EP0717591A4 - Insecticidal composition - Google Patents

Insecticidal composition

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Publication number
EP0717591A4
EP0717591A4 EP94926721A EP94926721A EP0717591A4 EP 0717591 A4 EP0717591 A4 EP 0717591A4 EP 94926721 A EP94926721 A EP 94926721A EP 94926721 A EP94926721 A EP 94926721A EP 0717591 A4 EP0717591 A4 EP 0717591A4
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
halo
group
substituted
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Withdrawn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
EP94926721A
Other languages
German (de)
French (fr)
Other versions
EP0717591A1 (en
Inventor
Ian Maxwell Russell
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.)
Commonwealth Scientific and Industrial Research Organization CSIRO
Original Assignee
Commonwealth Scientific and Industrial Research Organization CSIRO
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Application filed by Commonwealth Scientific and Industrial Research Organization CSIRO filed Critical Commonwealth Scientific and Industrial Research Organization CSIRO
Publication of EP0717591A1 publication Critical patent/EP0717591A1/en
Publication of EP0717591A4 publication Critical patent/EP0717591A4/en
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/006—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with wool-protecting agents; with anti-moth agents
    • 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
    • A01N37/28—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 containing the group; Thio analogues thereof

Definitions

  • the present invention is concerned with the use of insecticidally active compounds for the treatment of wool or wool-containing materials.
  • the invention is also concerned with insecticidally active compositions which are capable of protecting wool or wool-containing materials against insect attack.
  • Permethrin is currently the main commercial mothproofing chemical. In the UK, aquatic discharges of permethrin will be restricted from the start of 1993. This decision effectively stops the dyebath application of permethrin, as small amounts of insect resist chemical will always be discharged with the exhausted liquors even under the best industrial conditions. Although permethrin can still be used for treatment of wool, it must be applied in totally contained systems that do not give rise to environmental residues.
  • Dyebath application is the simplest, cheapest and most universal point in the wool processing sequence to apply mothproofing agents; no specialised equipment is needed, and the high temperature application provides a treatment with optimum fastness properties. If insect-resist agents are to be applied to wool in the dyebath, special compounds with very low hazard to aquatic organisms of all kinds must be used. Disclosure of the Invention
  • a further object of this invention is to provide a mothproofing treatment which is more environmentally acceptable that the prior art treatments referred to above.
  • substituents A, B, X, X', R 1 , R 2 , R 3 and R 4 are as defined in above-mentioned Australian application no. 76287/87, that is, wherein X and X' are the same or different O.S or NR;
  • R 1 is hydrogen; (C r C 6 ) alkyl; (C r C 6 ) alkoxy-(C r C 6 ) alkoxy-(C r C 6 ) alkyl having independently the stated number of carbon atoms in each alkyl group; (C r C 6 ) alkylthio- (C-C 6 ) alkyl having independently the stated number of carbon atoms in each alkyl group; (C 2 .-C 6 ) alkenyi; (C 2 -C 6 ) alkynyl; or phen-(C.,-C 4 ) alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C,-C 4 ) alkyl, halo-(C,-C 4 ) alkyl (C r C 4 )-alkoxy, halo-(C,-C 4 ) alkoxy, carb
  • R 2 and R 3 are the same or different hydrogen or (C C 4 ) alkyl;
  • R 4 is (C C 4 ) alkyl substituted with 1 to 4 fluoro; straight chain (C 2 -C 4 ) alkenyi; carboxyl; (C
  • a and B are the same or different unsubstituted or substituted naphthytyl where the substituents can be from one to three of the same or different halo; nitro; (C C 4 )- alkoxy; (C,-C 4 ) alkyl or NZZ';
  • the present invention provides a method of mothproofing wool or a wool- containing product said method including treating said wool or wool-containing product with an effective amount of a compound according to the formula (I)
  • the treatment compound has relatively low water solubility.
  • the water solubility of the treatment compound is less than 1 mg/l, although compounds with higher solubility may be used.
  • the treatment compound is a compound having the following formula:
  • the treatment compound may be of the formula:
  • the treatment compound may be applied at a level of about 0.001 % - 0.5%.
  • the treatment compound may be applied in a dyebath, either to the whole of the wool or wool blend lot, or by overtreatment of a small fraction with subsequent blending with untreated wool.
  • the treatment compound may be applied by continuous padding, scouring application, continuous application in chemical setting or tape scouring, foam application, encapsulation in particles, centrifuge, or minibowl.
  • the wool product may be subjected to steaming or heating following application of the treatment compound.
  • the treatment compound may be applied as a solution in an organic solvent, for example, ethanol.
  • the treatment compound may also be applied as a suspension of the micro- ground compound, a self-emulsifiable concentrate or other water-based formulation as application vehicles.
  • Compound (IV) which is relatively hydrophobic, has a specific activity to lepidoptera larvae and with water solubility below 1 mg/l, is more environmentally acceptable than permethrin.
  • the treatment compounds of the present invention have very high insecticidal activity against all five of our test strains of clothes moths: common clothes moth (Tineola bisselliella), dieldrin resistant and dieldrin susceptible strains; casebearing clothes moth (Tinea translucens), susceptible, dieldrin resistant and pyrethroid resistant strain.
  • Insect-resist activity is required to persist through the life-time of a wool product.
  • Application of 5-10 fold excess of active ingredient above the minimum active level may be used to ensure protection even after 80%-90% losses through volatility, exposure to light, and cleaning (washing, shampooing and dry-cleaning).
  • compound (IV) has more than adequate fastness for a commercial insect-resist treatment.
  • compound (IV) has similar washing performance to conventional synthetic pyrethroid (permethrin or cycloprothrin) mothproofing compounds and better dry cleaning resistance and light fastness.
  • the present invention provides, in a second aspect, a method of treating a wool or wool-containing product the method including treating the wool or wool-containing product with a compound according to formula (I) together with an agent which has an activity against beetles.
  • a treatment compound of the invention may have a synergistic effect on the activity of an agent having activity against beetles.
  • the agent active against beetles may be a compound selected from synthetic pyrethroids, repellants and disinfectant materials, and other specialty wool insect resist agents of the aryl ureido and amide class.
  • the agent active against beetles may be permethrin or bifenthrin, as examples of pyrethroids with a high activity against beetles.
  • the agent may be selected from hexahydropyrimidine derivative (HHP): N-(3,4-dichlorophenyl)-1,2,3,4-tetrahydro-6- hydroxy-1 ,3-dimethyl-2,4-dioxo-5-pyrimidinecarboxamide, flucofuron: N,N'-bis[4-chloro-3- (trifluoromethyl)phenyl] urea, butyl ester of 4-hydroxy benzoic acid, and sulcofuron:5- chloro-2-(4-chloro-2-(3,4-chlorophenyl)) phenoxyureido benzene sulfonate (as alkali salt, for example the sodium salt).
  • the agent having activity against beetles may be a nitromethylene of formula
  • the agent having activity against beetles is applied at a level of about 0.0001% to 0.1%.
  • the present invention provides a treatement composition suitable for use in the method of the present invention said composition including one or more compounds of formula (I) to (IV) and optionally including one or more compounds active against beetles.
  • Figure 1 shows the Freundlich adsorption isotherm for compound (IV) on wool at 100°C
  • Figure 2 is a graph showing light fastness of woolen fabrics treated with compound (IV);
  • Figure 3 is a graph showing the handwashing characteristics of fabrics treated with compound (IV).
  • Figure 4 is a graph showing the effect of dry cleaning on wool treated with compound
  • Compounds according to formula (III) may be prepared by benzoylation of a t-butyl hydrazine under Schotten-Baumann conditions. The product was recrystallised from methanol-ether; purity and structure were confirmed by nmr.
  • Wool was treated with the insecticide in an Ahiba dyeing apparatus at 100°C for 30 minutes as described in AS2001.
  • the insecticide was applied at the start of the dyeing cycle either as an ethanol solution, or as a micro-ground suspension (Compound (IV) 2F 23%ai or Compound (IV) FL 20%ai).
  • Fabrics were rinsed in cold water then air dried after application. Generally 20g of wool was treated in 500cm 3 of water.
  • Hot dyebath liquors (75ml) were taken from the dyebath and diluted to 100ml with methanol. The resulting solutions were used directly for HPLC analysis. Wash and Dry Clean Fastness testing
  • Permethrin was applied to wool from boiling dyebaths.
  • the treatment compounds caused 100% kill in the 14 day test. At levels around 0.00025%, approximately 50% of the larvae were still alive, but appeared abnormal. Even at levels of 0.0001%, larval feeding was only 30-40% of control wool. At high level (0.1%), the Tinea larvae crawled from their cases before dying, usually an indicator of distress.
  • Insect-resist activity is required to persist through the life-time of a wool product.
  • Application of a 5-10 fold excess of active ingredient above the minimum active level ensures insect protection even after 80-90% losses through volatility, exposure to light, and cleaning (washing, shampooing and drycleaning).
  • Exposures of 1 , 2, 3, and 4 weeks correspond to blue scale ratings of 3, 5, and 6 respectively.
  • Bracketed values in the body of the table are percentages of the initial application remaining after the specified exposure.
  • Compound (IV) has more than adequated light fastness for a commercial insect-resist treatment. Under these same accelerated testing conditions, only 40-50% of an initial application of permethrin would remain.
  • Compound (IV) has similar washing performance and better drycleaning resistance. Losses in handwashing are confirmed by both insect bioassay (Table 5) and by chemical analysis (Table 6, and Fig. 3). Losses in drycleaning are small (Table 6, Fig. 4).
  • Bracketed values in the body of the table are percentages of the initial amount remaining after the specified exposure.
  • Compound (IV) has little direct beetle activity at this treatment level, it greatly enhances the effect of the 4-hydroxybenzoic acid ester.

Abstract

A method of mothproofing wool or a wool-containing product, the method including treating the wool or wool-containing product with an effective amount of a compound according to formula (I).

Description

INSECTICIDAL COMPOSITION
Technical Field
The present invention is concerned with the use of insecticidally active compounds for the treatment of wool or wool-containing materials. The invention is also concerned with insecticidally active compositions which are capable of protecting wool or wool-containing materials against insect attack.
Background
Permethrin is currently the main commercial mothproofing chemical. In the UK, aquatic discharges of permethrin will be restricted from the start of 1993. This decision effectively stops the dyebath application of permethrin, as small amounts of insect resist chemical will always be discharged with the exhausted liquors even under the best industrial conditions. Although permethrin can still be used for treatment of wool, it must be applied in totally contained systems that do not give rise to environmental residues.
The suitability of permethrin for insect-resist treatment of wool in Australia has declined due to the occurrence of a pyrethroid-resistant strain of the case bearing clothes moth (Tinea translucens) Increased application levels of permethrin have been used as a temporary measure to combat this insect, but this has exacerbated the environmental problems by increasing dyebath discharges.
Dyebath application is the simplest, cheapest and most universal point in the wool processing sequence to apply mothproofing agents; no specialised equipment is needed, and the high temperature application provides a treatment with optimum fastness properties. If insect-resist agents are to be applied to wool in the dyebath, special compounds with very low hazard to aquatic organisms of all kinds must be used. Disclosure of the Invention
It is an object of the present invention to provide an insecticidally active composition and method of treatment which can be used to provide practical mothproofing for wool or wool product such as textiles. A further object of this invention is to provide a mothproofing treatment which is more environmentally acceptable that the prior art treatments referred to above. We have found that the insecticidally active N-optionally substituted-N'- substituted hydrazines of formula (I) below as disclosed in Australian Patent application no. 76287/87 (the disclosure of which is incorporated herein by reference) may be used to provide an effective mothproofing treatment of wool or wool-containing products.
(I)
where the substituents A, B, X, X', R1, R2, R3 and R4 are as defined in above-mentioned Australian application no. 76287/87, that is, wherein X and X' are the same or different O.S or NR;
R1 is hydrogen; (CrC6) alkyl; (CrC6) alkoxy-(CrC6) alkoxy-(CrC6) alkyl having independently the stated number of carbon atoms in each alkyl group; (CrC6) alkylthio- (C-C6) alkyl having independently the stated number of carbon atoms in each alkyl group; (C2.-C6) alkenyi; (C2-C6) alkynyl; or phen-(C.,-C4) alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C,-C4) alkyl, halo-(C,-C4) alkyl (CrC4)-alkoxy, halo-(C,-C4) alkoxy, carboxy, (C C4) alkoxy- carbonyl, (CrC4) aikanoyloxy or NZZ';
R2 and R3 are the same or different hydrogen or (C C4) alkyl; R4 is (C C4) alkyl substituted with 1 to 4 fluoro; straight chain (C2-C4) alkenyi; carboxyl; (C|-C3) alkoxy-carbonyl; cyano; cyano substituted (C,-C4) alkyl, tri(CrC4)- alkysilyl having independently the stated number of carbon atoms in each alkyl group; or tri(C C2) alkylsilylmethyl having independently the stated number of carbon atoms in each alkyl group; provided that R2 and R3 are both alkyl when R4 is carboxyl or alkoxycarbonyl; and
A and B are the same or different unsubstituted or substituted naphthytyl where the substituents can be from one to three of the same or different halo; nitro; (C C4)- alkoxy; (C,-C4) alkyl or NZZ';
unsubstituted or substituted phenyl where the substituents can be from one to five of the same or different halo; nitroso; nitro; cyano; hydroxy; (CrC6) alkyl; halo-(Cr C6)-alkyl; cyano-(C,-C6) alkyl; hydroxy-(C..-C6)-alkyl; (C C6)alkoxy; halo-(CrC6) alkoxy; (C C6) alkoxy-(C C6) alkyl having independently the stated number of carbon atoms in each alkyl group; (C|-C6) alkoxy-(C C6) alkoxy having independently the stated number of carbon atoms in each alkyl group; -ORSR' group; -OCO2R group; -OCO2H group; (C 6) alkanoyloxy-(C.|-C6) alkyl having independently the stated number of carbon atoms in each alkyl group; (C2-C6) alkenyi optionally substituted with halo, cyano, (Cr C4) alkyl, halo-(C C4)-alkoxy, (CrC4) alkylthio or (C C4)alkoxy; (C C4)alkadienyl; (C2- C6) alkenyloxy; (C2-C6) alkenyl-carbonyl; (C2C6)-alkenyloxy-carbonyloxy; (C2-C6) alkynyl optionally substituted with halo, cyano, nitro, hydroxy, (C C4) alkoxy, halo-(C C4)alkyl, (C,-C4) alkylthio or (CrC4)-alkyl; carboxy; -RCO2R' group; -COR; -COH; halo-(C C6) alkyl-carbonyl; -C02R group; (CrC6) haloalkoxy-carbonyl; -OCOR group; -ORC02R' group; amino (-NZZ'); amino substituted with hydroxy, (C C4) alkoxy or (C|-C4) alkylthio; -CONZZ' group; (C2-C6)- alkenyl-carbonylamino; hydroxy-(CrC6)-alkylamino- carbonyl; -OCONZZ' group; -NZCOZ' group; -NZC02Z' group; thiocyanato; isothiocyanato; (C,-C6) thiocyanatoalkyl; (CrC6) alkylthio; haio-(C1-C6) alkylthio; -S(O)Z group; -S02Z group; -OS02R group; -OS02H group; -S02NZZ' group; -CSR group; - CSH group; -SCOR group; -SCOH group -NSCSZ' group; unsubstituted or substituted phenyl having one to three of the same or different halo, cyano, nitro, hydroxy (C,-C4) alkyl, halo-(C1-C4)alkyl, (C-pC -alkoxy, carboxy, (CrC4)alkoxy-carbonyl, (C C4)alkanoyloxy, amino, (CrC4)-alkylamino or di(C C4) alkylamino having independently the stated number of carbon atoms in each alkyl group; phenoxy where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C C4) alkyl, halo-(CrC4) alkyl, (CrC4)-alkoxy, carboxy, (CrC4)alkyl- carbonyl, (C C4)alkanoyloxy, amino, (C C4)-alkylamino or di(C C4)alkylamino having independently the stated number of carbon atoms in each alkyl group; benzoyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C1-C4)alkyl, halo-(CrC4)alkyl, (CrC4)-alkoxy, carboxy, (Cr C4)alkoxy-carbonyl, (C C4) alkanoyloxy, amino, (C,-C4) alkylamino or di(Cr C4)alkylamino having independently the stated number of carbon atoms in each alkyl group; benzoyloxy (CrC6)alkyl; phenylthio-(C1-C6) alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy,(C C4) alkyl, halo-(CrC4)alkyl, (C C^-alkoxy, carboxy, (C C4)alkoxy- carbonyl, (C.,.C4)-alkanoyloxy, amino, (CrC4)alkylamino or di(C1-C4)alkylamino having independently the stated number of carbon atoms in each alkyl group; -CR=N-R'" group where R'" is hydroxy, (C C4)alkyl, (C.,-C4)alkoxy, amino (-NZZ'), phenylamino, -COR, - COH or benzoyl; (C2-c6) oxiranyl; acetylthiosemi- carbazone; pyrrolyl; oxazolyl, unsubstituted or substituted with one or two methyl group; or when two adjacent positions on the phenyl ring are substituted with alkoxy groups, these groups may be joined to form, together with the carbon atoms to which they are attached, a 5 or 6 membered dioxolano or dioxano heterocyclic ring; unsubstituted or substituted (Cr C10)alkyl having one to four of the same or different halo, cyano, nitro, hydroxy, (Cr C4)alkoxy, halo-(C.,-C4)alkoxy, carboxy, (C.,C4)-alkoxy-carbonyl, (CrC4) alkanoyloxy, phenyl or -NZZ';
unsubstituted or substituted (C3-C8) cycloalkyl or unsubstituted or substituted (C3-C8) cyclo (C,-C4) alkyl having one to four of the same or different halo, cyano, nitro, hydroxy, (C C4) alyl, halo-(CrC4)-alkyl, (C C4) alkoxy, halo-(C C4) alkoxy, carboxy, (C C4) alkanoyl, (C1-C4)-alkoxy-carbonyl, (C,-C4) alkanoyloxy or -NZZ';
unsubstituted or substituted (C2-C8)alkenyl or unsubstituted or substituted (C2-
C8)-alkadienyl having as substituent(s) a furyl, thienyl or pyridyl or one to four of the same or different halo, cyano, nitro, hydroxy, (C1-C4)alkyl, (C3-C6)cycloalkyl, halo-(C C4)alkyl, (C C4)alkoxy, halo-(C1-C4)alkoxy, carboxy, (C C4)-alkoxyl-carbonyl, (C C4) alkanoyloxy or -NZZ'; unsubstituted or substituted (C3-C8)cycloalkenyl or unsubstituted or substituted (C3-C8)cycloalkadienyl having as substituent(s) one to four of the same or different halo, cyano, nitro, hydroxy, (C C4)alkyl, halo-(C C4)alkyl, (C C4)-alkoxy, halo-(C C4)alkoxy, carboxy, (C1-C4)alkoxy-carbonyl, (CrC4)alkanoyloxy or -NZZ'; unsubstituted or substituted (C2-C8)alkynyl having as substituent(s) one to four of the same or different halo, cyano, nitro, hydroxy, (C.,-C4)alkyl, halo-(C C4)alkyl, (C C4)alkoxy, halo-(CrC4)alkoxy, carboxy, (C C4)alkoxy-carbonyl, (C,-C4)alkanoyloxy, phenyl or -NZZ'; phenalkyl having one to four carbon atoms in the alkyl group and wherein the alkyl group is unsubstituted or substituted with one to three of the same or different halo, cyano, hydroxy, (C C4)alkoxy, (C C4)-alkoxy-carbonyl or -NZZ' and the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C C4)alkyl, halo-(C C4)alkyl, cyano-CC^C^alkyl, (C C4)-alkoxy, halo-(C C4) alkoxy, carboxy, (C1-C4)alkoxy-carbonyl, (C C4)alkanoyloxy, (C2- C6)alkenyl, halo-(C2-C6)alkenyl, (C2-C6)alkynyl or -NZZ'; phenalkenyl having two to six carbon atoms in the alkenyi group and the alkenyi group is unsubstituted or substituted with one to three of the same or different halo, cyano, hydroxy, (C C4)alkyl, halo-(C1-C4)alkyl, (C,-C4)alkoxy, halo-(C C4)alkoxy, (Cr C4)-alkoxy-carbonyl or -NZZ', and the phenyl ring is unsubstituted or substituted with one to or three of the same or different halo, cyano, nitro, hydroxy, (CrC4) alkyl, halo- (C C4)alkyl, (C C4)alkoxy, halo-(C.,-C4)-alkoxy, carboxy, (C.,-C4)alkoxy-carbonyl, (C C4)alkanoyloxy or -NZZ'; unsubstituted or substituted five-membered heterocycle selected from furyl, thienyl, triazolyl, pyrrolyl, isopyrrolyl, pyrazolyl, isoimdazolyl, thizolyl, isothiazolyl, oxazolyl and isooxazolyl where the substituents can be from one to three of the same or different halo; nitro; hydroxy; (CrC6)alkyl; (CrC6)alkoxy; carboxy; (CrC6) alkoxy- carbonyl; -RCO2H group RCO2R' group; -CONZZ' group; amino (-NZZ'); -NZCOZ' group; (C C6)alkylthio; or unsubstituted or halo substituted phenyl having one to three of the same or differnt halo, nitro, (C1-C6)alkyl, halo-alkyl, (C C6)alkoxy, halo- (C.,-C6)- alkoxy, carboxy, (C1-C )alkoxy-carbonyl or amino (-NZZ'); or unsubstituted or substituted six-membered heterocycle having one, two, three or four nitrogen atoms and two to five nuclear carbon atoms where the substituents can be from one to three of the same or different halo; nitro; hydroxy; (CrC6)alkyl; (Cr C6)alkoxy; carboxy; (CrC6)-alkoxy-carbonyl; -RCO2H group; -RCO2R' group; -CONZZ' group; amino (-NZZ'); -NZCOZ' group; (C.,-C6)alkylthio; or unsubstituted or substituted phenyl having one to three of the same or different halo, nitro, (C1-C6)alkyl, halo-(Cr C6)alkyl, (CrC6) alkyl, (C C6)alkoxy, halo-(C1-C6)- alkoxy, carboxy, (C.,-C4)alkoxy- carbonyl or amino (-NZZ'); where R and R' are (CrC6)alkyl; Z and Z' are hydrogen or (CrC4)alkyl; "amino" means NZZ'.
Accordingly, the present invention provides a method of mothproofing wool or a wool- containing product said method including treating said wool or wool-containing product with an effective amount of a compound according to the formula (I)
Preferably the treatment compound has relatively low water solubility. Preferably the water solubility of the treatment compound is less than 1 mg/l, although compounds with higher solubility may be used. Preferably the treatment compound is a compound having the following formula:
(ll) wherein R5 and R6 which may be identical or different may be selected from H or C^ alkyl and n=1-5.
The treatment compound may be of the formula:
(III) Especially preferred is a compound of formula (IV) , the treatment compound has formula:
(IV)
The treatment compound may be applied at a level of about 0.001 % - 0.5%.
The treatment compound may be applied in a dyebath, either to the whole of the wool or wool blend lot, or by overtreatment of a small fraction with subsequent blending with untreated wool. Alternatively the treatment compound may be applied by continuous padding, scouring application, continuous application in chemical setting or tape scouring, foam application, encapsulation in particles, centrifuge, or minibowl. The wool product may be subjected to steaming or heating following application of the treatment compound.
The treatment compound may be applied as a solution in an organic solvent, for example, ethanol. The treatment compound may also be applied as a suspension of the micro- ground compound, a self-emulsifiable concentrate or other water-based formulation as application vehicles.
Compound (IV), which is relatively hydrophobic, has a specific activity to lepidoptera larvae and with water solubility below 1 mg/l, is more environmentally acceptable than permethrin. We have found that the treatment compounds of the present invention have very high insecticidal activity against all five of our test strains of clothes moths: common clothes moth (Tineola bisselliella), dieldrin resistant and dieldrin susceptible strains; casebearing clothes moth (Tinea translucens), susceptible, dieldrin resistant and pyrethroid resistant strain.
Insect-resist activity is required to persist through the life-time of a wool product. Application of 5-10 fold excess of active ingredient above the minimum active level may be used to ensure protection even after 80%-90% losses through volatility, exposure to light, and cleaning (washing, shampooing and dry-cleaning).
We have found that compound (IV) has more than adequate fastness for a commercial insect-resist treatment. We have also found that compound (IV) has similar washing performance to conventional synthetic pyrethroid (permethrin or cycloprothrin) mothproofing compounds and better dry cleaning resistance and light fastness.
In insect-resist treatment of wool products, it is highly desirable to also provide protection against beetles such as a carpet beetle species. Compounds according to formula (I) do not have significant activity against beetles.
Accordingly, the present invention provides, in a second aspect, a method of treating a wool or wool-containing product the method including treating the wool or wool-containing product with a compound according to formula (I) together with an agent which has an activity against beetles.
It has been surprisingly found that the presence of a treatment compound of the invention may have a synergistic effect on the activity of an agent having activity against beetles.
The agent active against beetles may be a compound selected from synthetic pyrethroids, repellants and disinfectant materials, and other specialty wool insect resist agents of the aryl ureido and amide class.
The agent active against beetles may be permethrin or bifenthrin, as examples of pyrethroids with a high activity against beetles. The agent may be selected from hexahydropyrimidine derivative (HHP): N-(3,4-dichlorophenyl)-1,2,3,4-tetrahydro-6- hydroxy-1 ,3-dimethyl-2,4-dioxo-5-pyrimidinecarboxamide, flucofuron: N,N'-bis[4-chloro-3- (trifluoromethyl)phenyl] urea, butyl ester of 4-hydroxy benzoic acid, and sulcofuron:5- chloro-2-(4-chloro-2-(3,4-chlorophenyl)) phenoxyureido benzene sulfonate (as alkali salt, for example the sodium salt). The agent having activity against beetles may be a nitromethylene of formula (V):
(V) where R2 is H or CH3; X is CH or N; and Y is
Preferably the agent having activity against beetles is applied at a level of about 0.0001% to 0.1%.
In a further aspect the present invention provides a treatement composition suitable for use in the method of the present invention said composition including one or more compounds of formula (I) to (IV) and optionally including one or more compounds active against beetles.
In order that the invention may more readily be understood the following examples are provided. It will be clear to the reader that the invention is not limited to the particular exemplification provided hereunder.
Brief Description of the Drawings
The following description makes reference to the attached figures in which:
Figure 1 shows the Freundlich adsorption isotherm for compound (IV) on wool at 100°C,
30 min;
Figure 2 is a graph showing light fastness of woolen fabrics treated with compound (IV);
Figure 3 is a graph showing the handwashing characteristics of fabrics treated with compound (IV); and
Figure 4 is a graph showing the effect of dry cleaning on wool treated with compound
(IV). EXPERIMENTAL
Insect Bioassay
Compounds according to formula (III) may be prepared by benzoylation of a t-butyl hydrazine under Schotten-Baumann conditions. The product was recrystallised from methanol-ether; purity and structure were confirmed by nmr.
For initial bioassay, compounds were dissolved in ethanol at appropriate concentrations, then applied to prewetted, centrifuged wool fabric so as to evenly cover the fabric without run-off. Less than 2ml of ethanol was applied to 2g of fabric. Formulated Compound (IV) was also applied by aqueous dilution of water suspension formulation (Compound (IV) FL 20%ai). Samples were air dried before testing. Treatment levels between 0.1% and 0.0001% were used. Insect bioassay was according to AS2001 [1]. Minimum effective concentrations (MECs) were determined as the amount sufficient to inhibit larval feeding to less than 8mg damage when untreated voracity control fabrics showed at least 30 mg damage. Reported values are the means of at least two determinations.
Dyebath Application
Wool was treated with the insecticide in an Ahiba dyeing apparatus at 100°C for 30 minutes as described in AS2001. The insecticide was applied at the start of the dyeing cycle either as an ethanol solution, or as a micro-ground suspension (Compound (IV) 2F 23%ai or Compound (IV) FL 20%ai). Fabrics were rinsed in cold water then air dried after application. Generally 20g of wool was treated in 500cm3 of water.
Chemical Analysis of Dyebath Liquors
Hot dyebath liquors (75ml) were taken from the dyebath and diluted to 100ml with methanol. The resulting solutions were used directly for HPLC analysis. Wash and Dry Clean Fastness testing
Hand washing methods have been described previously [2]. Drycleaning was performed in commercial equipment using perchloroethylene solvent.
Light Stability Studies
Accelerated exposure to light was conducted in fan ventilated boxes equipped with 500W Phillips G-74 mercury-tungsten fluorescent lamps. A thermostatically controlled fan was used to maintain the black body temperature at 67°C [2].
Chemical Analysis of Fabrics
Fabric samples (0.2g) were extracted with a solution of methanol/water (75:25 v/v) (5ml) with shaking at 80°C. After the vessels were treated for an additional 30 min in an ultrasonic bath, the methanol/water solution was filtered and taken for HPLC analysis. Compound. (II) (where R5 and R6 are H) is used as an internal standard for analysis of Compound (IV).
HPLC Chemical Analysis
A Varian Star System HPLC fitted with a diode array detector and a variable wavelength detector usually set at 210 nm was used. Samples from dry-cleaning showed an interfering peak at 210nm and 265nm detection was used. A Brownlee Labs Spheri-5 RP8S (10cm length, 4.6mm ID) cartridge column was maintained at 40°C with an elution solvent of acetonitrile/water (57:43).
Insecticidal Activity against Moth and Beetle Species
Compound in accordance with formula (I) have very high insecticidal activity against all five of our strains of clothes moths, but as expected, there was very weak beetle activity at the highest levels tested. However as indicated above, if beetle protection is also needed, the compounds of formula (I) will need to be used in a mixture with a compound active against carpet beetles to guarantee protection to wool goods.
TABLE 1 Minimum Effective Concentrations of Compounds (% of active compound by weight on wool).
Test Insect
Compound Tineola* Tinea* Anthrenus
Flavipes
Compd. (Ill) 0.001 >0.1
Cmpd. (IV) (FL formulation) 0.005 0.001 >0.1
Cmpd. (IV) (ethanol) 0.001 0.0025 >0.1
Permethrin** 0.004 0.002 0.008
Similar results were obtained with wild strains (dieldrin-resistant) and susceptible strains of common clothes moth (Tineola bisselliella) and case-bearing clothes moths (Tinea translucens).
Permethrin was applied to wool from boiling dyebaths.
At application levels above 0.005%, the treatment compounds caused 100% kill in the 14 day test. At levels around 0.00025%, approximately 50% of the larvae were still alive, but appeared abnormal. Even at levels of 0.0001%, larval feeding was only 30-40% of control wool. At high level (0.1%), the Tinea larvae crawled from their cases before dying, usually an indicator of distress.
To ensure that an active residue of insecticide remains to compensate for losses during application and use over the life time of the wool goods, levels of active ingredient higher than these minimum effective levels will need to be applied. Dyebath exhaustion
Chemical assay of liquors and fabrics (Table 2) indicated there were significant losses in the dyebath during application. Losses of Compound (III) were high, and appear related to the hgih water solubility of this compound. Compound (IV) gave better exhaustion.
TABLE 2 Dyebath Exhaustion of Compound (III) and Compound (IV)
Application Level Dyebath Loss in Wool Recovery
(%wool weight) Concentration Liquors Analysis on wool
(mg/L) (%) (mg/kg wool) (%)
Cmpd(III)(0.001)* 0.21 53
Cmpd (III) (0.002) 0.45 56
Cmpd.(lll)(0.005) 1.28 64
Cmpd.(lll)(0.01) 2.64 66 47(0.0047)* 47
Cmpd(lll)(0.02) 5.35 67 93(0.0093) 47
Cmpd(IV) (0.001) 0.16 43 7.2(0.00072) 72
Cmpd. (IV) (0.002) 0.26 33 12(0.0012) 60
Cmpd. (IV) (0.005) 0.60 30 33(0.0030) 66
Cmpd. (IV) (0.01) 1.20 30 57(0.0057) 57
Cmpd. (IV) (0.02) 2.3 29 125(0.0125) 63
Cmpd. (IV) (0.05) 2.9 15
* Bracketed values are concentration of compounds on wool expressed as
% weight on wool.
Exhaustion of Compound (IV) followed a Freundlich absorption isotherm (Fig 1) with slope near unity, indicating that concentration in the wool was proportional to the concentration in the liquor. Losses will therefore be dependent on the liquoπwool ratio used in the dyeing, and percentage losses will be smaller at liquor ratios shorter than the 25:1 used in this initial work. Levels in rinse liquors are very low, indicating good penetration of the fibre, and hydrolysis and volatility losses are low as indicated by the good overall recoveries of the active ingredient in wool and liquors.
Durability Requirements of Mothproofing Chemicals
Insect-resist activity is required to persist through the life-time of a wool product. Application of a 5-10 fold excess of active ingredient above the minimum active level ensures insect protection even after 80-90% losses through volatility, exposure to light, and cleaning (washing, shampooing and drycleaning).
Light Fastness and Volatility
Light stability and long-term volatility are the main factors in deciding durability of an insect-resist treatment over the anticipated life time of 20 years that can reasonable be expected from a domestic carpet. Volatility losses are an integral part of light fastness testing because high temperatures may be reached in exposure testing. Experience with permethrin has shown that it may be lost from the surface of fabric with a half-life of 12 days at 60°C if it is applied under conditions where it does no penetrate the fibre, but it can 'permanently' protect wool when applied from high temperature dyebaths.
Compound (IV) treated fabrics were subjected to accelerated light exposure testing to exceed blue scale fastness rating 6, by which stage the fabrics were significantly yellowed and were becoming weakened. Losses were monitored by insect bioassay (Table 3) and chemical assay (Table 4, Fig 2). TABLE 3 Insect Bioassay of Fabrics Treated with Compound (IV) after Accelerated Light Exposure Testing
Nominal Application Tineola Bioassay Results* (% on wool weight) Feeding Damage (mg)
Light Exposure Time
No 1 Week 2 Week 3 Week 4 Week** exposure
0.005 4 3 3 5 6
0.002 4 6 3 7 8
0.001*** 7 2,11 3,16 6,14 3,11
Control wool fabric feeding damage 30-78mg.
Exposures of 1 , 2, 3, and 4 weeks correspond to blue scale ratings of 3, 5, and 6 respectively.
Duplicate sets gave variable feeding damage; both sets reported.
TABLE 4 Chemical Analysis of Compound (IV) Treated Wools after Accelerated Light Exposure
Wool Analysis (Compound (IV) mg/kg wool)
Nominal
Application
(% on wool weight)
Light Exposure Time
No 1 Week 2 Week 3 Week 4 Week Exposure
0.001 7.2 (100)* 5.4 (75) 4.6 (64) 4.1 (57) 4.0 (56)
0.002 12 (100) 11 (92) 8.9 (75) 8.0 (67) 7.8 (66)
0.005 33 (100) 30 (90) 26 (77) 23 (70) 23 (70)
0.01 157 (100) 54 (94) 48 (84) 44 (77) 44 (76)
0.02 125 (100) 109 (87) 96 (77) 86 (68) 84 (67)
* Bracketed values in the body of the table are percentages of the initial application remaining after the specified exposure.
Compound (IV) has more than adequated light fastness for a commercial insect-resist treatment. Under these same accelerated testing conditions, only 40-50% of an initial application of permethrin would remain.
Drycleaning and Wash Fastness
In comparison with the synthetic pyrethroid mothproofing compounds, Compound (IV) has similar washing performance and better drycleaning resistance. Losses in handwashing are confirmed by both insect bioassay (Table 5) and by chemical analysis (Table 6, and Fig. 3). Losses in drycleaning are small (Table 6, Fig. 4).
TABLE 5 Insect Bioassay of treated fabrics after Washing and Drycleaning
Compound Nominal Tineola Bioassay Results Application Feeding Damage (mg) (% on wool weight)
As Hand Washing Drycleaning Treated
5 10 5 10 Cycles Cycles Cycles Cycles
4 9 58
Compd. (Ill)*
0.1 7 13 90
0.05 8 26 97
0.025
0.005 4 7 5 3 3
Cmpd. (IV)**
0.002 4 17 20 9 6
0.001 7 30 44 9 7
Control wool fabric feeding damage 109-140mg.
Control wool fabric feeding damage 48-65mg. TABLE 6 Chemical Analysis of Compound (IV) Treated Wools after Drycleaning and Washing.
Nominal Wool Analysis (%Cmpd. (IV) oww) Application (% on wool weight)
As Hand Washing Drycleaning Treated
5 10 5 10 Cycles Cycles Cycles Cycles
0.001 7 (100) 2.2 (30)* 1.5 (20)
0.002 12 (100) 4.8 (40) 2.8 (23) 12 (102) 10 (85)
0.005 33 (100) 13 (40) 6.6 (20) 29 (88) 29 (86)
0.01 57 (100) 24 (43) 16 (27) 58 (102) 54 (95)
0.02 125 (100) 55 (44) 29 (23) 119 (95) 120 (96)
* Bracketed values in the body of the table are percentages of the initial amount remaining after the specified exposure.
Dry cleaning is a severe test for the non-polar pyrethroids (permethrin or cycloprothrin) and 70% of an initial application would be removed after 5 commercial dry-cleaning treatments. Compound (IV) was largely unchanged. After 5 hand washing cycles, 45% of applied pyrethroid remained on the wool, and Compound (IV) showed similar performance. For the main end-use of carpeting, the most important wet treatment is carpet shampooing; losses of 30% after 5 cycles are usual for the pyrethroids, and Compound (IV) should behave similarly. These factors are important in deciding the ultimate application rate for each material. In practice, compound Compound (IV) may need to be applied at around 0.005-0.01% active ingredient to compensate for losses in application, light and wet treatments such as carpet shampooing.
Compositions containing Compounds active against Beetles
Permethrin Results:
SET 1 : Tinea translucens (long term test)
%Cmpd. (IV) owf 0 0.0025 0.0050 0.0075 0.010 feeding damage(mg) 200 21 1 1.5 1
(owf=on weight of fabric)
SET 2: Anthrenus flavipes (2 week test)
%Cmpd. (IV) owf 0 0.001 0.0025 0.005 0.0075 0.01 %permethrin owf 0 0 0 0 0 0 feeding damage(mg) 81 ,125 71 ,20 100,71 106,138 94,56 52,20
SET 3: Anthrenus flavipes (2 week test) %Cmpd. (IV) owf 0 0.001 0.0025 0.005 0.0075 0.01
%permethrin owf 0.003 0.003 0.003 0.003 0.003 0.003 feeding damage 17,15 9,13 9,5 5,18 10,15 2,5
These results clearly show that Compound (IV) has high activity against moths (set 1), but no activity agains beetles (set 2) except at the highest level in the concentration range studied. The presence of Compound (IV) does however, increase the activity of the permethrin (ie leads to lower feeding damage) from the comparison with damage of a permethrin-only treatment (15,17mg for duplicate samples). The effect roughly corresponds to a doubling in activity. As an example there may again be a synergistic effect with the HHP derivative, as the Compound (IV) improves its activity:
HHP derivative Results:
SET 4: Anthrenus flavipes (2 week test)
%Cmpd. (IV) owf 0 0 0.006 0 0.006
%HHP owf feeding 0 0.01 0.01 0.02 0.02
Feeding Damage (mg) 108 7.7 4.1 2.5 1.9
SET 5: pyrethroid-resistant Tinea translucens (4 week test) Bifenthrin on wool (mg/kg) 0 6 10 20 30
Feeding Damage 41 38 41 44 37
(Conclusion: Bifenthrin is inactive at 0.003% on wool weight against pyrethroid resistant clothes moths)
SET 6: pyrethroid-susceptible Tinea translucens (2 week test)
Bifenthrin on wool (mg/kg) 0 1 2 3 4 Feeding Damage (mg) 31 12 4 4 4
(Conclusion: Bifenthrin is active at 0.0002% on wool weight pyrethroid susceptible clothes moths)
SET 7: Beetles (Anthrenus flavipes) (2 week test)
Bifenthrin on wool 0 1 2 3 4 5
(mg/kg)
Feeding Damage (mg) 55 15 2 4 1 1
(Conclusion: Bifenthrin is active at 0.0002% on wool weight against carpet beetles). The results sets 1 , 5 and 7 indicate that a mixture of compound IV and Bifenthrin will control pyrethroid resistant clothes moths.
SET 8: Beetles (Anthrenus flavipes) (2 week test) % Compound (IV) owf 0 0 0.01
% Butyl ester of 0 0.25 0.25
4-hydroxybenzoic acids owf Feeding Damage (mg) 28 18 3
Although Compound (IV) has little direct beetle activity at this treatment level, it greatly enhances the effect of the 4-hydroxybenzoic acid ester.
References:
1. Australian Standard AS 2001.6.1 (1980)
2. R.J. Mayfield and I.M. Russell. J. Text. Inst.. 70, 53 (1979)
It will be clear to the reader that various modifications may be made to the particular embodiments described above without departing from the spirit and scope of the present invention.

Claims

CLAIMS:
1. A method of mothproofing wool or a wool-containing product the method including treating the wool or wool-containing product with an effective amount of a compound according to formula (I):
wherein X and X' are the same or different O, S or NR;
R1 is hydrogen; (CrC6) alkyl; (CpCe) alkoxy-(CrC6) alkoxy-(C C6) alkyl having independently the stated number of carbon atoms in each alkyl group; (CrC6) alkylthio- (C-C6) alkyl having independently the stated number of carbon atoms in each alkyl group; (C2-C6) alkenyi; (C2-C6) alkynyl; or phen-(C C4) alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C,-C4) alkyl, halo-(C C4) alkyl (CrC4)-alkoxy, halo-(C C4) alkoxy, carboxy, (Cr C4) alkoxy- carbonyl, (CrC4) alkanoyloxy or NZZ';
R2 and R3 are the same or different hydrogen or (C C4) alkyl;
R is (CrC4) alkyl substituted with 1 to 4 fluoro; straight chain (C2-C4) alkenyi; carboxyl; (CrC3) alkoxy-carbonyl; cyano; cyano substituted (CrC4) alkyl, tri(C C4)- alkysilyl having independently the stated number of carbon atoms in each alkyl group; or tri(CrC2) alkylsilylmethyi having independently the stated number of carbon atoms in each alkyl group; provided that R2 and R3 are both alkyl when R4 is corboxyl or alkoxycarbonyl; and A and B are the same of different unsubstituted or substituted naphthytyl where the substituents can be from one to three of the same or different halo; nitro; (CrC4)- alkoxy; (CrC4) alkyl or NZZ';
unsubstituted or substituted phenyl where the substituents can be from one to five of the same or different halo; nitroso; nitro; cyano; hydroxy; (C,-C6) alkyl; halo-(Cr C6)-alkyl; cyano-(CrC6) alkyl; hydroxy-(CrC6)-alkyl; (C1-C6)alkoxy; halo-(C,-C6) alkoxy; (CrC6) alkoxy-(C C6) alkyl having independently the stated number of carbon atoms in each alkyl group; (C,-C6) alkoxy-(C-,-C6) alkoxy having independently the stated number of carbon atoms in each alkyl group; -ORSR' group; -OC02R group; -OC02H group; (C 6) alkanoyloxy-(C,-C6) alkyl having independently the stated number of carbon atoms in each alkyl group; (C2-C6) alkenyi optionally substituted with halo, cyano, (Cr C4) alkyl, halo-(C|-C4)-alkoxy, (CrC4) alkylthio or (CrC4)alkoxy; (CrC4)alkadienyl; (C2- C6) alkenyioxy; (C2-C6) alkenyl-carbonyl; (C2C6)-alkenyloxy-carbonyloxy; (C2-C6) alkynyl optionally substituted with halo, cyano, nitro, hydroxy, (C C4) alkoxy, halo-(C C4)alkyl, (C C4) alkylthio or (C C4)-alkyl; carboxy; -RCO2R' group; -COR; -COH; halo-(CrC6) alkyl-carbonyl; -C02R group; (CrC6) haloalkoxy-carbonyl; -OCOR group; -ORC02R' group; amino (-NZZ'); amino substituted with hydroxy, (CrC4) alkoxy or (CrC4) alkylthio; -CONZZ' group; (C2-C6)- alkenyl-carbonylamino; hydroxy-(CrC6)-alkylamino- carbonyl; -OCONZZ' group; -NZCOZ' group; -NZC02Z' group; thiocyanato; isothiocyanato; (C C6) thiocyanatoalkyi; (C C6) alkylthio; halo-(C C6) alkylthio; -S(0)Z group; -S02Z group; -OS02R group; -OS02H group; -S02NZZ' group; -CSR group; - CSH group; -SCOR group; -SCOH group -NSCSZ' group; unsubstituted or substituted phenyl having one to three of the same or different halo, cyano, nitro, hydroxy (CrC4) alkyl, halo-(CrC4)alkyl, (C1-C4)-alkoxy, carboxy, (C C4)alkoxy-carbonyl, (C C4)alkanoyloxy, amino, (CrC4)-alkylamino or di(C-|-C ) alkylamino having independently the stated number of carbon atoms in each alkyl group; phenoxy where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C.,-C4) alkyl, halo-(CrC4) alkyl, (CrC4)-alkoxy, carboxy, (C C4)alkyl- carbonyl, (CrC4)alkanoyloxy, amino, (C^C^-alkylamino or di(CrC4)alkylamino having independently the stated number of carbon atoms in each alkyl group; benzoyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C,-C4)alkyl, halo-(C1-C4)alkyl, (C1-C4)-alkoxy, carboxy, (Cr C )alkoxy-carbonyl, (CrC4) alkanoyloxy, amino, (CrC4) alkylamino or di(Cr C4)alkylamino having independently the stated number of carbon atoms in each alkyl group; benzoyloxy (C1-C6)alkyl; phenylthio-(C C6) alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy,(C C4) alkyl, halo-(C C4)alkyl, (C1-C4)-alkoxy, carboxy, (C,-C4)alkoxy- carbonyl, (C|.C4)-alkanoyloxy, amino, (CrC4)alkylamino or di(CrC4)alkylamino having independently the stated number of carbon atoms in each alkyl group; -CR=N-R'" group where R'" is hydroxy, (CrC4)alkyl, (CrC4)alkoxy, amino (-NZZ'), phenylamino, -COR, - COH or benzoyl; (C2-c6) oxiranyl; acetylthiosemi- carbazone; pyrrolyl; oxazolyl, unsubstituted or substituted with one or two methyl group; or when two adjacent positions on the phenyl ring are substituted with alkoxy groups, these groups may be joined to form, together with the carbon atoms to which they are attached, a 5 or 6 membered dioxolano or dioxano heterocyclic ring; unsubstituted or substituted (C,- C10)alkyl having one to four of the same or different halo, cyano, nitro, hydroxy, (C C4)alkoxy, halo-(C1-C4)alkoxy, carboxy, (CTC^-alkoxy-carbonyl, (C C4) alkanoyloxy, phenyl or -NZZ';
unsubstituted or substituted (C3-C8) cycloalkyl or unsubstituted or substituted (C3-C8) cyclo (CrC4) alkyl having one to four of the same or different halo, cyano, nitro, hydroxy, (CrC4) alyl, halo-(C C4)-alkyl, (C C4) alkoxy, halo-(CrC4) alkoxy, carboxy, (C-|-C ) alkanoyl, (C.,-C4)-alkoxy-carbonyl, (C,-C4) alkanoyloxy or -NZZ';
unsubstituted or substituted (C2-C8)alkenyl or unsubstituted or substituted (C2-
C8)-alkadienyl having as substituent(s) a furyl, thienyl or pyridyl or one to four of the same or different halo, cyano, nitro, hydroxy, (C-,-C4)alkyl, (C3-C6)cycloalkyl, halo-(Cr C4)alkyl, (C^C^alkoxy, halo-(C1-C4)alkoxy, carboxy, (C,-C4)-alkoxyl-carbonyl, (C C4) alkanoyloxy or -NZZ'; unsubstituted or substituted (C3-C8)cycloalkenyl or unsubstituted or substituted (C3-C8)cycloalkadienyl having as substituent(s) one to four of the same or different halo, cyano, nitro, hydroxy, (CrC4)alkyl, halo-(C1-C4)alkyl, (C C4)-alkoxy, halo-(C C4)alkoxy, carboxy, (C C4)alkoxy-carbonyl, (C C4)alkanoyloxy or -NZZ'; unsubstituted or substituted (C2-C8)alkynyl having as substituent(s) one to four of the same or different halo, cyano, nitro, hydroxy, (CrC4)alkyl, halo-(CrC4)alkyl, (C C4)alkoxy, halo-(CrC4)alkoxy, carboxy, (C1-C4)alkoxy-carbonyl, (C1-C4)alkanoyloxy, phenyl or -NZZ'; phenalkyl having one to four carbon atoms in the alkyl group and wherein the alkyl group is unsubstituted or substituted with one to three of the same or different halo, cyano, hydroxy, (CrC4)alkoxy, (C1-C4)-alkoxy-carbonyl or -NZZ' and the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (CrC4)alkyl, halo-(C1-C4)alkyl, cyano-(C1-C4)alkyl, (C,-C4)-alkoxy, halo-(CrC4) alkoxy, carboxy, (CrC4)alkoxy-carbonyl, (CrC4)alkanoyloxy, (C2- C6)alkenyl, halo-(C2-C6)alkenyl. (C2-C6)alkynyl or -NZZ'; phenalkenyl having two to six carbon atoms in the alkenyi group and the alkenyi group is unsubstituted or substituted with one to three of the same or different halo, cyano, hydroxy, (C C4)alkyl, halo-(C C4)alkyl, (C1-C4)alkoxy, halo-(C,-C4)alkoxy, (C C4)-alkoxy-carbonyl or -NZZ', and the phenyl ring is unsubstituted or substituted with one to or three of the same or different halo, cyano, nitro, hydroxy, (CrC4) alkyl, halo- (CrC4)alkyl, (CrC4)alkoxy, halo-(C1-C4)-alkoxy, carboxy, (C1-C4)alkoxy-carbonyl, (Cr C4)alkanoyloxy or -NZZ'; unsubstituted or substituted five-membered heterocycle selected from furyl, thienyl, triazolyl, pyrrolyl, isopyrrolyl, pyrazolyl, isoimdazolyl, thizolyl, isothiazoiyl, oxazolyl and isooxazolyl where the substituents can be from one to three of the same or different halo; nitro; hydroxy; (C1-C6)alkyl; (C1-C6)alkoxy; carboxy; (C C6) alkoxy- carbonyl; -RC02H group RC02R' group; -CONZZ' group; amino (-NZZ'); -NZCOZ' group; (C C6)alkylthio; or unsubstituted or halo substituted phenyl having one to three of the same or differnt halo, nitro, (CrC6)alkyl, halo-alkyl, (C1-C6)alkoxy, halo- (CrC6)- alkoxy, carboxy, (C C4)alkoxy-carbonyl or amino (-NZZ'); or unsubstituted or substituted six-membered heterocycle having one, two, three or four nitrogen atoms and two to five nuclear carbon atoms where the substituents can be from one to three of the same or different halo; nitro; hydroxy; (C|-C6)alkyl; (C C6)alkoxy; carboxy; (C C6)-alkoxy-carbonyl; -RC02H group; -RC02R' group; -CONZZ' group; amino (-NZZ'); -NZCOZ' group; (C.,-C6)alkylthio; or unsubstituted or substituted phenyl having one to three of the same or different halo, nitro, (CrC6)alkyl, halo-(Cr C6)alkyl, (CrC6) alkyl, (C-rC^alkoxy, halo-(C C6)- alkoxy, carboxy, (CrC4)alkoxy- carbonyl or amino (-NZZ'); where R and R' are (C C6)alkyl; Z and Z' are hydrogen or (Cι-C4)alkyl; "amino" means NZZ'.
2. A method according to claim 1 wherein the treatment compound is a compound of formula (II)
where R5 and R6 may be the same or different and may be H or C-,,3 alkyl and may be 1-6.
3. A method according to claim 2 wherein the treatment compound is a compound formula (III)
4. A method according to claim 2 wherein the treatment compound is a compound of formula (IV)
(IV)
5. A method according to any one of the preceding claims wherein the treatment compound is applied at a level of about 0.001 %-0.5% based on the wool weight. 6. A method according to any one of the preceding claims wherein treatment compound is applied as a solution in an organic solvent.
7. A method according to any one of claims 1 to 5 wherein the treatment compound is applied as a suspension, self-emulsifiable concentrate or other water-based formulation.
8. A method according to any one of the preceding claims wherein the treatment compound is applied in a dyebath, by continuous padding or in a scouring application.
9. A method according to any one of the preceding claims wherein the treatment compound is applied at 5-10 fold excess of the minimum active level of the treatment compound.
10. A method according to any one of the preceding claims wherein the wool or wool-containing product is also treated with an agent having an activity against beetles.
11. A method according to claim 10 wherein the agent active against beetles is selected from the group natural or synthetic pyrethroids, repellants and disinfectants, and insect resist agents of the aryl ureido and amide classes.
12. A method according to claim 11 wherein the beetle agent is selected from permethrin or bifenthrin.
13. A method according to claim 11 wherein the beetle agent is selected from the group N-(3,4-dichlorophenyl)-1 ,2,3,4-tetrahydro-6-hydroxy-1 ,3-dimethyl-2,4-dioxo-5- pyrimidine carboxamide or N,N'-bis[4-chloro-3-(trifluoromethyl)phenyl] urea, butyl ester of 4-hydroxybenzoic acid and 5-chloro-2-(4-chloro-2-(3,4-chlorophenyl))phenoxyureido benzene sulphonate or alkali salt thereof. 14. A method according to claim 10 wherein the beetle agent is a compound of formula (V)
where R2 is H or CH3; X is CH or N; and Y is
15. A method according to any one of claims 10 to 14 wherein the beetle agent is applied at a level of about 0.0001% to 0.1%.
16. A method according to any one of claims 10 to 15 wherein the treatment compound is applied simultaneously with the beetle agent.
17. A treatment composition containing a treatment compound according to any one of claims 1 to 5.
18. A treatment composition according to claim 17 further including an agent having activity against beetles.
19. A treatment composition according to any one of claims 16 and 17 in the form of a dye bath composition.
EP94926721A 1993-09-06 1994-09-06 Insecticidal composition Withdrawn EP0717591A4 (en)

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EP0883710A4 (en) * 1995-12-21 2000-11-29 Wool Res Organisation A method for insect-resist treatment of carpet and textiles
US6723531B2 (en) 1996-04-05 2004-04-20 The Salk Institute For Biological Studies Method for modulating expression of exogenous genes in mammalian systems, and products related thereto
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WO1995007021A1 (en) 1995-03-16
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JPH09502189A (en) 1997-03-04

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