Classifications

• • 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
  • A01N37/34—Nitriles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
  • C07C331/16—Isothiocyanates
  • C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
  • C07C331/22—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
  • C07C331/24—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing six-membered aromatic rings
• • 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
  • A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
  • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
  • A01N47/44—Guanidine; Derivatives thereof
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
  • A01N47/46—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C265/00—Derivatives of isocyanic acid
  • C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
  • C07C265/06—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
  • C07C265/08—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1612—Non-macromolecular compounds
  • C09D5/1625—Non-macromolecular compounds organic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
  • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes

Definitions

• the invention relates to new and known compounds as well as methods for preventing the attachment of aquatic organisms to surfaces which are submerged for extensive periods of time in water. More particularly, this invention relates to the protection of submerged surfaces with new isonitrile, formamide, isocyanate and isothiocyanate anti-fouling agents.
• fouling organisms such as barnacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidians, tubeworms, Asiatic clams and the like causes economic damage in various ways: for example, attachment to the hulls of ships reduces fuel efficiency and causes loss of profitable sailing time because of the need to clean the hulls. Similarly, the attachment of these organisms to cooling water equipment decreases heat conductivity which eventually reduces or block the cooling power of the equipment and drives up cost.
• a variety of agents useful for controlling fouling organisms in fresh water or sea water have been used to prevent the attachment and overgrowth of these organisms.
• a common method of controlling the presence or attachment of fouling organisms is to coat or permeate the underwater structure with a composition which comprises mixtures of toxic compounds such as tri-n-butyl tin or copper compounds.
• Anti- fouling agents in the form of a paint can contain up to 60% by weight of the active ingredients and can be used to paint surfaces such as the hull of ships. The paint prevents attachment and growth of fouling organisms by continuously releasing anti- fouling agents underwater.
• the disadvantage of many of the present anti-fouling agents is that they are persitant in the environment, are often acutely toxic and degrade too slowly in aquatic environments and are, therefore, ecologically harmful. Hazardous anti-fouling agents can eventually bioaccumulate and enter the food chain and therefore represent a threat to marine and human life.
• the present invention provides new and known compounds and a method to prevent settlement on surfaces by marine or freshwater fouling organism which comprises contacting said organism or the locus thereof with an anti-fouling-effective amount of at least one compound of formula 11-113
• R 1 represents NR 2 R 3 wherein
• R 2 represents a hydrogen atom, Cl - C8-alkyl
• R 4 represents a hydrogen atom or one of the groups OR 5 or NHR 5 wherein R 5 designates Cl - C8-alkyl or aryl, each optionally substituted by halogen; or
• R 6 represents a hydrogen atom, Cl - C6-alkyl or aryl
• R 7 represents Cl - C6-alkyl or aryl, each optionally substituted by halogen; or
• R 1 represents an isonitrile, isocyanate, isothiocyanate or a guanidino group; and n represents 0 or 1.
• halogen has the meaning of Cl, Br, I or F
• alkyl has the meaning of straight-chain or branched alkyl with 1 to 8, preferably 1 to 4 carbon atoms
• aryl has the meaning of aromatic, mono- or polycyclic hydrocarbon rings such as for example and preferred: naphthyl, anthranyl, phenanthryl, especially phenyl.
• R 1 represents NR 2 R 3 wherein
• R 2 represents a hydrogen atom or Cl - C4-alkyl and R 3 represent .s wherein R represents a hydrogen atom or one of the groups OR 5 or NHR 5 wherein R 5 represents Cl - C4-alkyl or aryl, each optionally substituted by halogen; or
• R 6 represents a hydrogen atom, methyl or optionally halogen substituted aryl
• R 7 represents Cl - C4-alkyl or optionally halogen substituted aryl
• R 1 represents an isonitrile, isocyanate, isothiocyanate or guanidino moiety.
• R 2 represents a hydrogen atom
• R 4 represents OR 5 or NHR 5 wherein
• R 5 represents methyl, ethyl, n- or i-propyl or n-,s-,i- or t-butyl, or phenyl which is optionally substituted by halogen.
• R 6 represents methyl, ethyl, n- or i-propyl, n-,s-,i- or t-butyl, or preferred a hydrogen atom or and
• R 7 represents methyl, ethyl, n- or i-propyl, n-,s-,i- or t-butyl or phenyl. Especially preferred are also compounds of formula 11 - 113 wherein
• R 1 represents an isonitrile, isocyanate, isothiocyanate or guanidino moiety.
• the aforementioned compounds are accessible by standard procedures of organic chemistry which can be adopted to the Rosin moiety.
• the starting Rosin derived from Tall Oil, Gum or Wood is commercially available; for example Rosin amine as Hercules® Amine D.
• Rosin amine as Hercules® Amine D.
• An overview on the different isomers of abietic acid as well as their preparation is given by Gang-Fung Chen in Progress in Organic Coatings 20, 1992, 139-167.
• the reaction sequences can be adopted easily to the other pure isomers and rosin oxidation/reduction products and also to mixtures of them.
• Ureas of formula III can be synthesized by reacting Rosin amine with an isocyanate in an inert solvent (benzene, toluene, hydrocarbons etc.); see: Houben-Weyl Vol. E4, 1983, 352-357 or alternatively via reaction of Rosin isocyanate (s. below) with an aliphatic or aromatic amine.
• an inert solvent benzene, toluene, hydrocarbons etc.
• Rosin isothiocyanate (CAS-Nr.: 115 269-93-7) can be synthesized from Rosin amine through reaction with thiophosgene (see analogous sequence with phosgene: Ozaki, Chem Rev. 72, 457-460), or alternatively with a thiophosgene substitute, namely thiocarbonyl-diimidazole (see example 3).
• a fouling organism which may be combatted or controlled by the method of the invention can be any marine or freshwater organism which can attach to an inner or outer surface of a structure which is submerged or in continual contact with water.
• Examplary organisms include algae, including members of the phyla Chlorophyta, Pharophyta and Rhodophyta; tunicates, including members of the class Ascidiacea such as Ciona intestinalis, Diplosoma listerianium and Botryllus sclosseri, and members of the class Hydrozoa including Clava squamata, Hydractinia echinata, Obelia geniculata and Tubularia larynx;
• Bivalves including Mytilus edulis, Cassostrea virginica, Ostrea edulis, ostrea chilensia, Lasaea rubra and members of the family Dreissenidae (or zebra mussels) and members of the family Corbuculidae (or Asiatic clams), bryozoans including Electra pilosa, Conopeum reticulatum, Bugula neritina and Bowerbankia gracilis;
• Polychaete worms including Hydroides norvegica, Pomatoceros triqueter, Mercierella enigmata and Spirorbis spp.;
• Sponges and members of the class Cirripedia such as Balanus amphitrite, Lepas anatifera, Balanus balanus, Balanus balanoides, Balanus hameri, Balanus creatus, Balanus improvisus, Balanus galeatus, Balanus eburneus, Elminius modestus, Balanus tulipiformis and Balanus perforatus.
• barnacles such as Balanus amphitrite, Lepas anatifera, Balanus balanus, Balanus balanoides, Balanus hameri, Balanus creatus, Balanus improvisus, Balanus galeatus, Balanus eburneus, Elminius modestus, Balanus tulipiformis and Balanus perforatus.
• Organisms of the genus Balanus are frequent foulers of aquatic structures.
• Specific fouling organisms to which this invention is especially directed include barnacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidians, tube worms and asiatic clams, but also the bacterial slime.
• compound of formula II - 113 may be brought into contact with a fouling organism by:
• the amount of Rosin Amine Derivative to be used in the method of invention will vary according to the specific compound used, the identity of the fouling organism to be controlled, degree of fouling pressure of the surrounding aquatic environment, the water temperature, the mode of contact and the like.
• the Rosinamine derivatives can be used as individual active compounds or else in combination with active compounds usually employed in the anti-fouling sector.
• These can preferably be heavy metals, such as Cu, or heavy metal compounds, such as, for example, bis(trialkyltin) sulphides, tri-n-butyl laurate, tri-n-butyl chloride, copper(I) oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)-tin, tri- butyltin oxide, molybdenum disulfide, antimony oxide, polymeric butyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, the zinc salt or copper salt of 2-pyridinethiol-l -oxide, bisdimethyl
• the action spectrum of the rosinamine derivatives is extended further or particular effects are achieved by these combinations of active compounds. Synergistic effects are obtained in many cases. The synergistic effect manifests itself particularly clearly if the active compound combinations are present in certain weight ratios. However, the weight ratios of the active compounds in the active compound combinations can vary within a relatively wide range.
• Preferred combination partners for the rosinamine derivatives are algicides, such as diuron, dichlorophen, endothal, fentin acetate or quinoclamine, molluscicides, such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb, fungicides, such as dichlofluanid, tolylfluanid, iodopropargyl butylcarbamate, fluor- folpet and azoles, such as propiconazole, metconazole, cyproconazole and tebucona- zole or conventional antifouling active compounds, such as 2-(N,N-dimethylthio- carbamoylthio)-5-nitrothiazyl, tetrabutyldistannoxane, 2-tert-butylamino-4-cyclopro- pylamino-6-methylthio-l
• the anti-fouling composition preferably comprises the rosinamine derivatives in concentrations of 0.5 to 60% by weight, preferably between 1 to 25% by weight.
• Compositions of the invention comprise an aquatically acceptable inert carrier and an antifouling-effective amount of a Rosin Amine Derivative of formula I.
• preferred compositions of the invention include a film-forming component such as a polymer resin solution.
• Exemplary polymer resins include unsaturated polyester resins formed from: a) unsaturated acids or anhydrides, such as maleic anhydride , fumaric acid, itaconic acid and the like; b) saturated acids or anhydrides, such as phthalic anhydride, isophthalic anhydride, terephthalic anhydride, tetrahydrophthalic anhydride, tetrahalophthalic anhydride, adipic acid, subacic acid, and the like; c) glycols, such as ethylene glycol, and the like; d) vinyl monomers, such as styrene, vinyl toluene, chlorostyrene, bromostyrene, acrylates like methylmethacrylate, ethylene glycol dimethacrylate and the like.
• Other suitable resins include vinyl ester-, vinyl acetate-, and vinyl chloride-based resins, elastomeric components, vulcanized rubbers, rosins, metalresinates
• Rosinamine (Hercules® Amine D) is a mixture of primary amines derived from modified Rosin. It is described as dehydroabietylamine of technical grade and was used in the following syntheses without further purification.
• Dishes are incubated for 24h at a temperature of 27°C ⁇ 2. After incubation the cyprids are screened for signs of toxicity. Larvae are classified in three categories: A) alive and swimming; B) alive but not active; C) dead. The test is terminated by addition of a drop of 20% formaldehyde and the numbers of settled and non-settled larvae are counted.
• Categories 2 and 3 are considered to be settled. Percentage settlement in test solution is compared with controls. Estimates of the median effect concentration (EC-50) after 50 hrs. are calculated using the Spearman-Karber method.
• the stock solutions are used to prepare several dilution series in seawater. Controls are made of seawater, or, if appropiate, in a mixture of seawater and solvent.
• the solvent concentration in the controls is equal to the highest concentration in the test solution.
• As an internal standard (positive control) a concentration range of 0 to

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• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Dentistry (AREA)
• Environmental Sciences (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
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• Agronomy & Crop Science (AREA)
• Zoology (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Paints Or Removers (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 1999
  • 1999-03-16 EP EP99105349A patent/EP1036786A1/en not_active Withdrawn
• 2000
  • 2000-03-10 DK DK00910806T patent/DK1163210T3/da active
  • 2000-03-10 ES ES00910806T patent/ES2215617T3/es not_active Expired - Lifetime
  • 2000-03-10 US US09/936,124 patent/US6972111B1/en not_active Expired - Fee Related
  • 2000-03-10 AT AT00910806T patent/ATE258915T1/de not_active IP Right Cessation
  • 2000-03-10 CA CA002367343A patent/CA2367343A1/en not_active Abandoned
  • 2000-03-10 KR KR1020017011754A patent/KR20020003549A/ko not_active Ceased
  • 2000-03-10 PT PT00910806T patent/PT1163210E/pt unknown
  • 2000-03-10 WO PCT/EP2000/002118 patent/WO2000055117A1/en not_active Ceased
  • 2000-03-10 JP JP2000605548A patent/JP2002539184A/ja active Pending
  • 2000-03-10 NZ NZ514174A patent/NZ514174A/en unknown
  • 2000-03-10 AU AU32881/00A patent/AU771014B2/en not_active Ceased
  • 2000-03-10 MX MXPA01009319A patent/MXPA01009319A/es not_active Application Discontinuation
  • 2000-03-10 CN CNB008051399A patent/CN1192013C/zh not_active Expired - Fee Related
  • 2000-03-10 DE DE60008078T patent/DE60008078T2/de not_active Expired - Fee Related
  • 2000-03-10 HK HK02107162.5A patent/HK1045499B/zh not_active IP Right Cessation
  • 2000-03-10 EP EP00910806A patent/EP1163210B1/en not_active Expired - Lifetime
• 2001
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