claim 1.
A suitable compound according to the present invention is a compound of the formula I
Figure imgf000003_0001
wherein Rl, R2 individually are C1-C4 aliphatic hydrocarbon or, taken together, are cycloalkane. Examples of suitable hydrocarbon are e.g. alkyl, alkynyl or alkenyl. 'Cycloalkane' refers to a R1-(CH2)X-R2 structural moiety; given the presence of the nitrogen atom in the cyclic structure thus formed, examples of type I compounds wherein R1,R2 are cycloalkane are e.g. 2-piperidino-3 2-pyrrolizidino- or 2-pyrrolidino-2-(p- ethoxyphenyl)-acetonitrile. Preferably, the R1,R2 residues individually are methyl, ethyl, n-propyl or iso-propyl and may be the same or different. More preferably, R1,R2 are methyl or ethyl. Most preferably, R1,R2 are ethyl.
Compounds of formula I comprise a chiral carbon atom denoted in the formula (*). Further preferred, the compound of formula I is the L-enantiomer thereof. The L- enantiomer of formula I is more potent in its algicidal effect. It is equally possible though, to employ the racemic compound or a mixture having any other quantitative ratio of the two enantiomeric forms for use as an algicide. More preferably, the compound I is the L- enantiomer with R1,R2 being methyl, ethyl, n-propyl or iso-propyl. Most preferably, the compound of formula I is L-2-(p-ethoxyphenyl)-2-N,N'-diethylamino-acetonitrile.
Compound I may be synthesized by methods well-known in the art, namely Strecker synthesis suitably employed for synthesis of α-aryl-α-amino-nitriles as described in e.g. Suginome eta 1., Chemical Communications (of the Royal Society), 2002, 13:1392-1393. Since the established synthetical methods usually result in racemic compound, separation of enantiomers can be achieved by well-established enantioselective separation methodology, for example by preparative HPLC enantioselective chromatography emplyoing a chiral column material or separation in the presence of a soluble chiral auxiliary. In this way, isolation of the pure L-enantiomer from racemic compound I as usually obtained by unselective chemical synthesis, may be achieved e.g. by the method of Sokolieβ, T. et al., Separation of racemic drugs on chiral resorcinarene-bonded HPLC columns, Pharmazie 2002, 57:589-590. Further examples of suitable HPLC stationary phases are in particular chiral cyclodextrin separation columns such as e.g. ChiraDex ® or ChiraDex Gamma ® (VWR it., UK) or chiral, microcrystalline cellulose-triacetate HPLC columns (VWR Int., UK), the latter being particularly suited for preparative chiral HPLC. For chromatographic separations using such chiral separation matrices, always the mobile solvent system needs to be selected based on polarity and the elution conditions carefully optimized for the specific separation problem as is well known to the skilled person.
Suitable dosing of the compound of formula I in the range of preferably of from 0.1 ppm up to 100-200 ppm, more preferably in the range of 0.5 to 50 ppm, most preferably in the range of 1-10 ppm, allows of algicidal effect. In the context of the present application, algicidal is understood as to mean to have at least cytostatic, preferably a cytotoxic effect on growth and survival of microalgae. Details of suitable testing method can be found in the experimental section.
Experiments
Example A:
Synthesis of DL-2-(p~ethoxyphenyl)-2-N,N'-diethylamino~acetonitrile
Synthesis was carried out according to the method of Hauser et al., J. Am. Chem. Soc, 82, 1786f (1960). Para-ethoxybenzaldehyd was reacted with sodium bisulfite to yield an addition product that was further reacted with Diethyl-amine and sodium cyanide in a cold ethanol solution. For product isolation, (precipitated) product and educt were separated by acid-treatment followed by filtering off the educt and further recrystallizing from the liquid by pH adjustment a few times, essentially as described. Example B:
Algicidal Performance of DL-2-(p-ethoxyphenyl)-2-N,N'-diethylamino-acetonitrilβ
1. Scope and Application:
This method allows to determine the qualitative algicidal efficacy of biocides against the freshwater algae Chlorella vulgaris (green spherical algae), compare ISO 7218/Microbiology: General guidance for microbiological examinations and test method DIN 38412 from the German Institute for Standardization, 'Testing Testverfahren mit Wasserorganismen (group L) ' .
It is intended to determine the minimum concentration, which prevented algae growth. Other algae than the above mentioned may be tested with this method, provided that it is adapted accordingly. This procedure is not suitable for testing algicidal products reacting with ingredients of the nutrient solution.
2. Brief Description of the Test:
Aqueous nutrient solutions with different concentrations of the products to be tested, inoculated with the selected alga, are placed on a shaker under specified conditions. The algicidal efficacy is determined visually by controlling the growth or the absence of growth of the test algae.
3. Safety Precautions:
Since the selected alga might be toxic, only qualified operators with a microbiological training can carry out the tests following this method. Any safety precaution for microbiological laboratories and national reglementations must be strictly observed.
5. Reagents and Culture Media: 5.2 Reagents & Culture Media: 5.2.1 Nutrient Solution for Test:
Figure imgf000006_0001
5.2.1.1 Preparation of Nutrient Solution:
A. Stock solutions:
Figure imgf000006_0002
B. Iron - EDTA - Complex - Solution *:
Figure imgf000007_0001
* Preparation of the Fe-EDTA complex: 0.695 g FeSO4 ° 7 H2O and 0.93 g disodium salt of EDTA (Titriplex m ex Merck) are dissolved in 80 ml of distilled water by boiling for a short time. After the solution has cooled down to room temperature it is filled up to 100 mi. It contains in 1 ml the amount of iron stated above.
C. Trace Elements Solution:
Figure imgf000007_0002
Pipette the afore mentioned volumes of the solutions A, B and C in a 1 liter-flask and fill up with 948 ml of distilled water.
6. Test Organism:
The following alga is used:
Chlorella vulgaris Bejerinck (green spherical algae, 5 - 10 μ)
Usually found in: Freshwater like seas, streams, pools etc.
The test strain can be freely obtained from the Algae collection, Physiological Plant Institute of University Gδttingen (SAG), Germany, Strain N° 211-ll b ( C. vulgaris Bejerinck) or is publically available from the American Type Culture Collection (ATCC), P.O.Box 1549, Manassas, VA 20108 /USA under accession number ATCC 13482. ATCC is an official national culture depository.
Depending on the range of application and on the specific requirements, the spectrum of test strains maybe enlarged. If other algae were used than the described, their cultivation, media and incubation temperature might need to be adjusted. Changes must be indicated in the report.
7. Cultivation of Reference Alga:
The reference alga is suspended in an adequate nutrient solution regarding enhancement (100-ml sterile Erlenmeyer flask or Pyrex bottle filled with 25 ml nutrient solution). This culture is incubated for 2 weeks at room temperature on a mini shaker, continuous lighting (2000 - 3000 LUX) under following conditions:
Mini shaker Shake movement: planetary shaking Amplitude: 12.5 mm 0
Shake frequency: 85 rpm
Light source OSRAM neon lamp according DIN IEC 81, 38412, Light color 25 universal white L 80, 25W For having good, uniform growth it is required to avoid a sedimentation of the algae by shaking and also take care for an optimal ventilation as well as continuous lighting of the nutrient solution.
After two weeks the algal suspension should have attained a concentration of approx. 2.5x107 cells /ml. Cell counting can be performed e.g. by means of a counting chamber as is routine in the art.
Opening and closing of the test bottles, inoculation etc. should be done near to a flame. The edge should be flamed in order to avoid contamination. The bottles are closed with a cotton plug. 8. Cultivation of Test Alga:
The method of section 7 immediately above was employed as well.
9. Sterilization of the Nutrient Solutions:
The iron - EDTA complex solution should be only sterilized by a filtration procedure. The other solutions should be sterilized in an autoclave at 121 °C.
10. Test Procedure:
The algicidal product or formulation should be diluted with an adequately sterilized nutrient solution down to the required test concentrations (ppm range usually). The pH-value is not adjusted. In the proper concentration range, a dilution series of several different concentrations is tested. The lower the effective concentration threshold at which still some algicidal activity can be observed, the more potent the compound proves to be in the test.
Add 25 ml of the accordingly prepared nutrient solution (one without algicide as control sample) into the sterilized 100-ml test vessel such as a sterilized 100-ml Erlenmeyer flask or Pyrex bottle. Inoculate with 0.1 ml of the algae suspension so that the test solution contains approx. 105 cells / 25 ml.
11. Assessment of the Test:
The assessment is based on the qualitative absence or presence of algae growth in the nutrient solution. The following scheme presents the evaluation of the algicidal effect of materials with regard to algae growth in the nutrient solution:
Figure imgf000010_0001
The lowest algicidal performance will be determined after two weeks incubation time and finally one week later in comparison to the control sample. Following this method, an algicidal compound is considered to have a good perfomance if effective in the < 100 ppm range, ideally in the < 20 ppm range.
Analytically pure (>98% w/w pure) DL-2-(p-ethoxyphenyl)-2-N,N'-diethylamino- acetonitrile as obtained from example A showed algicidal effect in dilutions below a 100 or 20 ppm, with some dependency on the solubilizing method and apparently on enrichment of the L-enantiomer as tested after chiral chromato graphic processing of the racemic mixture . This data refers to about neutral pH of solution in the presence of a surfactant and/or using a suitable DMSO/water 1 : 1 system for initial solubilization of the test substance . The aromatic aminonitrile compound according to the present invention is, due to its simple structure, biodegradable. In particular the amino- function does not give rise to exotic, harmful degradation products. Surprisingly, the 4- ethoxy-substituent at the aromatic core proved to be important for potency of algicidal effect and long term biodegradability in free waters.
Example C:
Synthesis of 2-(p-ethoxyphenyl)-2-NsNs-diethylammo-acβtonitriIe with simplified work-up
In a 500 ml flask at 20°C under nitrogen atmosphere, a sodium bisulfite solution (40%, 68.3 g, 262 mmol, 1.05 eq) was added to a mixture of 4-ethoxybenzaldehyde (37.5 g, 250 mmol, 1 eq.) in 335 ml water in about 15 min. The pH was raised to pH 7.0 by adding a 30% NaOH solution. Within 10 min. , diethylamine (27.4g, 375 mmol, 1.5 eq) and NaCN (12.9 g, 262 mmol, 1.05 eq, in 50 ml water) were added to the reaction mixture under stirring and heated up to 60°C. Conversion is followed by GC analysis of samples until yield is stable (in situ yield ~88%).
The reaction mixture is then cooled to 20°C and separated into two phases. The water phase is extracted with toluene (2x100 ml) and combined with the organic phases. After vacuum distillation of the solvent, the title compound is obtained as a yellow-orange oil (bp»100°C) comprising up to 10% impurity from the unreacted aldehyde educt (GC area analysis). Stoechiometric yield is 85% at this stage.
Example D:
Algicidal Performance of crude quality 2-(p-ethoxyphenyl)-2-N,N'-diethyIamino- acetonitrile
3 g orange oil product (*) obtained from example C were dissolved in water in the presence of the nonionic surfactant Glucopon 600 CS UP. Glucopon 600 CS UP is a C12_ 14 Alkyl poly glycoside (Cognis/Henkel, Germany). Screening showed that a 1 : 1 ratio of the title compound aminonitrile and Glucopon 600 CS UP was feasible. The aqueous test dilutions were clear (only 250 and 500 ppm solutions showed a slight opaque behaviour). Product concentrations referred to are normalized to the weight ratio of pure title compound as comprised in the crude product.
Except for the surfactant system, the algicidal performance was tested essentially as described above for example B against the algae Chlorella vulgaris 211-1 lb. Below test concentrations refer to pure racemic 2-(p-ethoxyphenyl)-2-N,N'- diethylamino-acetonitrile resp. Glucopon 600 CS UP. From the controls with pure Glucopon 600, it is apparent that the presence of the specific surfactant did not negtively impact algal growth. - The results are shown in Table I. The title compound 2-(p- 0 ethoxyphenyl)-2-N,N'-diethylamino-acetonitrile showed sufficient aligicidal properties against the test algal organism at <50 ppm similar to the pure compound, rendering use of more pure compound less desireable in view of the lower yield/more lengthy and laborious purification steps needed. The byproducts did not interfere with aligicidal properties. 5
Table I
Figure imgf000012_0001
Legend : growth = + weak growth = +/- no growth = -

Claims

Claims
1. Compound of the formula I
Figure imgf000013_0001
wherein Rl, R2 individually are C1-C4 aliphatic hydrocarbon or, taken together, are cycloalkane.
2. Compound according to claim 1, characterised in that Rl, R2 are selected from the group consisting of methyl, ethyl, n-propyl or iso-propyl, wherein R1,R2 may be the same or may be different.
3. Compound according to claim 2, characterised in that the compound of formula I is 2-(p-ethoxyphenyl)-2-N,N' -diethylamino-acetonitrile.
4. Compound according to claim 2 oder 3, characterised in that it is the L- enantiomer.
5. L-2-(p-ethoxyphenyl)-2-N,N' -diethylamino-acetonitrile.
PCT/EP2004/005023 2003-05-13 2004-05-11 Algicidal compound WO2004101500A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1783128A1 (en) 2005-11-07 2007-05-09 Eidgenössische Technische Hochschule Zürich Heterocyclic compounds and their use as antifouling agents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2268108A (en) * 1938-03-11 1941-12-30 Ici Ltd Insecticidal composition
US3313683A (en) * 1963-04-22 1967-04-11 Lilly Co Eli Nematocidal and fungicidal methods

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2268108A (en) * 1938-03-11 1941-12-30 Ici Ltd Insecticidal composition
US3313683A (en) * 1963-04-22 1967-04-11 Lilly Co Eli Nematocidal and fungicidal methods

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ARMYANSKII KHIMICHESKII ZHURNAL , 23(10), 624-8 CODEN: AYKZAN; ISSN: 0515-9628, 1970 *
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MNDZHOYAN, A. L. ET AL: "Guanidine derivatives. VIII. Substituted guanidines as possible hypotensive substances", XP002297586, retrieved from STN Database accession no. 1971:99806 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1783128A1 (en) 2005-11-07 2007-05-09 Eidgenössische Technische Hochschule Zürich Heterocyclic compounds and their use as antifouling agents

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