EP1204320A2 - Neue juvenilhormonanaloge und deren verwendung zur als bewuchshemmende mittel - Google Patents

Neue juvenilhormonanaloge und deren verwendung zur als bewuchshemmende mittel

Info

Publication number
EP1204320A2
EP1204320A2 EP00944147A EP00944147A EP1204320A2 EP 1204320 A2 EP1204320 A2 EP 1204320A2 EP 00944147 A EP00944147 A EP 00944147A EP 00944147 A EP00944147 A EP 00944147A EP 1204320 A2 EP1204320 A2 EP 1204320A2
Authority
EP
European Patent Office
Prior art keywords
dimethylcyclopropyl
compound
methylpent
general formula
pyridine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00944147A
Other languages
English (en)
French (fr)
Inventor
Henry R. Hovde
Karsten Kleveland
Nils Olav Nilsen
Yngve Stenstroem
Lars Skatteboel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bioparken AS
Original Assignee
Bioparken AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bioparken AS filed Critical Bioparken AS
Publication of EP1204320A2 publication Critical patent/EP1204320A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P17/00—Pest repellants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • the present invention relates to the field of preventing or reducing fouling of surfaces of structures that are intermittently or continuously immersed in water. More specifically, there is provided novel juvenile hormone compounds that are effective in respect of inhibiting the settlement, attachment and/or metamorphosis of crustacean larval stages, in particular cy- prid larvae of barnacles and Cirripedia species. Juvenile hormone analogues having this biological activity can be used in antifouling compositions.
  • marine organisms such as algae, tubeworms, ascidians, bryozoans, hydroids, barnacles and mussels live in both fresh water and saline water bodies.
  • a structure such as a ship, a boat, a fishing net, a drainage pipe or an off-shore oil drilling rig is placed in or on the water, marine organisms become attached to the structure and grow to give various kinds of damage to the structure. This phenomenon is generally referred to as fouling or bio-fouling.
  • antifouling paints In order to solve the fouling problem several antifouling paint technologies have been developed. Currently, most antifouling paints contain biocides directed against one or more of the antifouling organisms. The majority of antifouling paints currently in use are effective because toxic components based on heavy metals are included in their formulation. In use, these heavy metals are leached out at various rates and concentrations from the matrix of the paint. However, the steady accumulation of these metals in the marine environment has adversely affected marine life, and restrictions have been or are being applied to their use. Examples of such antifouling components include cuprous oxide and triphenyl- or
  • barnacles An important group of marine organisms that contributes significantly to the fouling process is the group of crustacean organisms that are collectively referred to as barnacles. These organisms belong to the Cirripedia subclass of the order Crustacea.
  • the Cirripedia subclass includes four orders: Thoracica, Acrothoracica, Ascothorica and Rhizocephala. Of these, species of Thoracica that belong to the genus Balanus, also referred to as acorn shell or rock barnacles, are commonly involved in fouling of submersed surfaces.
  • insects include molting hormones (MHs), also referred to as ecdysones, and juvenile hormones (JHs), the latter class of compounds being terpenoid compounds.
  • MHs molting hormones
  • JHs juvenile hormones
  • JHs The natural juvenile hormones
  • the natural juvenile hormones (JHs) are a class of compounds that regulate both metamorphosis and gametogenesis in insects. 1 Five compounds have been isolated and cha- racterized. 2 They can all be considered as derivatives of methyl 10,11 -epoxyfarnesoate and appear to be universally distributed among insects. Despite their potential as natural insecticides there has been no widespread use of the JHs as such. This is due in part to the facile hydrolysis of the epoxide ring to the biologically inactive diols but also to the lack of species specificity.
  • One approach to overcome these problems is to use structurally dif- ferent compounds with JH activity, so-called juvenile hormone analogues (JHAs) or juvenoids.
  • the present invention has now provided a large range of novel, structurally diverse juvenile hormone analogues, of which many, even at very low concentrations such as ⁇ 100 ppb or even ⁇ 10 ppb affect the metamorphosis of barnacle larvae and it has been found that a substantial number of such compounds can prevent that cyprid larvae of barnacles settle on solid surfaces. This opens up for a systematic approach for developing and selecting non-toxic antifouling agents that are selectively controlling the fouling by barnacles.
  • the invention relates to a juvenile hormone analogue (juvenoid) compound selected from the group consisting of
  • R is alkyl or branched alkyl including alkenyl, alkadienyl and alkatrienyl, optionally substituted isoprenoid or alkoxy substituted alkyl
  • R 2 is hydrogen or alkyl
  • X is oxygen, sul- fur, methylene, carbinol or carbonyl
  • Y is nitrogen or methinine and Z is nitrogen, methine or nitrogen oxide;
  • R 1 is 2,2-dimethylcyclopropyl, 2,2-dihalo-3,3-dimethylcyclopropyl, 2-methyl-1- propenyl or 3-methyl-1 ,2-butadienyl
  • R 2 is hydrogen or methoxy
  • R 3 is alkyl, alkenyl, acetyl, formyl or carbomethoxy
  • R 4 is hydrogen or R 3 and R 4 together is methylenedioxy and
  • X is oxygen or sulfur
  • R 1 is 2-methylbutyl, 2,2-dimethylcyclopropyl or 2,2-dihalo-3,3-dimethylcyclopropyl and R 2 is methyl, ethyl or isopropyl,
  • the compound is not 5-(3',7'-Dimethylocta-2',6'-dienyloxy)-2- methylpyridine, 3-(3',7 , -Dimethylocta-2',6'-dienyloxy)pyridine, 5-(3',7'-Dimethylocta-2',6'- dienylsulfanyl)benzo[1 ,3]dioxole or Methyl 7,11-dimethyl-dodeca-2,4-dienoate.
  • a juvenile hormone analogue compound that, at a concentration of at the most 10 ppm, inhibits the settlement and/or attachment of cyprid larvae of a Cirripedia species onto a solid surface in contact with an aqueous medium containing said concentration of the compound and/or the metamorphosis of such larvae in the aqueous medium, by at least 50% (EC-50), relative to cyprid larvae contained in a medium not containing the compound.
  • the invention relates to a method of controlling the fouling of a surface with a living organism, the method comprising applying to said surface an effective amount of a juvenile hormone analogue compound including any of the above compounds, an antifouling composition comprising a juvenile hormone compound as defined above, methods of preparing the novel compounds of the invention and the use of a juvenile hormone analogue as an antifouling agent in a paint composition.
  • novel juvenile hormone compounds as defined above which are structurally varied so as to provide compounds that are useful as antifouling agents.
  • Useful classes of compounds according to the invention are compounds of the general formula I where R 1 is alkyl or branched alkyl including alkenyl, alkadienyl and alkatrienyl, optionally substituted isoprenoid or alkoxy substituted alkyl, R 2 is hydrogen or alkyl, X is oxygen, sulfur, methylene, carbinol or carbonyl, Y is nitrogen or methinine and Z is nitro- gen, methine or nitrogen oxide; compounds of the general formula II where R 1 is 2,2-dimethylcyclopropyl, 2,2-dihalo-3,3-dimethylcyclopropyl, 2-methyl-1-propenyl or 3-methyl- 1 ,2-butadienyl, R 2 is hydrogen or methoxy, R 3 is alkyl, alkenyl, acetyl, formyl or carbome
  • alkyl refers to a straight or branched chain saturated or unsatu- rated aliphatic group e.g. having one to eleven carbon atoms, such as methyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl or octyl.
  • the compound of the invention is a compound of the general formula I where R 1 is straight chain or branched alkyl or an alkoxyy substituted alkyl.
  • R in compounds of general formula I is isoprenoid including cyclopropyl substituted isoprenoid such as famesyl or R1 is ⁇ /em-dihalocyclopropyl substituted isoprenoid.
  • X is oxygen or sulfur.
  • Particularly useful compounds of the invention include compounds of the general formula I where Y and/or Z is nitrogen.
  • R-2 (3' )-5-(3',7'-Dimethyloctyloxy)-2-methylpyridine;
  • F-1 3-[2'-(4"-Phenoxyphenoxy)ethoxy]pyridine
  • 25 F-3 2-[2'-(4"-Phenoxyphenoxy)ethoxy]pyridine
  • Further useful compounds of the invention include compounds of the general formula II in- 30 eluding such compounds having saturated side chains to the aromatic ring and compounds of the general formula II where R 3 and R 4 together is methylenedioxy and such compounds where X is oxygen.
  • Specific compounds of the general formula II include compounds selected from the group 35 consisting of 17: 5-(3',7'-Dimethyloctyloxy)benzo[1 ,3]dioxole;
  • I-205 3,3-dimethylocta-2,6-dienoic acid dimethylamide
  • juvenile hormone analogues are provided that, at a concentration of at the most 10 ppm, inhibit the settlement and/or attachment of cyprid larvae of the Cirripedia species Balanus balanoides, Balanus improvisus or Balanus amphitrite onto a solid surface in contact with an aqueous medium containing said concentration of the compound and/or the metamorphosis of such larvae in the aqueous medium, by 50% (EC-50), relative to such cyprid larvae contained in a medium not containing the compound.
  • the EC-50 values for any of these Balanus species is determined in accordance with the specific settlement test procedures described for each species in the following Example 2.
  • this high biological activity against Balanus balanoides, Balanus improvisus and Balanus amphitrite that is observed with compounds of the invention is due to inhibition of the metamorphosis from the cyprid larval stage to the adult, sessile stage.
  • the biological effect may also be directed against the settling capacity of the barnacles such as an abnormal development of the organs whereby the organisms attach to solid surfaces.
  • Juvenile hormone activity may be determined using newly-molted (4-8 hours) Tenibrio mo- litor pupae.
  • the compounds to be evaluated are formulated to contain 10 ⁇ g in 1 ml of solution. Acetone is a preferred solvent and is used in both topical and vapor tests.
  • Topical application is with a micro applicator (Isco model M) fitted with a tuberculin syringe and a 27 gauge needle.
  • One ⁇ l of the desired solution is administered/pupa on the venter of the last three abdominal segments.
  • Vapor action is determined by applying the candidate compound to the lower 1/3 of a 1 pint freezer type jar and then inverting the jar into a 1/2 pint container, containing 5 pupae.
  • a dosage of 1 ⁇ l of the desired solution per pupa (5 ⁇ l/jar) is used. All pupae are held until the following molt to determine juvenile hormone activity, which is indicated by the presence of immature characters; e.g. i) retention of gin traps, ii) retention of gin traps and urogomphi, iii) retention of gin traps and urogomphi plus retention of pupal cuticle around area of treatment, and iv) 2nd pupae - retention of all pupal characters. If a perfect adult is obtained after molting, the compound has no juvenile hormone activity. Farnesyl methyl ether is used as the standard for both topical and vapor tests.
  • the structure of the compounds according to the invention has a significant effect on their biological activity.
  • pyridyl ethers in general had the highest biological activity in the below test system. Specifically it was shown that such compounds where the ether lin- kage is attached to the pyridine ring at the 3-position are more active than corresponding compounds having the ether linkage attached to the 2-position. It was also found for these pyridyl ether compounds that when the substituent in the 6-position of the pyridine ring is changed from ethyl to methyl to hydrogen the activity decreases in that order. Replacing the oxygen in pyridyl ether compounds with sulfur resulted in compounds that were practi- cally inactive in the test system described in the examples below.
  • the molecule should have a polarity that is sufficient for optimum solubility in the cytoplasm of cells of the target organisms as well as a lipophilic character that enables penetration of the cuticle of the target organism. Accordingly, it is believed that the most active compounds of the invention are those having an appropriate balance between hydrophobicity and lipophi- licity.
  • the juvenile hormone analogue is a compound that in a settlement test as described hereinbelow using Balanus balanoides, Balanus improvisus or Balanus amphitrite as the test organisms has an EC-50 of at the most 10 ppm such as at the most 1 ppm including at the most 100 ppb e.g. 80 ppb such as at the most 60 ppb including at the most 50 ppb such as at the most 30 ppb including at the most 20 ppb, such as at the most 10 ppb or even at the most 1 ppb.
  • the expression "applying to said surface” includes embodiments where the juvenile hormone analogue is dissolved or suspended in water.
  • the juvenile hormone ana- logue compound used in such a method is a compound according to the invention as de- fined above.
  • the target organisms in the method is any arthropod species that causes fouling of submersed vessels and other structures such as e.g. oil drilling rigs and fishing nets that are occasionally or permanently immersed in fresh water or saline water.
  • Such target species include larval stages of fouling crustacean species, in particular barnacle species of the Cirripedia subclass including Balanus galeatus, Balanus amphitrite, Elminius modestus, Balanus improvisus, Balanus balanoides and Balanus crenatus.
  • barnacle species of the Cirripedia subclass including Balanus galeatus, Balanus amphitrite, Elminius modestus, Balanus improvisus, Balanus balanoides and Balanus crenatus.
  • the juvenile hormone analogue is applied to the surface to be protected from fouling by incorporating the compound into a coating composition such as a paint composi- tion including paints for ships and immersed stationary structures such as e.g. fishing nets or oil drilling rigs.
  • a coating composition such as a paint composi- tion including paints for ships and immersed stationary structures such as e.g. fishing nets or oil drilling rigs.
  • such compositions can be prepared according to conventional manufacturing technology and the compositions may, in addition to the juvenile hormone analogue, contain components that are usual for paint compositions including binders, pigments, extenders, additives and solvents (e.g. as previously de- scribed in US 5,332,430).
  • the amount of juvenile hormone analogue in such compositions is generally in the range of 0.1-50% by weight of the composition, such as in the range of 0.5-25%, including the range of 1-20%, such as in the range of 1.5-15% by weight of the composition. In one embodi- ment the amount of juvenile hormone analogue is in the range of 2-10% by weight of the composition.
  • Suitable binders for such coating composition include functionalised acrylates (like methacrylates, metal acrylates and silyl acrylates), vinyls (like copolymer of vinyl chloride and vinyl isobutyl ether), chlorinated rubbers and rosins (like gum rosin, wood rosin and tall oil rosin).
  • functionalised acrylates like methacrylates, metal acrylates and silyl acrylates
  • vinyls like copolymer of vinyl chloride and vinyl isobutyl ether
  • chlorinated rubbers and rosins like gum rosin, wood rosin and tall oil rosin.
  • pigments include titanium dioxide, zinc oxide, carbon black, iron oxide and colour pigments.
  • extenders/fillers include sulfates, oxides, silicates and carbonates.
  • additives include thixotropic agents (like bentonite and aerosil), plasticizers (like chlorinated paraffins, tri cresyl phosphate, phtalates and polyvinyl ethyl ether).
  • solvents include aliphatic and aromatic hydrocarbons (like heptane and xylene), alcohols (like butanol), ke- tones (like methyl isobutyl ketone), esters (like ethyl acetate and butyl acetate), water and others (like 1-metoxy-2-propanol), and mixtures of these. It will be appreciated that a coating composition according to the invention may contain two or more different juvenile hormone analogues to obtain a broad range activity against a variety of barnacle species and other fouling arthropod organisms that are susceptible to juvenile hormone analogues.
  • the antifouling coating composition may contain at least one further biocidally active compound including any of the currently used antifouling agents including algicides.
  • biocidally active compounds includes copper metal, cuprous oxide, cuprous thiocyanate, bis (2-pyridinethiol 1 -oxide) zinc, bis (2-pyridinethiol 1 -oxide) copper, 4,5-dichloro-2-octyl-3(2H)-isothiazolinone, 2-methylthio-4-tert-butylamino-6- cyclopropylamino-triazine, zinc ethylenebis (dithiocarbamate) and pyridine triphenylborane.
  • the antifouling composition of the invention may contain any juvenile hormone analogue that is effective against one or more fouling arthropod organisms, including any of the novel compounds according to the invention.
  • the antifouling composition of the invention comprises a juvenile hormone analogue of the general formula I where Z is nitrogen.
  • Aromatic and heteroaromatic ethers and thioethers General.
  • the heteroaromatic ethers and thioethers 1-15, the phenyl ethers 17-38, and the piperidyl ether 16 were all prepared by the same general procedure used for the preparation of compound 2 ( see below). The preparation of some of the halides are given below.
  • 2-(3', 7'-Dimethyloctylsulfanyl)thiophene (57) was obtained using the general procedure by Fedorov and Stoyanovich 28 starting from 1.93 g (23 mmol) thiopene, 16 mL (24 mmol) 1.53 M BuLi in hexane, 0.74 g (23 mmol) sulphur and 5.00 g (23 mmol) 1-bromo-3,7- dimethyloctane in 5 mL ether and 15 mL dry DMF. Short path distillation (bath 98°C/0.02 mmHg) yielded 3.1 g (53%) of 57.
  • 4,8-Dimethyl-1-pyridin-3-ylnonan-1-one was prepared according to Frank and Weater- bec's procedure 23 starting with 22.1 g (0.10 mol) of 1-bromo-3,7-dimethyloctane, 2.7 g (0.11 mol) Mg and 9.4 g (0.09 mol) 3-cyanopyridine in 150 mL dry ether. Extraction with dichloromethane, drying (MgSO 4 ), evaporation and short path distillation (bath 109-114 °C/0.02 mmHg) gave 9.4 g (42%) of 54.
  • the allenes 22 and 27 were prepared from the corresponding dibromocyclopropanes 21 and 26, respectively, by reactions with methyllithium at -78°C. 19
  • Citronellol tetrahy- dropyranyl ether (67) was prepared in the usual way in 91% yield. To an ice-cooled and stirred mixture of 17.8 g (74 mmol) of 67, 12.0 g (100 mmol) of CHCI 3 and 0.2 g triethyl- benzylammonium chloride in CH 2 CI 2 (50 ml) was added dropwise 50% aq. NaOH (50 ml). The mixture was stirred vigorously for 19 h at room temperature and then diluted with water (150 ml).
  • the acids 72 were converted in the usual way to the esters 40-45.
  • R-2 (3'f?)-5-(3',7'-Dimethyloctyloxy)-2-methylpyridine
  • S-2 (3'S)-5-(3',7'-Dimethyloctyloxy)-2-methylpyridine
  • acorn barnacles The life cycle of acorn barnacles consists of six planktonic naupliar stages followed by a final larval stage, the cyprid, which after some time normally attaches itself to a substrate and undergoes metamorphosis into the sedentary adult form. Most species are hermaphrodites and after internal fertilization, the egg masses develop in two separate lamellae in the mantle cavity of the adults until the larvae are liberated as fully developed stage I nauplii. For the present study cultured cyprid larvae of three different barnacle species were used: two common marine and brackish water species of Western Europe and Eastern Atlantic North America (Balanus balanoides and B. improvisus), and one warm- water species with a global distribution ( ⁇ . amphitrite).
  • the carboys were kept at a temperature of 27°C and a 15/9h light/dark photo period. To prevent bacterial growth, a mixture of the antibiotics streptomycin and penicillin was added to the vessels at the start of the culture. When the majority (>75%) of the larvae had reached the cyprid stage (usually after 4-5 days), the culture was filtered through plankton sieves in order to separate the cyprids from the nauplii.
  • Cyprids were kept at 2-5°C in filtered seawater before settlement assays were carried out.
  • the settlement assay compares the relative percent settlement of cyprids in control sea- water with settlement in serial dilutions of test compounds.
  • the settlement experiments with the cyprids were performed in static tests in 250 ml beakers using as medium filtered sea water (33-34%o salinity) containing antibiotics (sodium benzylpenicillinate (65 mg) and dihydrostreptomycin sulphate (135 mg) in 4.4 litres of medium).
  • antibiotics sodium benzylpenicillinate (65 mg) and dihydrostreptomycin sulphate (135 mg) in 4.4 litres of medium.
  • the incubation temperature was 7.5°C for ⁇ . balanoides and 17.3°C for B. improvisus, After 6 days the number of permanently settled and non-settled larvae was counted. In order to achieve settlement of cyprid larvae of ⁇ .
  • cyprids were injected (using a pasteur pipette) into the wells of polystyrene 96-well plates containing serial dilution series of test compounds (4 concentra- tions). Each well contained 300 ⁇ l of test solution. Tests were carried out in four replicates. Controls were filtered seawater and seawater with the solvent used to prepare test solutions (dimethyl sulfoxide). Test plates were incubated for 24 hours at a temperature of 27°C and with a 15:9 light-dark cycle. After 24 hours the number of permanently settled and non-settled larvae was counted using a dissection microscope. The following catego- ries were regarded as permanently settled: 1) attached, non-metamorphosed cyprids, 2) decorticated cyprids, and 3) juvenile barnacles.
  • the ether function on the pyridine ring should be at the 3-position.
  • the significance of the ether oxygen may be questioned since the 3-alkylpyridine derivative 51 was highly active, and the related compounds 52-54 exhibited considerable activity as well.
  • replacing the ether oxygen with sulfur does not cause a significant decrease in activity, indicating that the degree of polarity at this end of the molecule is not crucial for activity on barnacles. Branching in the alkyl chain is not essential, but it seems to improve the activity slightly.
  • Replacing the terpenoid moiety of the 3-alkoxy pyridine derivatives with n-alkyl chains (C9-C12) (cf.
  • the antifouling paint was prepared by blending and subsequently grinding for one hour: 35 30 g of binders (15 g acrylate solution and 15 g rosin solution, both 60% solutions in aro- matic hydrocarbon solvent; the acrylate was a copolymer of butyl methacrylate, methacrylic acid and methyl methacrylate), 35 g of pigments (30 g zinc oxide and 5 g titanium dioxide), 15 g of extenders (7 g carbonate and 8 g silicate), 8 g of additives (3 g poly vinyl ethyl ether, 1 g bentonite with ethanol and up to 4 g active ingredients; 2 g juvenile hormone analogue (low level), 4 g juvenile hormone analogue (high level) and 2 g juvenile hormone analogue + 2 g algicide (2-methylthio-4-tert-butylamino-6-cyclopropylamino- triazine) in combination and 12 g solvents (8 g aromatic hydrocarbons and 4 g 2-met
  • the antifouling effectiveness of the tested juvenile hormone analogues against marine organisms was evaluated by exposure tests in tropical seawater (Singapore). For this purpose, paint compositions comprising juvenile hormone analogues were applied on test panels of polyvinyl chloride (20 x 30 x 0.5 cm).
  • test panels were degreased and subsequently coated with the antifouling paint for 48 hours.
  • the thickness of the dry film was 100-150 ⁇ m.
  • the test panels were mounted on larger frames and immersed in seawater at a depth of 0.5-1 m for 8 months.
  • the fouling attachment on the test panels was measured regularly, and a rating of the performance was determined. The calculation of the rating was based on the amount and type of fouling present on the test panel
  • the fouling on the test panels was rated from 0 to 4. Traces of fouling were rated 1 (0- 25% of surface), slight fouling 2 (25-50% of surface), medium fouling 3 (50-75% of surface) and heavy fouling 4 (75-100% of surface). Each fouling organism was given a weight as shown in the Table 2 below. Table 2
  • the fouling organisms referred to in Table 2 are as follows:
  • Dense slime is not easily removed from the surface.
  • Algae Green algae, red algae and brown algae. Animals: Barnacles, tubeworms, mussels, hydroids and bryozoa.
  • the total fouling resistance was calculated by adding up the weightings and then subtract from 100. Zero growth then gives the rating 100 (100-0), and heavy fouling gives the rating 0 (100-100).
  • the antifouling performance was rated as follows: excellent: 98-100, very good: 90-98; good: 70-90; poor: 50-70 and bad: 0-50.
  • control test panel without paint composition comprising juvenile hormone analogues was almost covered with barnacles after 4 months and completely covered after 8 months. After 4 months the rating was "poor” and after 8 months the rating was "bad” (rating 0).

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)
EP00944147A 1999-07-23 2000-07-20 Neue juvenilhormonanaloge und deren verwendung zur als bewuchshemmende mittel Withdrawn EP1204320A2 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DKPA199901055 1999-07-23
DK105599 1999-07-23
US16592199P 1999-11-17 1999-11-17
US165921P 1999-11-17
PCT/IB2000/001003 WO2001006853A2 (en) 1999-07-23 2000-07-20 Novel juvenile hormone analogues and their use as antifouling agents

Publications (1)

Publication Number Publication Date
EP1204320A2 true EP1204320A2 (de) 2002-05-15

Family

ID=26065140

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00944147A Withdrawn EP1204320A2 (de) 1999-07-23 2000-07-20 Neue juvenilhormonanaloge und deren verwendung zur als bewuchshemmende mittel

Country Status (4)

Country Link
EP (1) EP1204320A2 (de)
AU (1) AU5838000A (de)
NO (1) NO20020359D0 (de)
WO (1) WO2001006853A2 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1705171A1 (de) * 2001-12-19 2006-09-27 Flexitral, Inc. Verbesserte Aromastoffe
AU2002366778A1 (en) * 2001-12-19 2003-07-09 Flexitral Inc Improved aromachemicals
US7342042B2 (en) 2001-12-19 2008-03-11 Flexitral, Inc. Lily of the valley aromachemicals
US7309795B2 (en) 2001-12-19 2007-12-18 Luca Turin Citral derivatives
CN101124189A (zh) * 2005-02-17 2008-02-13 弗莱克特瑞尔公司 芳香化学品
CN104222079A (zh) * 2014-08-14 2014-12-24 江西农业大学 一种含有香茅醛乙二缩醛的小黄家蚁驱避剂
CN104222083A (zh) * 2014-08-14 2014-12-24 江西农业大学 一种含有香茅醛1,3-丙二缩醛的小黄家蚁驱避剂

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3709914A (en) * 1970-07-30 1973-01-09 Zoecon Corp Methylenedioxyphenyl compounds
CA1005821A (en) * 1971-02-01 1977-02-22 Clive A. Henrick 2,4-diolefinic compounds and the control of insects
GB1420533A (en) * 1971-09-27 1976-01-07 Cheminova As Pyridine derivatives having juvenile hormone activity
AU5620873A (en) * 1972-06-16 1974-11-28 F. Hoffmann-Laroche & Co. Aktiengesellschaft Polyene derivatives
FR2413877A1 (fr) * 1978-01-06 1979-08-03 Lilly Co Eli Utilisation de derives de pyridine pour reguler la croissance de plantes aquatiques
JPS59199673A (ja) * 1983-04-25 1984-11-12 Sumitomo Chem Co Ltd 含窒素複素環化合物、その製造法およびそれを有効成分とする有害生物防除剤
JPS6036403A (ja) * 1983-08-08 1985-02-25 Sumitomo Chem Co Ltd 混合殺虫組成物
JPS6038303A (ja) * 1983-08-11 1985-02-27 Sumitomo Chem Co Ltd ハエ類の駆除方法
JPS60215671A (ja) * 1984-04-10 1985-10-29 Sumitomo Chem Co Ltd 含窒素複素環化合物、その製造法およびそれを有効成分とする有害生物防除剤
EP0164721A3 (de) * 1984-06-13 1986-02-26 Chisso Corporation Flüssigkristalline Verbindung und flüssigkristalline Zusammensetzung welche diese enthält
DE3522905A1 (de) * 1985-06-27 1987-01-08 Basf Ag O-substituierte 3-oxypyridiniumsalze, verfahren zu ihrer herstellung und ihre verwendung als fungizide fuer den pflanzenschutz
DE3614706A1 (de) * 1986-04-30 1987-11-05 Basf Ag Mittel zur bekaempfung von mikroben
DE3825172A1 (de) * 1988-07-23 1990-01-25 Bayer Ag, 5090 Leverkusen Mittel zur bekaempfung von floehen
CA2020826A1 (en) * 1989-07-11 1991-01-12 Junji Yokoi Antifouling composition
AU660205B2 (en) * 1991-12-23 1995-06-15 Virbac, Inc Systemic control of parasites
DE4409039A1 (de) * 1993-12-21 1995-06-22 Bayer Ag Antifouling-Mittel
US5902808A (en) * 1995-09-29 1999-05-11 Buckman Laboratories International Inc. Methods and compositions for controlling biofouling using N-alkyl heterocyclic compounds
WO2001007047A2 (en) * 1999-07-23 2001-02-01 Bioparken As Control of crustacean infestation of aquatic animals

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0106853A2 *

Also Published As

Publication number Publication date
NO20020359D0 (no) 2002-01-23
AU5838000A (en) 2001-02-13
WO2001006853A3 (en) 2001-12-20
WO2001006853A2 (en) 2001-02-01

Similar Documents

Publication Publication Date Title
CN102234251B (zh) 一种苯并异噻唑酮类化合物及其应用
Xu et al. Potent antifouling compounds produced by marine Streptomyces
Krug Bet-hedging dispersal strategy of a specialist marine herbivore: a settlement dimorphism among sibling larvae of Alderia modesta
US8177896B2 (en) Antifouling furan-2-one derivatives
Willemsen The screening of sponge extracts for antifouling activity using a bioassay with laboratory-reared cyprid larvae of the barnacle Balanus amphitrite
CN102757677B (zh) 一类吲哚生物碱在制备抗海洋生物污损涂料中的应用
EP1204320A2 (de) Neue juvenilhormonanaloge und deren verwendung zur als bewuchshemmende mittel
US8258178B2 (en) Agents for preventing attachment of barnacle consisting of organic solvent extracts of red alga Laurencia sp. and compounds isolated therefrom
EP0706758B1 (de) Mittel gegen den bewuchs durch meeresorganismen
KR100391528B1 (ko) 수생 부착성 유기물의 부착 방지제
Inoue et al. Isocyanides Derived from α, α‐Disubstituted Amino Acids: Synthesis and Antifouling Activity Assessment
Kitano et al. Synthesis and anti-barnacle activities of novel 3-isocyanotheonellin analogues
KR100314105B1 (ko) 오염방지성코팅조성물및이를이용한구조물의보호방법
Vetere et al. A non-toxic antifouling compound for marine paints
CN103396372B (zh) 一类2,5-二酮哌嗪衍生物及其制备方法和在制备抗海洋污损生物防除剂中的应用
KR19990081985A (ko) 트리페닐보란-로진 아민 부가 화합물 및 이의 용도
JP4592153B2 (ja) ジアリールボラン−第１級アミン錯化合物及び水中付着生物防汚剤
Anil et al. Barnacles and their significance in biofouling
US4022903A (en) α-Thienyl and α-substituted thienyl, phenyl and substituted phenyl cyclopropylomethanols useful as biodegradable insecticides and mollusicides
JPS6227057B2 (de)
JP2840965B2 (ja) 漁網防汚剤
CN119684831A (zh) 对羟基苯化合物作为海洋防污剂的用途及其防污剂和涂料
EP0573635A1 (de) Zusammensetzung und Verwendung von substituierten 1,3-Dithiolo- und 1,4-Dithiino-Chinoxalinen als Antimikrobielle Mittel
WO2016204127A1 (ja) 海中付着生物忌避組成物
CN120058491A (zh) 一类三联苯化合物及其作为海洋防污剂的应用

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20020620

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20040203