NZ336826A - Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing N-quinoxalylanilines - Google Patents

Abstract

An industrial antibacterial/antifungal agent, algicide and an agent for preventing the adhesion of organisms, containing at least one compound of N-quinoxalylanilines as represented by the above formula, wherein: R1 and R2 each independently represent H, halogen, CF3, C1-C5 alkyl, C1-C5 alkoxy or NO2 R3 represents H, halogen or C1-C5 alkyl R4 represents H, C1-C5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkylcarbonyl, C1-C5 alkylsulfonyl or C1-C5 alkylsulfenyl. The alkylsulfenyl group may be substituted with halogen. X and Y independently represent NO2, CF3 or halogen Z represents H, halogen, NO2 or OH m and n each independently represent 0 or 1, but not m=n=1 j and k each independently represent 0, 1, 2 or 3 provided that j+k<3

Description

New Zealand Paient Spedficaiion for Paient Number 336826 * Intellectual Property Office of New Zealand IP Summary Report (51) Classification: A01N43/60, C07D241/44 IPC Edition: IPC Status: 70 Accepted Client Ref: JB212330 Page: 1 of 1 Date: 19 May 2000 Time: 11:53:40 (iprip02 2.00.21) 336826 Version number: 4 IP type: Patent PCT Inward (86) International Application number JP98/00208 (87) WO Publication number: 98/31228 Elected: N (22) NZ Filing date: 21 January 1998 Date entered National phase: 19 July 1999 (30) Priority Data: (31)97 8520 (32) 21 January 1997 (33) JP (71) Applicant. NISSAN CHEMICAL INDUSTRIES LTD, 7-1, tCandanlshiki-cho, 3-chome, Chiyoda-ku, Tokyo 101-0054, Japan (72) inventors: Igarashi, Shlnichi Futagawa, Mitsugu Contact: BALDWIN SHELSTON WATERS, Level 14, NCR House, 342 Lambton Quay, Wellington, NZ Journal: 1452 Date actions completed: Application Accepted Next renewal date: 19 May 2000 21 January 2002 Office title: Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing N-qulnoxalylanillnes (54) Applicant title: Industrial antlmlcrobial/mildew-proofing agents, algicides and antifouling agents containing N-qulnoxaiylanilines (57) Abstract: Patent 336826 An industrial antibacterial/antifungal agent, algicide and an agent for preventing the adhesion of organisms, containing at ieast one compound of N-quinoxalylaniiines as represented by the above formula, wherein: R1 and R2 each independently represent H, halogen, CF3, Ci-C5 alkyl, CrC5 alkoxy or N02 R3 represents H, halogen or Ci-C5 alkyl R4 represents H, Ci-C5 alkyl, C^Ce alkenyl, CrC9 alkynyl, C2-C„ alkylcarbonyl, C1-C5 alkylsulfonyl or Ci-Cs alkylsulfenyl. The alkylsulfenyl group may be substituted with halogen. X and Y independently represent N02, CF3 or halogen Z tepresents H, halogen, N02 or OH m and n each independently represent 0 or 1, but not m=n=1 ) and k each independently represent 0, 1, 2 or 3 provided that j+k<3 Drawing: *• End of report" SPECIFICATION INDUSTRIAL ANT I BACTERIAL/ANT I FUNGAL AGENTS, ALGICIDES, AND AGENTS FOR PREVENTING ADHESION OF ORGANISMS CONTAINING N-QUINOXALYLANILINES The present invention relates to antibacterial/antifungal agents and algicides for industrial products, to antibacterial/antifungal agents and algicides for use In the process of producing industrial products, and to agents for preventing the adhesion of aquatic organisms, particularly harmful aquatic organisms such as shells.

Industrial antibacterial/antifungal agents and algicides are used to eliminate various evil effects due to growth and propagation of bacteria, fungi and algae on various industrial products or in various Industrial facilities.

Heretofore, as such industrial antibacterial/antifungal agents and algicides, there have been used organic nitrogen compounds, organic nitrogen-sulfur compounds, organic halogen compounds, nitrogen-containing aliphatic polymers, and heavy metal coordinated compounds and the like.

Ag< its for preventing the adhesion of organisms are used for preventing the adhesion of harmful aquatic organisms such as shells to fishing nets, bottoms of ships, marine equipments such as buoys, marine constructions, steam condenser cooling water systems for thermal or atomic power plants, inlet channels for cooling water for heat exchangers for use in chemical industries, underwater constructions, or reservoirs and the like.

If the aquatic organisms adhere to a culture net, the meshes of the net are clogged to cause a decrease in flow of sea water, along with which growth of cultured fish is Inhibited and there arise fish diseases frequently.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION DESCRIPTION OF THE RELATED ART The adhesion of the aquatic organisms t l increase in fluid resistance, which results in a decrease in navigation speed, an increase in fuel consumption, and further an increase in loss such as a cost for cleaning the bottom of ships or for cessation of navigation service.

In marine facilities and marine and underwater constructions , adhesion of aquatic organisms thereto causes an increase in weight and extreme inconvenience in handling and operation while their adhesion to inlet channels causes problems such as a decrease in thermal conductivity, blockage of the inlet channels, and a decrease in the amount of inlet water.

Hitherto, to prevent the adhesion and growth of the aquatic organisms in see water and fresh water, there have been used antifouling paints containing organic tin compounds such as bistributyltlp oxide, or copper compounds such as copper sulfate and cuprous oxide.

Japanese Patent Application Laid-open No. Sho 60-97964 discloses N-quinoxalylaniline compounds and their production method an£ their use as agricultural and horticultural antimicr< l ial, insecticidal, and acaricidal agents.

H< ,;ever, this publication discloses nothing about the use of the co ounds as industrial antibacterial/antifungal agents and algicidal agents as well as agents for preventing the adhesion of orgai isms.

The above-described organic nitrogen compounds, organic nit/ogen-sulfur compounds, organic halogen compounds, nitrogen-containing aliphatic polymers and heavy metal coordinated compounds include those chemicals which have irritating properties and hence are prescribed by labor safety law, those chemicals which are used in large doses and are questioned from the viewpoint of environmental preservation, those chemicals which release formalin or halogens and Influences on humans and environmental pollution thereby are feared, and those chemicals which are feared of environmental pollution by heavy metals, so that all of the Industrial antibacterial/antifungal agents and algicidal agents cannot be said to be constituted by preferable chemicals only. 2 Though the above-described organic tin compounds as agents for preventing the adhesion of organisms are being effective in preventing the adhesion of aquatic organisms, those compounds are highly toxic and are especially prone to accumulate in the bodies of fishes and shells and promote the environmental pollution. Thus the use of those compounds is now under legal controls because of the defects thereof.

For example, in the United States of America, the application of organic-tin ship paints to ships having a length of 65 feet or less is inhibited under the Organic Tin Antifouling Paint Regulation (1987). In the United Kingdom, the application of tributyltln-contalning antifouling agents to ships having a length of 25 m or less and marine agriculture is Inhibited under the Food and Environment Protection Law (1987).

Further, in Japan, tributyltin oxide is designated as a first-class specific chemical substance, and triphenyltin compounds and tributyltin compounds are specified as a second-class chemical substances, according to the Chemical Substance Examination Rule (Kashinhow) (1990). The application of those compounds to fishing nets is inhibited.

Furthermore, it is also taken a measure for control of the use of ship bottom paints containing tributyltin compound(s) (Notification by the Ministry of Transportation, 1990).

The above-mentioned copper compounds are widely used in antifouling paints for inlet channels and ship bottoms. However, the use thereof is anxious for environmental pollution in future, because such copper compounds contain heavy metals similar to tin compounds. Therefore, it cannot be said that such compounds are preferable agents for preventing the adhesion of aquatic organisms.

The compounds used in the present invention are not described in the above-described controlling laws and the above-mentioned publication describes nothing about the effectiveness of N-quinoxalylanlllnes as industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms. 3 SUMMARY OF THE INVENTION As a result of intensive investigation to solve the above-mentioned problems, the present inventors have found that N-quinoxalylanilines are highly safe and develop a wide spectrum at doses low enough to avoid environmental pollution, and have found that the N-quinoxalylanilines can be highly practical and useful active agents as industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms. And the inventors have completed the present invention based on those new facts found.

That is, the present invention relates to industrial antibacterial/antifungal agent(s), algicide(s) and agent(s) for preventing the adhesion of organisms, characterized by containing at least one compound of N-quinoxalylanilines represented by general formula (1) (wherein R*and R2, each Independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, or a nitro group; R1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1-5 carbon atoms; R4 represents a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkenyl group having 2-6 carbon atoms, an alkynyl group having 2-6 carbon atoms, an alkylcarbonyl group having 2-6 carbon atoms, tn alkylsulfonyl group having 1-5 carbon atoms, or an alkylsulfenyl group having 1-5 carbon atoms which may be substituted with a halogen atom(s); X and Y each independently represent a nitro group, a trifluoromethyl group or a halogen atom; Z represents a hydrogen atom, a halogen atom, an alkoxy group having 1-5 carbon atoms, or a phenoxy group which may (0)m 0) be substituted with a halogen atom(s), a nitro group(s) or a hydroxy 1 group(s); m and n each independently represent 0 or 1 provided that m and n are not 1 simultaneously; j and k each independently represent 0, 1, 2 or 3 provided that j+k always are 3 or less).

Each substituent in formula (1) will be described concretely.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group having 1-5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 1-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neo-pentyl, t-pentyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and the like.

Examples of the alkenyl group having 2-6 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-ethyl-2-vinyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-1-butenyl, 1-i-propylvinyl, 2,4-pentadienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 2,4-hexadienyl, 1-methyl-l-pentenyl and the like.

Examples of the alkynyl group having 2-6 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like.

Examples of the alkoxy group having 1-5 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, pentyloxy and the like.

Examples of the alkylcarbonyl group having 2-6 carbon atoms include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, n-butylcarbonyl, i-butylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, 1-pentylcarbonyl, 2-pentylcarbonyl, 3-pentylcarbonyl, 1-pentylcarbonyl, neo-pentylcarbonyl, t-pentylcarbonyl, cyclopropylcarbonyl, 1- methylcyclopropylcarbonyl, 2-methylcyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl and the like.

Examples of the alkylsulfonyl group having 1-5 carbon atoms include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-propvlsulfonyl, n-butylsulfonyl, i-butylsulfonyl, s-butylsulfonylf t-butylsulfonyl, 1-pentylsulfonyl, 2-pentylsulfonyl, 3-pentylsulfonyl, 1-pentylsu.lfonyl, neo-pentylsulfonyl, t-pentylsulfonyl, cyclopropylsulfonyl, 1-methylcyclopropylsulfonyl, 2-methylcyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl and the like.

Examples of the alkylsulfenyl group having 1-5 carbon atoms include methylsulfenyl, ethylsulfenyl, n-propylsulfenyl, i-propylsulfenyl, n-butylsulfenyl, i-butylsulfenyl, s-butylsulfenyl, t-butylsulfenyl, 1-pentylsulfenyl, 2-pentylsulfenyl, 3-pentylsulfenyl, i-pentylsulfenyl, neo-pentylsulfenyl, t-pentylsulfenyl, cyclopropylsulfenyl, 1-methylcyclopropylsulfenyl, 2-methylcyclopropylsulfenyl, cyclobutylsulfenyl, cyclopentylsulfenyl and the like.

The industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms according to the present invention may be any so long as they contain at least one compound of the N-qulnoxalylanlllnes represented by general formula (1) as an active ingredient.

Preferred compounds contained as an active ingredient in the industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms according to the present invention are listed in Tables 1 to 3 below. However, the compounds used in the present invention are not limited to these compounds.

In Tables, the symbols have the following meanings. Me: a methyl group, Et: an ethyl group, COMe: an acetyl group, COEt: an ethylcarbonyl group, SOaMe: a methanesulfonyl group, MeO: a methoxy group, EtO: an ethoxy group, n-PrO: a n-propoxy group, m-HO-PhO: a m-hydroxyphenoxy group.

Table 1 1 XXX,J-'^. XI,X _&. xxx_fy. •ry^ ,.r\^ j -r\-4 z z z the substituents on the benzene ring R1 R8 R4 2 co 4 6 H H H NO: H NO* h CF. h h h H H NO: H NO 2 H H H H h NO 2 h CF* h h h NO 2 h NO: h NO* h h h NO: H CF, h NO* h H H NO: H H H NO: H H H CF, H NO 2 H CF* H H H NO: CI CF, H NO* H H H NO: OEt CFi H NO: H H H H CI CFi H NO* H H H NO: Br CF.

H NO* H H Me NO* CI CFj H NO* H Me H NO: CI CF» H NO* H Et H NO* CI CFi h NO* H CI H NO 2 CI CFi h NO* H H H NO* F CFi H NO* F H H NO: H NO i H CF.

F H H H H NOi H NO* F H H H H NO i H CF, F H H NO: H NO* H NO* F H H CI H NO: H CI F H H NO* h CF* H NO* F H H NO: h h H NO* F h h CF» h NO* h CF.

F h h NO: CI CF* H NO* F H H NO* OEt CF* H NO* F H H NO* OPh-OH-m CF* H NO* F H H H CI CF, H NO* 7 Table 1 (continued) the substituents on the benzene ring Rl R8 R4 2 cs3 co 4 6 F H H NO 2 OPr-n CF.

H NO* F H H NO* Br CFs H NO 2 F H Me NO 2 CI CF, H NO 2 F H COMe NO 2 CI CF 3 H NO 2 F H SO j Me NO 2 CI CFs H NO 2 F H SCCI3 NO 2 CI CF3 H NO 2 F H COEt NO 2 CI CF3 H NO 2 F Me H NO2 CI CF3 H NO 2 F Et H N02 CI CF.

H NO* F CI H NO 2 H H H NO* F H H NO 2 F CF.

H NO* CI H H NO* H NO* H CF, CI H H H H NO* H NO* CI H H H H NO* H CF, CI H H NO* H NO* H NO* CI H H CJ H NO* H CI CL H H NO; H CF, H NO* CI H H NO 2 H H H NO* CI H H CF, H NO* H CF* CI H H NO* CI CF* H NO* CI H H NO* OEt CF, H NO* CI H H NO* OPh-OH-m CF, H NO* CI H H K CI CF* H NO* CI H H NO 2 OPr-n CF, H NO* CI H H NO* Br CF, H NO* CI H Me NO: CI CF, H NO* CI H COMe NO* CI CF, H NOa CI H SO,Me NO* CI CF, H NO* CI H SCC1, NOi CI CF, H NO* CI H COEt NO 2 CI CF, H NO* CI Me H NO* CI CF, H NO* CI Et H NOa CI CF, H NO* CI CI H NOa H H H NO* Ci H H NOa F CF* H NO* Br H H NO* CI CF* H NO.

Br H H NO.

OEt CFa H NOi 8 Table 1 (continued) the substituents on the benzene ring Rl R8 R4 2 3(Z) 4 6 Br Me H no 2 ci cf> H no 2 i H H no2 ci cf, h no 2 cf, H H no 2 H no 2 H cfi cf.

H H H H no 2 H no 2 cf i H H H H no 2 H cf, cf3 H H no 2 H NO 2 H no 2 cf3 H h no 2 h cf 3 H no 2 CFi •H h no 2 H H H NO, CFj h h cf, H no, H cf, cf, H H no 2 ci cf, h NO, cf3 h h no 2 OEt cfi H NO, cf, h h h ci CFi h NO, CFi h h no2 Br CFi h NO, CFi h Me NO, CI CFi h NO, cf, Me h NO, CI CFi h NO, cf, Et h NO, CI CF, h NO, cfi ci h NO, CI cf, h NO, CFi h k NO, f cf, h NO, h h ch, =chch, NO, h NO, h CF, h h chscch, h h NO, h NO, h h ch,=chch, h h NO, h CF, h h cheCCHi NO, h NO, h NO, h h CH, =CHCHi NO, CI CF, h NO, h h checch, NO, OEt CF, h NO, h ii cheCCH, NO, CI CF, h NO, h Me ch, =chchi NO, CI CF, h NO, H Et CHsCCH, NO, CI cf, h NO, H ci ch,=chch, NO, ci cfi h NO, h h CHsCCH, NO, f cf, h NO, F H ch, =chch, NO, h NO, H CF, f H CHeCCH, H H NO, H NO, f H ch,=chch, H h NO, K CF, f H chscch, NO, h NO, h NO, F H CH,=CHCH, NO, CI CF, H NO, F H CHeCCH, NO, OEt CF, H NO, F H CHeCCH, NO, CI CF, H NOs 9 Table 1 (continued) the substituents on the benzene ring r1 r8 r4 2 3(Z) 4 6 F Me CHa=CHCH2 no2 CI CFj H NOa F Et CHsCCH* no2 CI CFj H N02 F CI CH2=CHCH2 no2 CI CFj H noa F H CH=CCH2 NO 2 F CFj H NO 2 CI H CHz =CHCHz NO 2 H NOa H CFj CI H CH=CCH2 h H NOa H noa CI H CHa=CHCH2 H H no2 H CFj CI H ch=cch2 no2 H NOa h NOa ci h chi=CHCH* NO 2 ci CFj h NOa ci H ch=cch2 NO 2 CEt CFj h NOa CI H ch-cch: NO 2 ci CFj H NOa ci Me chi=CHCH2 NOa CI CFj H NOa ci Et CHsCCIIj NO 2 CI CFj H NOa ci CI ch2=chch* NO i ci CFj H NOa ci H ch=cch2 NO 2 F CFj H NOa Br H chi=CHCH2 NO 2 H NOa h CFa Br h chsCCHj h h NOa h NOa Br H :h«=chch2 h H NOa h CFa Br h cheCCHi NOi h NOa H NOa Br H CHa=CHCHa NOi ci CFj h NOa Br h cheCCHi NOa OEt cfa h NOa Br h chsCCHi NOa ci cf, H NOa I H CHi =CHCHi NOa CI CFa H NOi I h chscchi NOa OEt CFj h NOa CFj h CHa=CHCHa NOa h NOa H CFa cf» h CHeCCHi h h NOa h NOa CFj H CHi =CHCHi H h NOa H CFi CFj H CHeCCH2 NOa h NOa H NOa cfs H CHa=CHCHa NOa CI CFj H NOa CFj h cheCCHi NOa OEt CFa h NOa CFj H cheCCHi NOa CI CFa h NOa Me H H NOa H NOa H CFi Me H h H H NOa H NOi Me h H H H NOa H CFi Me H H NOa H NOt K NOa Me H H NOi CI CFi H NOt 1 0 Table 1 (continued) the substituents on the benzene ring Rl Rs R4 2 co 4 6 Me H H NO 2 OEt CFj H NOa Me Me H NO2 CI CFj H NOa Me Et H NO 2 CI CFj H N02 Me CI H NO2 CI CFj H NO 2 Me H H NO2 F CFj H NOz Me H Me NO 2 CI CFj H NO2 Me H COMe NO2 CI CF, H NO2 Me H SO 2 Me NO 2 CI CFj H NO: Me h scc1 j NO2 ci CFj h NO: Me H CH2=CHCH: NO 2 h NO: h CFj Me h ch=cch2 h H NO 2 h NO: Me h CHa=CHCHa h H NOa h CFj Me H ch=CCH2 NO 2 H NOa h NOa Me H CHa=CHCH: NOi ci CFj h NOa Me H CHsCCHa NO 2 OEt CF, h NOa Me h ch=CCH2 NO2 CI CFa h NOa MeO h h NO: H NOa h CF.

MeO h h h H NOa h NOa MeO h h h h NOa h CFj MeO h H NO: H NOa h NOa MeO h h NO: CI CFj h NO: MeO H h N02 OEt CFj h NO: MeO Me h NOa CI CFi h NOa MeO Et H NOi CI CFi h NOa MeC CI h NOa CI CFj h NOa MeO h h NOa F CFj h NOa MeO h Me NOa CI CFj h NO: MeO 11 COMe NOa CI CFj h NOa MeO H SOiMe NOa CI CFj h NO: MeO h SCCl, NOa CI CFj h NOa MeO H CHi=CHCH2 NOa H NOa h CFi MeO h CHsCCHi H H NOa h NOa MeO 11 CHa=CHCHa h H NOa h CFj MeO H CHeCCHa NOa h NOa h NOa MeO H CHi =CHCHa NOt CI CFi H NOi MeO H CHeCCHi NOt OEt CFi H NOt 1 1 Table 1 (continued) the substituents on the benzene ring R1 R3 R* 2 S(Z) 4 6 MeO H CH=CCH2 NO2 CI CFj H NO 2 NOt H H NO 2 CI CFj H NO 2 NO 2 H H NO 2 OEt CFj H NO 2 NO 2 Me H NO 2 CI CFj H NO 2 NO 2 Et H NO 2 CI CFj H NO 2 NO 2 CI H NO 2 CI CFj H NO 2 NO2 H H NO 2 F CFj H NO 2 NO2 H Me NO 2 CI CFj H NO 2 NO 2 H COMe NOt CI CFj H NOt NO2 H SO 2 Me NO2 CI CFj H NO 2 NO i H SCCIt NOt CI CFj H NO 2 NOt H CHt=CHCHt NO2 H NOt H CF, NOi H CHsCCHt H H NOt H NOt NO 2 H CHt=CHCHt H H NOt H CF, NO* H CHsCCHt NO 2 H NOt H NO* NOt H CHt=CHCHt NO2 CI CFj H NOt NOt H CHsCCH, NOt OEt CFj H NOt NOt H CHeCCH, NOt Ci CFj H NOt 1 2 Table 2 the substituents on the benzene ring R2 R8 R4 2 8(Z) 4 6 F H H NOa H NOa H CFi F H H H H NOa H NO: F H H H H NOa H CFj F H H NO 2 H NO2 H NO: F H H CI H NOa H CI F H H NO* H CFi H NOa F H H NO: H H H NOi F H H CFj H NOa H CFi F H H NO: CI CFj H NOi F H H NO i OEt CFj H NOi F H H NOi OPh-OH-m CFs H NOi F H H H CI CFi H NOi F H H NOa OPr-n CFi H NOi F H H NOa Br CFj H NOi F H Me NO, CI CF» H NOi F H COMe NOi CI CFi H NOi F H SOsMe NOa CI CFi H NOi F H SCC1, NOa CI CFj H NOi F H COEt NOa CI CFj H NOi F Me H NOa CI CFj H NOi F Et H NOa CI CFj H NOi F CI H NOa H H H NOi F H H NOa F CFi H NOi CI H H NOa H NOi H CFi CI H H H H NOi H NOi CI H H H H NOi H CF, CI K H NOi H NOt H NOi CI H H CI H NO* K CI 1 3 Table 2 (continued) the substituents on the benzene ring R2 R8 R4 2 £3 1 00 1 1 4 6 CI H H NO 2 H CFa H NO2 CI H H NO 2 H H H NO 2 CI H H CFs H NO 2 H CF, CI H H NO 2 CI CFj H NO 2 CI H H NO 2 OEt CFa H NO 2 CI H H NO 2 OPh-OH-m CFj H NO 2 CI H H H CI CFa H NO 2 CI H H NO 2 OPr-n CFj H NO2 CI H H NO 2 Br CFj H NOa CI H Me NO 2 CI CFj H NO* CI H COMe NO 2 CI CF, H NOa CI H SOaMe NO2 CI CF, ' H NOa CI H SCCl, NO 2 CI CFj H NOa CI H COEt NO2 CI CF, H NOa CI Me H NO2 CI CFj H NOa CI Et H NO2 CI CFj H NOa CI CI H NO, H H H NOi CI H H NOi V CFj H NOa Br H H NOa CI CFi H NOa Br H H NOa OEt CFi H NOi Br Me H NOa CI CFi H NOa I H H NOa CI CFi H NOa CFi H H NOa H NOi H CFi CFi H H H H NOi H NOs CFi H H H H NOi H CFi CFi H H NOi H NOa H NOi CFi H H NOi H CFi H NOi CFi H H NOa H H H NOa CFi H H CF, H N02 H CF, CFi H H NOa CI CFj H NOi CFi H H NOa OEt CFj H NOi CFi H H H CI CFi H NOi CFi H H NOa Br CFi H NOi CFi H Me NOa CI CFi H NOi CFi Me H NOi CI CFi H NOt CFi Et H NOi CI CFi H NOt CFi CI H NOi CI CFi H NOt 1 4 Table 2 (continued) the substituents on the benzene ring R2 R8 R4 2 GO 4 6 CF, H H NO; F CF, H NO, Me H H NO, H NO 2 H CF, Me H H H H NO, H NO 2 Me H H H H NO, H CF, Me H H NO z H NO 2 H NO, Me H H CI H NO 2 H CI Me H H NO* H CFJ H NO, Me H H NO 2 H H H NO 2 Me H H CF, H NO, H CF, Me H H NO 2 CI CF, H NO 2 Me H H MO.

OEt CF, H NO 2 Me H H K'O, OPh-OH-m CFj H NO, Me H H H CI CF, H NO, Me H H NO: OPr-n CFa H NO, Me H H NO* Br CFi H NO, Me H Me NOt CI CFi H NO, Me H COMe r.

CI CFa H NO, Me H SOxMe i CI CFa H NO, Me H SCCl, NO, CI CFi H NO, Me H COEt NO, CI CFa H NO, Me Me H NO: CI CFa H NO, Me Et H NO, CI CFa H NO, Me CI H NOa H H H NO, Me H H NOt i CF, H NO, MeO H H NO 2 i; NO, H CF, MeO H H H H NO, H NO, MeO H H H H NO, H CF, MeO H H NO, H NO, H NO, MeO H H CI H NO, H CI MeO H H NO, H CF, H NO, MeO H H NO, H H H NO, MeO H H CFi H NO, H CF, MeO H H NOi CI CF, H NO, MeO H H NOi OEt CF, H NO, MeO H H NO, OPh-OH-m CF, H NO, MeO H H H CI CF, H NO, MeO H H NO, OPr-n CF, H NO, 1 5 Table 2 (continued) the substituents on the benzene ring R2 R8 R4 2 3(Z) 4 6 MeO H H NO2 Br CFs H NO 2 MeO H Me NO2 CI CF3 H NO 2 MeO H COMe NO2 CI CFs H NO 2 MeO H SO 2 Me NO 2 CI CF3 H NO 2 MeO H SCCl 3 NO 2 CI CFs H NO 2 MeO H COEt NO2 CI CF3 H NO 2 MeO Me H NO 2 CI CF3 H NO 2 MeO Et H NO2 CI CF3 H NO 2 MeO CI H NO2 H H H NO 2 MeO H H NO 2 F CF3 H NO 2 NO 2 H H NO 2 H NO 2 H CFa NO 2 H H H H NO 2 H NO2 NO 2 H H H H NO 2 H CFa NO 2 h H NO 2 h NO 2 h NO 2 NO 2 H H NO 2 H CFs H NO 2 N02 H H NO 2 H H H NO2 NO2 H H CF3 H NOa H CFa NO: H H NO 2 CI CFa H NOa NO2 H H NO2 OEt CFa H NOa NO: H H H CI CFa H NOa NO: H H NO 2 Br CFa H NO 2 NO: H Me NO 2 CI CFa H NO 2 NOa Me H NOa CI CFa H NOa NOa Et H NO 2 CI CFa H NOa NO 2 CI h NO 2 CI CFa h NO 2 NO 2 h h NO 2 F CFa h NOa F h CHa=CHCH2 NO 2 ci CFa h NOa F k CH=CCHa NO* OEt CFa h NOa F h ch=cch2 NO2 CI CFa h N02 F Me CHa=CHCHa NOa CI CFa h NO 2 F CI CHa=CHCHa NO2 CI CFa H NO 2 F H CH=CCHa NOa F CFa H NOa CI H CHa=CHCHa NO2 CI CFa H NOa CI H CHsCCHa NOa OEt CFi H NOa CI H CHsCCHa NOa CI CK.

H NOa CI Me CHa=CHCHa NOi CI CFs H NOa 1 6 Table 2 (continued) the substituents on the benzene ring R2 R8 R4 2 3(Z) 4 6 CI CI CH:=CHCH: NO: CI CFj H NO: CI H CHsCCH: NO: F CFj H NO: Br H CH:=CHCH: NO: CI CFj H NO: Br H CH = CCH: NO: OEt CFj H NO: Br H CH=CCH: NO: CI CFj H NO: I H CH:=CHCH: NO: CI CFj H NO: I H CH=CCH: NO: OEt CFj H NO: I H CH=CCH: NO: CI CF, H NO: CFj H CH:=CHCH: NO: CI CFj H NO: CFj H CH-CCH: NO: OEt CFj H NO: CFj H CH-CCH: NO: CI CFj H NO: CFj Me CH:=CHCH: NO: CI CFj H NO: CFj CI CH:=CHCH: NO: CI CFj H NO: CFj H CH=CCH: NO: F CFj H NO: Me H CH:=CHCH: NO: CI CFj H NO: Me H CH=CCH: MO: OEt CFj H NO: Me H CH-CCH: NO: CI CF, H NO: Me Me CH:=CHCH: NO: CI CF, H NO: Me CI CH:=CHCH: NO: CI CF, H NO: Me H CHsCCH: NO: F CF, H NO: MeO H CH:=CHCH: NO: CI CF, H NO: MeO H CHsCCH: NO: OEt CF, H NO: MeO H CHsCCHi NO: CI CFi H NO: MeO Me CHi =CHCH: NO: CI CF, H NO: MeO CI CHi =CHCH: NO: CI CF, H NO: MeO H CH=CCH: NO: F CF, H NO: NO: H CH:=CKCH: NO: CI CF, H NO: NO: H CH=CCH: NO: OEt CF, H NO: NO: H CHsCCH: NO: CI CF, H NO: NO: Me CHi =CHCH: NO: CI CF, H NO: NO: CI CH:=CHCH: NO: CI CF, H NO: NO: H CH=CCH: NO: F CF, K NO: 1 7 the substituents on the benzene ring R1 R2 R8 R4 2 co /""n 4 6 F F H H NO 2 H NO: H CF, F F H H H H NO: H NO: F F h H H H NO: k CF, F F h h NO: H NO: H NO: F F H H NO: CI CF, H NO: F F H H NO: OEt CF, H NO: F F Me H N02 CI CF, H NO: F F Et H NO 2 CI CF, H NO: F F CI H N02 CI CF, H NO: F F H H NO: F CF, H NO: F F H Me NO: CI CF, H NO: F F H COMe NO: CI CF, H NO: F F H SOsMe NO 2 CI CF, H NO: F F H SCCli N02 CI CF, H NO: F F H CHj =CHCH: NO: CI CF, H NO: F F H CHsCCHi NO: OEt CF, H NO: F F H CH-CCH: N02 CI CF, H NO: CI CI H H NO: H NO: H CF, CI CI H H H H NO: H NO: Ci CI H H H H NO: H CF, CI CI H H NO: H NO: H NO: CI CI H H NO: CI CF, H NO: CI CI H H NO: OEt CF, H NO: CI CI Me H N02 CI CF, H NO: CI CI Et H NO: CI CF, H NO: CI CI CI H NO: CI CF, H NO: CI CI H H NO: F CF, H NO: CI CI H Me NO: CI CF, H NO: Table 3 (continued) the substituents on the benzene ring R1 R2 R8 R4 2 8(0 4 6 CI CI H COMe NO2 CI CF, H no 2 CI ci H so 2 Me no 2 ci CFs H no: CI CI H sccl 3 no 2 ci CFs H no 2 ci ci H ch2=CHCH2 no 2 CI CFs H no 2 ci ci H ch=cch2 no 2 OEt CFs H no 2 CI ci H chscchz no 2 ci CFs H no 2 CI no 2 H H NO 2 H no 2 H CFs CI no 2 H H H H NO 2 H NO 2 CI NO 2 H H H H NO* H CF, CI NO 2 H H NO 2 H NO 2 H NO 2 CI NO2 H H NO2 CI CF, H NO 2 CI NO 2 H H NO: OEt CF, H NO2 C).

NO2 Me H NO 2 CI CF H NO 2 CI NO2 Et • H NO2 CI CF, H NO2 CI NO 2 CI H NO 2 CI CF, H NO 2 CI NO2 H H NO2 F CF, H NO 2 CI NO2 H Me NO2 CI CF, h NO* CI NO 2 h COMe NO2 ci CFs h NO* ci NO2 h SO*Me NO2 ci CF, h NO2 CI NO* h SCCl, NO2 CI CF, h NO* CI NO 2 h ch*=chch* NO2 ci CF, h NO 2 CI NO 2 h ch=cch* NO 2 OEt CF, h NO2 ci NO* h CHsCCHj NO* CI CF. h NO* Me CI h h NO* h NO* h CF, Me CI h h h h NO* h NO* Me CI h h h h NO* h CF, Me CI h h NO* h NO* h NO* Me CI h h NO* CI CF, h NO 2 Me CI H H NO2 OEt CF, H NO* Me CI Me H NO2 CI CF, H NO 2 Me CI Et H NO 2 ci CF, H NO 2 Me ci CI H NO2 CI CF, H NO* Me CI H H NO: F CF, H NO* Me ci H Me NO* ci CF, h NO* Me ci h COMe NO* ci CF, h NO* Me CI h SOsMe NO* CI CF» h NO* Table 3 (continued) the substituents on the benzene ring R1 R2 R8 R4 2 3(Z) 4 6 Me ci H SCCl 3 NO 2 ci CF3 H NO 2 Me Ci H CH2=CHCH2 NO 2 ci CF3 H NO 2 Me ci H ch=cch2 NO 2 OEt CFs H NO 2 Me CI H CH^CCHz NO 2 CI CFs H NO 2 MeO NO z H H NO 2 H NO 2 H CFs MeO NO 2 H H H H NO 2 H NO 2 MeO NO 2 H H H H NO 2 H CFs MeO NO 2 K H NO 2 H NO 2 H NO 2 MeO NO 2 H H NO 2 ci CFj H NO2 MeO NO 2 H H NO2 OEt CFs H NO 2 MeO NO2 Me H NO 2 ci CFs H NO 2 MeO NO2 Et H NO2- CI CFj H NO 2 MeO NO 2 ci H NO2 CI CFj H NO 2 MeO NO 2 H H NO 2 F CFj H NO 2 MeO NO2 H Me NO 2 CI CFj H NO 2 MeO NO 2 H COMe NO 2 CI CFj H NO 2 MeO NO: H SOsMe NO 2 CI CFj H NO 2 MeO NO2 H SCCls NO2 CI CFj H NO 2 MeO NO.

H CHi=CHCH2 NO 2 CI CFj H NO 2 MeO NO2 H ch=cch2 NO 2 OEt CFj H NO 2 MeO NO2 H CH=CCH* NO2 CI CF, H N02 The N-quinoxalylanlllnes used In the present Invention can be produced usually by, for example, the method (a), (b) or (c) below referring to Japanese Patent Application Laid-open No. Sho 60-97964. Note that Zl, Z1 and Zs in the following reaction schemes are included by Z in the above-described general formula (1). (a) In the case where Z1 represents a hydrogen atom or a halogen atom: wi acid Ri "k acceptor (0)m T N. -R3 + Hal N NH2 4 In the above-described reaction scheme, R1, R2, R3, X, Y, m, n, j and k have the same meanings as defined above, Hal represents a halogen atom such as chlorine or fluorine, Z1 represents a hydrogen atom or a halogen atom.

The acid acceptor used in this reaction includes, for example, hydroxides, carbonates, hydrogen carbonates, and hydrides of alkaline metals, or hydroxides and carbonates of alkaline earth metals, desirably potassium hydroxide and sodium hydride.

The above-described reaction may be carried out preferably in an aprotic polar solvent such as dlmethylformamide, dimethyl sulfoxide, sulfolane, tetrahydrofuran, or dioxane at an appropriate temperature, for example, -50 to 100°C for 0.5 to 24 hours with stirring. (b) In the case where Z3 is an alkoxy group or a phenoxy group which may be substituted with a halogen atom(s), a nitro group(s) or a hydroxyl group(s): In the above-described reaction scheme, Z2 represents a halogen atom such as chlorine or bromine, R1, R2, R3, X, Y, m, n, j and k have the same meanings as defined above, Z3 is an alkoxy group or a phenoxy group which may be substituted with a halogen atom(s), a nitro group(s) or a hydroxyl group(s). (0)m (0)m 21 The acid acceptor used in this reaction is the same as that can be used in the above-described method (a) and the solvent which is usually used includes, in addition to the above-described aprotic polar solvents, alcohols such as methanol and ethanol, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and m-dichlorobenzene.

The reaction temperature is usually -30°C to 150°C and the reaction time is 0.5 to 24 hours. (c) In the case where R4 is an alkyl group, an alkenyl group, an alkynyl group, an alkylcarbonyl group, an alkylsulfonyl group, or an alkylsulfenyl group which may be substituted with a halogen atom(s): In the above-described reaction scheme, R* is an alkyl group, an alkenyl group, an alkynyl group, an alkylcarbonyl group, an alkylsulfonyl group, or an alkylsulfenyl group which may be substituted with a halogen atom(s), R1, R2, R3, X, Y, Z, m, n, j and k have the same meanings as defined above, Hal is a halogen atom such as chlorine, bromine, or iodine.

The acid acceptor used in this reaction includes, in addition to those used in the method (a) above, tertiary amines and pyridines. It is desirable that sodium hydride is used suitably for alkylation, alkenylation or alkynylation, and triethylamlne or pyridine is suitable for other purposes.

The above-described reaction can be carried out in solvents which include. In addition to the aprotic polar solvents cited for the method (a) above, lialogenated hydrocarbons such as carbon tetrachloride, chloroform, and m-dichlorobenzene, or aromatic hydrocarbons such as benzene, toluene, and xylene. The reaction (0)m (0)m acid acceptor 22 temperature is generally -30°C to 150°C and the reaction time is 0.5 to 24 hours.

The target compounds obtained by the methods (a), (b) or (c) can be purified by recrystallization from a suitable solvent, column chromatography or the like to give a pure compound.

The N-quinoxalylanilines used as an active ingredient in the present invention may be used singly. Alternatively, when the industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms of the present invention are used, they may be used as mixed agents by further adding thereto one or more known industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms.

Hereafter, representative examples thereof are listed. However, the present invention is not limited thereto.

Cuprous oxide, quaternary ammonium compounds, allyl lsothlocyanate, 2-amino-3-chloro-1,4-naphthoquinone, ethylene-bls-thiocyanate, 2-n-octyl-3-isothiazolone, glutara3.dehyde, 5-chloro-2-n-decyl-3-isotlazolone, 5-chloro-2,4-difluoro-6-methoxyisophthalonltrile, 2-chloro-4-methylamino-6-isopropylamlno-s-triazine, 5-chloro-2-methyl-3-isothiazolone, 2,3-dlchloro-1,4-naphthoquinone, diiodomethyl-p-tolylsulfone, N,N-dimethyl-N' -phenyl-N' - (fluorodichloromethylthio) sulf amide, N-(3,4-dlchlorophenyl)-N1-methylurea, N,N-dimethyl-N'-{3,4-dlchlorophenyl)urea, zinc dimethyldithiocarbamate, 2,6-dichloro-3,5-dicyano-4-phenylpyridine, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 4,5-dichloro-2-(4-ch2orobenzyl)-3-isothiazolone, 4,5-dichloro-2-(4-chlorophenyl)-3-isothlazolone, 4,5-dlchloro-2-n-hexyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone, 1,2-dlbromo-2,4-dicyanobutane, 2,2-dibromo-3-nitrilopropionamide, 2- thiocyanomethylthiobenzothlazole, 2-(4-thlazolyl)benzimidazole, thiabendazole, tetrafluoroisophthalonitrile, 2,3,5,6-tetrachlo.ro - 4 - (methylsulf onyl) pyridine, tetraphenylbornnepyridine salts, tetramethylthluram disulfide. 23 tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, tetra-n-butylthiuram disulfide, tetrachloroisophthalonitrile, tetrachlorophthalonitrile, Cu-10% Ni solid solution alloy, N-trichloromethylthlotetrahydrophthalimide, N-trichloromethylthiophthalimlde, 2,3,6-trichloro-4 -propylsulfonylpyridine, N-(2,4,6-trlchlorophenyl)maleimide, 4,5-trimethylene-2-methyl-3-isothiazolone, 2-pyridinethiol-l-oxide zinc salt, 2,3,3-triiodoallyl alcohol, N-(fluorodichloromethylthio)phthalimide, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, N-phenethyldlchloromaleimide, 2-bromo-2-nltropropanediol, 5-bromo-5-nitro-l,3-dioxane, bromochlorodimethylhydantoin, N-benzyldichloromaleimide, 1,2-benzlsothlazoline-3-one, 2-(methoxycarbonylamlno)benzimidazole, 4-methyl-5-chloro-2-n-octyl-3-isothiazolone, 2-methylthlo-4-t-butylamino- 6 -cyclopropylamino-s-triazine, N-2-methyl-6-ethylphenyldichloromalelmide, 2-methyl-3-isothiazolone, methylene-bis-thlocyanate, 3-lodo-2-propynylbutyl carbamate, and iodopropargylbutyl carbamate.

Further, the N-quinoxalylanillnes which is used as an active Ingredient in the present invention may be constituted by a single compound or a mixture of several kinds of the N-quinoxalyJ anilines.

In the present invention, the N-quinoxalylanilin * sed as an active ingredient may be added singly to the systems of the above-described applications, or may b«. blended as mixtures of the active ingredient with a suitable carrier or solvent or as an aqueous emulsions or dispersions.

To give an outline of the formulation of industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms of the present invention in the field of application as Industrial antibacterial/antifungal agents and algicides, the N-quinoxalylanilines used as the active ingredient in the present invention may be blended and mixed with suitable carriers and auxiliaries, for example, surfactants, binders, stabilizers and the like, and formulated into a wettable 24 powder, an emulsion, a sol i_gent (a flowable agent) and other suitable forms.

When these formulations are prepared, no upper limit is posed on the concentration of N-quinoxalylaniline, as active ingredient, so long as wettable powders, emulsions, liquid agents, sol agents, and other suitable formulations can be prepared. However, it may be blended in a proportion of 1-90% by weight, preferably 3-40% by weight, based on the weight of the formulation.

As the carrier, either solid or liquid carriers can be used so long as it is usually used for industrial antibacterial/antifungal agents and algicides but not limited to particular ones.

Examples of the solid carriers include mineral powders, for example, kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphorus lime, white carbon, hydrated lime, silica sand, ammonium sulfate, urea and the like, or plant powders, for example, soybean powder, starch, crystalline cellulose and the like, alumine, silicates, sugar polymers, highly disperslble silicic acid, wax s and the like.

Examples of the liquid carriers Include wo*" _sr, alcohols, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol is propyl alcohol, ethylene glycol, benzyl alcohol and the like, aromatic hydrocarbons, for example, benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene and the like, or halogenated hydrocarbons, for example, chloroform, dichloromethane, ethylene dichloride and the like, ethers, for example, ethyl ether, dioxane, tetrahydrofuran and the like, ketones, for example, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone and the like, esters, for example, ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate and the like, nltriles, for example, acetonitrile, propionitrile, acrylonitrlle and the like, sulfoxides, for example, dimethyl sulfoxide and the like, alcohol ethers, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like, amines, for example, trlethylamlne and the like, as well as aliphatic and alicyclic hydrocarbons, for example, n-hexane, cyclohexane and the like, and further industrial gasoline (petroleum ether, solvent naphtha and the like) and petroleum fractions (paraffins, kerosene, gas oil and the like) and the like.

In the case of formulations such as emulsions, wettable powders, and sol agents (flowable agents), surfactants are blended for the purpose of emulsification, dispersion, solubilization, wetting, foaming and spreading. As such surfactants, the followings are exemplified but not limited thereto.

Examples of the nonionic surfactants Include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester and sorbitan alkyl ester and the like.

Examples of the anionic surfactants include alkyl benzenesulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, lauryl sulfate and the like.

Examples of the cationlc surfactants include alkylamlnes (laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonlum chloride and the like) and the like.

Examples of the amphoteric surfactants include carboxylic acid (betaine type) sulfuric acid esters and the like.

In addition to the above, there can be blended, thickening agents and various auxiliaries such as polyvinyl alcohol (PVA), carboxymethylcellulose (CMC), gum Arabic, polyvinyl acetate, gelatin, casein, sodium alginate, tragacanth gum, guar gum, xanthan gum, hydroxypropyl cellulose and the like.

Further, if needed, suitable amounts of stabilizing agents such as antioxidants and ultraviolet radiation absorbents and the like may be added.

The Industrial antibacterial/antifungal agents, algicides containing N-quinoxalylanilines as an active ingredient of the present invention can be used in the following applications.

Inhibition of growth of bacteria, fungi and algae in emulsion products such as aqueous paints, adliesives, latex, and aciylics, slurry products such as starch, pigments, calcium carbonate, and 26 joint cements; preservation of woods in construction materials (building construction materials, civil engineering construction materials and the like); preservation of cutting oils; fungi-proofing of surfactants; sterilization and prevention of generation of slime in cooling towers in production facilities in factories and air conditioning systems in buildings, as well as in pulp and paper making factories; antibacterial and antifungal treatment of cloths and leathers by spraying onto them or dipping them; protection from the attacks by bacteria, fungi and algae occurring while coating films, particularly exterior coating films, are exposed to the weather; preventing and protection from bacteria, fungi and algae on Interior or exterior materials (for houses and medical facilities), construction materials (building construction materials, civil engineering construction materials and the like), house electric products, home-use general goods, sport goods and the like, composed of resins such as polyvinyl chloride, pc"iyurethane, polyethylene, polypropylene, silicone, modified silicone, nylon, and epoxy resin; prevention of accumulation of slime in sugar cane and beet sugar production apparatus; prevention of accumulation and deposition of microbes in air washers, scrubber systems and supply system for industrial fresh water; retention of hygienic environment in food factories and the like; deodorization and sterilization when cleaning production facilities and for sewerage disposal factories, excrement disposal factories and the like; prevention of contamination and deposition of microbes in oil field cutting oil, muddy water, and secondary petroleum recovery process; prevention of growth of bacteria and fungi in paper covering materials and covering processing; prevention of microbial contamination of cosmetics and toiletry products; inhibition of growth of algae in pools and the like; prevention of microbial contamination of agricultural blends, electrodeposition systems, diagnostic and pharmaceutical products, medical apparatus and the like; and prevention of accumulation of microbes in photographic treatments.

The agents for preventing the adhesion of organisms 27 containing N-quinoxalylanilines as an active ingredient can be used, for example, fcr preventing the adhesion of harmful aquatic organisms such as blue mussel (Mytilus edulis), barnacle (Balanus sp.), oyster, Hydrozoa, hydra (Hydra sp.), serpula (Serpula sp.), ascidian, bryozoan, and shellfish such as pond snail, algae such as sea lettuce (Ulva sp.). Enteromorpha sp., and Ectocarpus sp. to fishing nets, bottom of ships, facilities placed in the sea such as buoys, marine constructions, steam condenser cooling water systems for thermal or atomic power plants, inlet channels for cooling water for heat exchangers for use in chemical industries, underwater constructions such as equipment attached to a dam, and reservoirs.

Next, synthetic examples of N-quinoxalylanilines will be described. However, the compounds which are used in the present invention are not limited to thereto.

Synthesis Example 1 N-(6-Chloro- 2 -quinoxalyl) - 2,6 -dinitro-3-chloro-4-trlfluoromethylaniline (Compound 1) (1) Synthesis of 2-amino-6-chloroqulnoxaline In a 2-liter autoclave were charged 150 g of 2,6-dichloroquinoxaline and 500 ml of 28% ammonium water and heated at 120°C for 24 hours. After leaving the reaction mixture to cool, the resultant crystals were washed with water and dried, recrystalllzed from ethanol to obtain 86 g of pale brown crystals of 2-amino-6-chloroquinoxaline(mp 217-220°C). (2) Synthesis of Compound 1 2-Amino-6-chloroquinoxaline (5 g) obtained in the above- described reaction (1) was dissolved in 50 ml of dlmethylformamide and cooled to -30°C with stirring. After adding 3.7 g of powdery potassium hydroxide, a solution of 8.5 g of 2,4-dichloro-3,5-dlnitrobenzotrifluoride in 15 ml of dlmethylformamide was added. The mixture was slowly warmed to ambient temperature and stirred for 24 hours. The reaction solution was poured into water and rendered acidic with diluted hydrochloric acid, followed by extraction of the product with benzene. The benzene layer was 28 washed with water and dried over sodium sulfate and then the solvent was evaporated to obtain yellow crystals. The crystals were purified by silica gel column chromatography (eluent: benzene/ethyl acetate=4/l) to obtain 8.1 g of N-(6-chloro-2-quinoxaly1) - 2,6 -dinitro-3-chloro-4-trifluoromethylaniline (mp 182-187°C) .

Synthesis Example 2 Synthesis of N-(6-chloro-2-quinoxalyl)-2,6-dlnitro-3-ethoxy-4-trifluoromethylaniline (Compound 2) To 15 ml of ethanol was added 0.4 g of sodium hydride and stirred sufficiently until hydrogen gas generation ceased. Then a solution of 2 g of N-(6-chloro-2-qulnoxalyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline obtained in Synthesis Example 1 in 20 ml of dimethyl sulfoxide was added and the mixture was stirred at 80°C for 3 hours. After leaving the reaction mixture to cool, the reaction solution was poured into water and rendered acidic with diluted hydrochloric acid, and the product was extracted with benzene. The benzene layer was washed with water and dried over sodium sulfate, followed by evaporating the solvent to obtain yellow crystals. The crystals were purified by silica gel column chromatography (eluent: chloroform) to obtain 1.1 g of N-(6-chloro-2-qulnoxalyl)-2,6-dinitro-3-ethoxy-4-trifluoromethylaniline (mp 150-155°C).

Synthesis Example 3 Synthesis of N-(6-chloro-2-qulnoxalyl)-2,4-dinitro-6-trifluoromethylaniline (Compound 3) 2-Amino-6-chloroquinoxaline (1 g) was dissolved in 15 ml of dlmethylformamide and cooled to -30°C with stirring. Then, powdery potassium hydroxide (0.8 g) was added thereto and a solution of 1.5 g of 2-chloro-3,5-dinitrobenzotrlfluoride in 5 ml of dlmethylformamide was added. The mixture was slowly warmed to ambient temperature and stirred for 3 hours. The reaction solution was poured into water and rendered acidic with diluted hydrochloric acid to precipitate yellow crystals, which were collected by 29 filtration. The crystals were washed with water and dried, and purified by silica gel column chromatography (eluent: chloroform/ethyl acetate=5/l) to obtain 0.9 g of N-(6-chloro-2-quinoxalyl)-2,4-dinitro-6-trifluoromethylaniline (mp 90-93°C) .

Synthesis Example 4 Synthesis of N-(6-chloro-2-qulnoxalyl)-2,4,6-trinitroaniline (Compound 4) 2-Amino-6-chloroquinoxaline (1 g) was dissolved in 15 ml of dlmethylformamide and cooled to -50°C with stirring. Then, powdery potassium hydroxide (0.8 g) was added thereto and a solution of 1.3 g of 2,4,6-trinltrofluorobenzene in 5 ml of dlmethylformamide was added. The mixture was slowly warmed to ambient temperature and stirred for 10 hours. The reaction solution was poured into water and rendered acidic with diluted hydrochloric acid to precipitate yellow crystals, which were collected by filtration. The crystals were washed with water and dried, and purified by silica gel column chromatography (eluent: benzene/ethyl acetate=4/l) to obtain 0.9 g of N-(6-chloro-2-qulnoxalyl)-2,4,6-trlnitroaniline (mp 120-130°C) .

Synthesis Example 5 Synthesis of N-acetyl-N-(6-chloro-2-qulnoxalyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline (Compound 5) N-(6-Chloro- 2-qulnoxalyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline (1 g) obtained in Synthesis Example 1 was dissolved in 20 ml of benzene and 0.4 g of triethylamine was added thereto. To the mixture was added 0.3 g of acetyl chloride and the resulting mixture was stirred at ambient temperature for 6 hours. The salts produced were filtered and the filtrate was washed with diluted hydrochloric acid and with water and dried, followed by evaporating the solvent to obtain a transparent yellow glassy substance. The glassy substance was purified by silica gel column chromatography (eluent: benzene/ethyl acetate»4/l) to obtain 0.8 g of N-acetyl-N-(6-chloro-2-quinoxalyl)-2.6-dinitro-3-chloro- 4-trifluoromethylaniline (glassy).

Synthesis examples 6-20 In the same manner as in Synthesis Examples 1-5, Compounds 6-20 were synthesized and shown in Table 4.

Table 4 compound No.

R1 Rs the substituents on the benzene ring physical value R4 2 3(Z) 4 5 6 tnpOC) 6 H H H NOz CI CFj H NOi 89- 90 7 H CHj H NO: CI CFj H NOi 183-185 8 CFj H H NO: CI CFj H NOi 163-165 9 CFi H H NOi OEt CFj H NOi 164-166 CI H H NOi H CF, H NOi 182-186 11 CI H H NOi OPh-OH-m CFj H NOi 234-242 12 H H H NOi H NOi H CF, 100-105 13 CI H H H CI CFj H NOi 226-227 14 CI H H H H NOi H NOi 232-235 CI H H H H NOi H CF, 215-220 16 CI H H CI H NOi H CI glass 17 H CI H NOi CI CFj H NOz 173-174 18 CI H CHi NOi CI CFj H NOi glass 19 CI H SOiCH, NOi CI CFj H NOi glass CI H SCCIi NOi CI CFj H NOi glass Examples of formulations in the case where the N-quinoxalylanilines are used as industrial antibacterial/antifungal agents and algicides will be shown by use of compounds 1 and 3. However, the blending proportion of active ingredient, and the kind and addition 31 amount of carrier and auxiliaries arr .lot limited thereto.

CI "co , O2N CI O2N compoud 1 compoud 3 Formulation Example 1 (Emulsion) Component % by weight Compound 1 5 Dimethyl sulfoxide 85 Methyl isobutyl ketone 5 Sorpol 800A (Emulslfler produced by Toho Chemical) 5 The above components were mixed and dissolved to obtain an emulsion containing 5% of the active ingredient.

Formulation Example 2 (Wettable powder) Component % by weight Compound 3 20 Lauryl sulfate 7 Clay 73 The above components were mixed and ground uniformly to obtain a wettable powder containing 20% of the active Ingredient. 32 Formulation Example 3 (Flowable agent) Component % by weight Compound 1 Lauryl sulfate Xanthan gum Hydroxypropyl cellulose Deionized water 2 2 1 75 The above components were charged in a ball mill and ground and mixed for 12 hours to obtain a flowable agent containing 20% of the active ingredient.

The formulated industrial antibacterial/antifungal agents and algicides of the present invention may be used by various methods conventionally practiced for industrial antibacterial/antifungal agents and algicides including methods for adding and mixing the formulations in various industrial raw materials or products and for coating or spraying the formulations on the surface of various industrial raw materials or products, as they are or after diluting them with water or suitable organic solvents, and dipping various industrial raw materials and products in diluted solutions of industrial antibacterial/antifungal agents and algicides of the present invention. However, the present invention is not limited to any particular method.

To give an outline of the formulation of Industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms of the present invention in the field of application as the agents fo. preventing the adhesion of organisms, the N-quinoxalylanilines used as the active ingredient in the present invention may be used after they have been formulated into the form of paints(coatings), solutions, emulsions and the like.

For the formulations of those paints(coatings), solutions. 33 emulsions and the like, the general formulation methods usually employed can be ur-fd.

Where the agents for preventing the adhesion of aquatic organisms of the present invention are used in the form of antifouling coatings, the N-quinoxalylanillne which is the active ingredient, for example, is blended with a film-forming agent to prepare a coating, and the coating is coated on bottoms of ships, marine constructions, inlet channels for cooling water, underwater constructions or the like, whereby the adhesion and propagation of aquatic organisms can be prevented.

Oil varnishes, synthetic resins, artificial rubbers and the like are used as the film-forming agent.

Further, if necessary, solvents, pigments or the like may be used.

In the preparation of coatings, no upper limit is posed on the concentration of the N-qulnoxalylanillne as the active ingredient so long as a coating film can be formed, but the N-quinoxalylanillne is blended in a proportion of 1-50% by weight, and preferably 5-20% by weight, based on the weight of the antifouling coating.

Formulation examples in the case where the agents for preventing the adhesion of aquatic organisms of the present invention are used as antifouling coatings will be described below. 34 Formulation Example 4 Component % by weight Compound 1 8 VYHH (vinyl-base synthetic 7 resin produced by UCC) Rosin 7 Trlcresyl phosphate 3 Talc 20 Barium sulfate 15 Iron red 10 Xylene 20 Methyl isobutyl ketone 10 100 Formulation Example 5 Component % by weight Compound 3 CR-10 (chlorinated rubber 13 resin produced by Asahi Denka) Zinc white Talc Plasticlzer 2 Iron red Xylene 100 Where the agents for preventing the adhesion of aquatic organisms of the present invention are used in the form of solutions, a solution is prepared by dissolving the N-quinoxalylaniline which is the active ingredient in a solvent together with a film-forming agent and the solution is coated on fishing nets for breeding, fixed fishing nets or the like, thereby allowing the adhesion and propagation of aquatic organisms to be prevented.

Examples of the film-forming agents used are synthetic resins, artificial rubbers, natural resins and the like, and examples of the solvents used are xylene, toluene, cumene, methyl ethyl ketone, methyl isobutyl ketone, acetone and the like.

Further, if necessary, additives such as plasticizers may be added for use.

In the case of preparing the solutions, the N-quinoxalylanillne as the active ingredient does not have the upper limit on the concentration so long as the solution can be formed, but the compound is blended in the proportion of 1-50% by weight, and preferably 5-30% by weight, based on the weight of the solution.

Formulation examples in the case where the agents for preventing the adhesion of aquatic organisms of the present invention are used as antifouling solutions will be described below.

Formulation Example 6 Component % by weight Compound 1 15 Acrylic resin (50% 50 xylene solution) Xylene 35 100 Formulation Example 7 Component % by weight Compound 3 10 Acrylic resin (50% 40 xylene solution) Di-tertiary nonylpenta-sulfide 5 Liquid paraffin 5 Xylene 40 100 Where the agents for preventing the adhesion of aquatic organisms of the present Invention are used in the form of emulsions, a surfactant is added to a solution of the N-quinoxalylaniline as the active ingredient according to a generally practiced method when usually preparing emulsions to prepare a desired emulsion and 36 there is no limitation on the kind of surfactant used.

The emulsions thus prepared can be used by kneading them in raw materials, such as polymeric resins, of fishing nets for breeding, fixed fishing nets or the like used in sea or water.

In the case of preparing emulsions, the N-quinoxalylaniline as the active ingredient does not have the upper limit on the concentration so long as the emulsion can be formed but is blended in a proportion of 1-50% by weight, and preferably 3-30% by weight, based on the weight of the emulsion.

The above-mentioned solutions or emulsions of the present invention can be used by adding to service water, reservoir water or the like in order to prevent the adhesion of and propagation of aquatic organisms in inlet channels for cooling water or reservoir.

DESCRIPTION OF PREFERRED EMBODIMENTS Hereafter, the present invention will be described more concretely and in further detail by examples using the compounds described above 1 and 3, and the compounds described below 4, 7 and 9. However, the present invention is not limited thereto.

"YYinrY- FiCrA^ OjN ) ( 02N OEt O2N CI compoud 4 compound 7 compond 9 Example 1 (Evaluation of antibacterial/antifungal activities) Test bacteria (6.6 ml) of Bacillus subtilis was added to 125 ml of bouillon agar medium and test fungi(31.3 ml) of Trichophyton mentagrophyf-.es was added to 125ml of Sabouraud agar medium and each was stirred carefully so that no foaming can occur and spread over a plate uniformly and allowed to solidify. Then, a predetermined 37 • amount of the compound of the present invention was weighed and diluted with acetone to a predetermined concentration. Samples thus prepared, each of which containing a compound of the present invention of the predetermined concentration were absorbed by paper disks each of which were placed on filter paper and air dried. Thereafter, the disks were equidistantly placed on a plate on which test microbe was spread. Bacillus snbtilis was incubated in an incubator at 37"C for 1 day whereas Trichophyton mentaqrophytes was incubated in an incubator at 28°C for 3 days. The diameter of each inhibitory circle was measured and evaluation of activity was performed. Table 5 shows the results obtained by use of samples in a concentration of 100 ppm. Note that the symbols in Table 5 have the following meanings.

A: Bacillus subti]is B: Trichophyton mentaarophyt.es + : Inhibitory circle (A: 10-13 mm, B: 10-20mm) was observed.

No inhibitory circle was observed.

Table 5 Compound Judgment No. A B 1 + + 3 + + 4 + + 7 + Example 2 (Evaluation of antibacterial/antifungal activities) A dilution series (20,000, 10,000, 5,000, 2,500, 1,250, 626, 313, 156, 78, 39 mg/1) of the solutions of the compound of the present invention was prepared using dimethyl sulfoxide. One half (0.5) ml of each of those solutions was added to 9.5 ml of sensitivity agar-N (Nlssui Seiyaku) for bacteria or to 9.5 ml of potato dextrose agar medium (Nlssui Seiyaku) for fungi and mixed and the mixture was spread over a Petri dish to form a solidified plate. The concentration of the present compound in the agar medium was each 38 1,000, 500, 250, 125, 62.5, 31.3, 15.6, 7.8, 3.9, or 2.0 rag/1. The inoculated bacteria were incubated in sensitivity assay bouillon (Nissui Seiyaku) at 37°C for 20 hours. On the other hand, fungi were incubated on a potato dextrose agar medium (Nissui Seiyaku) for 10 days and then a 106 CFU/ml suspension was prepared from each of them. The test bacteria or fungi suspension was streaked on a agar plate containing the compound of the present invention and the agar plate was incubated at 37±1°C for 18-20 hours for bacteria or at 27°C for 7 days for fungi. And the concentration at which no growth was observed was defined as the minimum inhibitory concentration (MIC). The results are shown in Tables 6 and 7. Note that the symbols in the tables have the following meanings. A: Bacillus snbtilis B: Trichophyton mentagrophytes C: Staphylococcus aureus D: Escherichia coll E: Pseudomonas aeruginosa F: Aspergillus nlaer G: Penicllllnm fnniculosum H: Candida albicans Table 6 Results of MIC measurement on bacteria (mg/1) Compound Test Bacteria No.

A C D E 1 <2.0 <2.0 31.3 .6 3 <2.0 <2.0 .6 31.3 Table 7 Results of MIC measurement on fungi(mg/1) Compound Test Fungi No. F G B H 1 2.0 <2.0 15.6 <2.0 3 3.9 3.9 <2.0 15.6 Example 3 (Evaluation of antibacterial/antifungal activities) A dilution series (20,000, 10,000, 5,000, 2,500, 1,250, 626, 39 313, 156, 78, 39 rng/1) of the solutions of the compound of the present invention was prepared using dimethyl sulfoxide. One half (0.5) ml of each of those solutions was added to 9.5 ml of sensitivity agar-N (Nissui Seiyaku) for bacteria or to 9.5 ml of potato dextrose agar medium (Nissui Seiyaku) for fungi and mixed and the mixture was spread over a Petri dish to form a solidified plate. The concentration of the present compound in the agar medium was each 1,000, 500, 250, 125, 62.5, 31.3, 15.6, 7.8, 3.9, or 2.0 mg/1. The inoculated bacteria were incubated in sensitivity assay bouillon (Nissui Seiyaku) at 37°C for 20 hours. On the other hand, fungi were Incubated on a potato dextrose agar medium (Nlssui Seiyaku) for 10 days and then a 106 CFU/ml suspension was prepared from each of them. The test bacteria or fungi suspension was streaked on a agar plate containing the compound of the present invention and the agar plate was incubated at 37±1°C for 18-20 hours for bacteria or at 27°C for 7 days for fungi. And the concentration at which no growth was observed was defined as the minimum inhibitory concentration (MIC). The results are shown in Tables 8 and 9. Note that the symbols in the tables have the following meanings.

I: Micrococcus lutea J: Corynebanteyliim aquaticnm K: Alcallgenes faecalls L: Salmonella typhymnrium M: Chetomlum globosum N: Rhlzopus oryzae O: Rodotorula rubra P: Saccharomyces cervlslaes Table 8 Results of MIC measurement on bacteria (mg/1) Compound Test Bacteria 2 0 • I J K L 1 <2.0 <2.0 <2.0 >1,000 40 Table 9 Results of MIC measurement on fungi (mg/1) Compound Test Fungi No.

M N 0 P 1 <2.0 >500 <2.0 >500 Example 4 (Evaluation of Bac> ericidal effect on Legionella strain) A 2,000 mg/1 solution of the compound of the present invention in dimethyl sulfoxide was prepeared and 1 ml of the sample solution was diluted with 19 ml of sterilized tap water to prepare a solution of a concentration of 100 mg/1. To 20 ml of this solution containing the compound of the present invention was Inoculated 0.1 ml of test bacteria solution fLegionella pneumophila. 3.1X108 cells/ml]. After the combined solution was allowed to stand at 30°C for 24 hours, the number of survival cells was counted. The results are shown in Table 10.

Table 10 Compound No. Number of survival cells/ml after 24 hours 1 <10 3 <10 Control 1.2X106 (sterilized tap water) Example 5 (Evaluation of growth inhibition activity on a fresh water green alga) A predetermined amount of a compound of the present invention was dissolved in a medium containing 10s cells /ml of a fresh water green alga (Selenastrum caprlcornntiiml in a logarithmic growth stage to prepare a sample, and the concentration of the compound of the present invention in the medium of the sample was 500 ppb or 50 ppb, respectively. And the sample was incubated by stationary culture at 23±1°C under continuously illuminated conditions all day long.

After 72 hours, the number of cells In the sample was counted 41 using a hemocytometer and growth rate was obtained therefrom. The growth inhibition rate was calculated by comparison with the non-treated lot.

The results are shown in Table 11.

Table 11 Compound No.

Growth Inhibition rate(%) 500 ppb 50 ppb 1 89 33 3 95 69 4 93 34 7 59 17 9 82 9 Example 6 (Evaluation of growth Inhibition activity on sea diatom) A predetermined amount of a compound of the present invention was dissolved In a medium containing 10s cells /ml of a sea water diatom (Nltzschla closterium) in a logarithmic growth stage to prepare a sample, and the concentration of the compound of the present invention in the medium of the sample was 500 ppb or 50 ppb, respectively. And the sample was Incubated by stationary culture at 23±1°C under continuously illuminated conditions all day long.

After 72 hours, the cells were collected by centrlfugation and broken by the addition of methanol and the chlorophyll thereof was extracted.

The amount of the chlorophyll was decided from the absorbance of the chlorophyll measured with a spectrophotometer and the growth rate was obtained from the amount. Growth inhibition rate was calculated by comparison with the non-treated lot.

The results are shown In Table 12. 42 Table 12 Compound No.

Growth inhibition rate(%) 500 ppb 50 ppb 1 3 4 7 9 100 96 89 100 98 98 43 0 100 23 Example 7 (Evaluation of activity of preventing the adhesion of organisms) 2.8 mg of compound 1 was completely dissolved in about 1 ml of acetone and each of the resulting sample solution was uniformly coated on a zone having a diameter of 4 cm drawn on test paper.

A zone having only acetone coated on the test paper was provided as a blank, and a zone having 1.0 mg of copper sulfate coated thereon were provided as comparative agent.

After drying, four blue mussels (Mytilus edulis) having a shell length of about 2-2.5 cm were adhered to the circumference of the respective zones using a rubber piece as a spacer. The prepared test plates were dipped in a water tank Into which sea water flows, and the tank was allowed to stand in a dark place for 3 hours. The test plates were taken out of the water tank, and the adhered position of byssus of Mytilus edulis and the number thereof were counted. In the same manner, tests were conducted using 2.6 mg and 1.3 mg, respectively, of compound 3.

In comparison with copper sulfate used as the comparative agent, the effect for preventing the adhesion (adhesion repellent activity) was obtained.

The evaluation method of the adhesion repellent activity was used according to Kazuo Ina and Hideo Etoh, (Evaluation method of adhesion repellent substances to marine adhesion organisms using Mytilus edulis (Kagaku To Selbutu (Chemistry and Biology), Vol. 28 (No. 2), pages 132-138 (1990)).

The results are shown in Table 13 43

Claims (27)

Table 13 Active Ingredient Dosage (mg) Judgment Compound 1 2.8 ++ Compound 3 2.6 ++ 1.3 ++ Comparative agent 1.0 ++ (copper sulfate) 0.5 + Blank - - Note that symbols in the Table have the following meanings. ++: No adhesion at all in the zone, i.e., strong repellent effect is observed. +: Adhesion in the zone is observed, but adhesion Is substantially outside the zone, i.e., repellent effect is observed. -: Adhesion is observed inside and outside the zone to the same extent, i.e., repellent effect is not observed. The N-qulnoxalylanlllnes represented by general formula (1) are highly safe and present a wide spectrum at low doses, and are useful as industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms. 44 WHAT IS CLAIMED IS:

1. An industrial antibacterial/antifungal agent, characterized by containing at least one compound of N-quinoxalylanilines represented by formula (1) (wherein R1 and R2, each independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, or a nitro group, R3 represents a hydrogen atom, a halogen atom, or an alkyl group having 1-5 carbon atoms, R* represents a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkenyl group having 2-6 carbon atoms, an alkynyl group having 2-6 carbon atoms, an alkylcarbonyl group having 2-6 carbon atoms, an alkylsulfonyl group having 1-5 carbon atoms, or an alkylsulfenyl group having 1-5 carbon atoms which may be substituted with a halogen atom(s), X and Y each independently represent a nitro group, a trifluoromethyl group or a halogen atom, Z represents a hydrogen atom, a halogen atom, an alkoxy group having 1-5 carbon atoms, or a phenoxy group which may be substituted with a halogen atom(s), a nitro group( s) orahydroxyl group(s), m and n each independently represent 0 or 1 provided that m and n are not 1 simultaneously, j and k each independently represent 0, 1, 2 or 3 provided that j+k always are 3 or less).

2. An industrial antibacterial/antifungal agent containing at least one compound of N-quinoxalylanilines according to claim 1, wherein m and n are each 0. 45

3. An Industrial antibacterial/antifungal agent containing at least one compound of N-quinoxalylanilines according to claim 1, wherein m is 1 and n is 0.

4. An industrial antibacterial/antifungal agent containing at least one compound of N-quinoxalylanilines according to claim 1, wherein m is 0 and n is 1.

5. An industrial antibacterial/antifungal agent containing at least one compound of N-quinoxalylanillnes according to claim 2, wherein R2 is a hydrogen atom.

6. An Industrial antibacterial/antifungal agent containing at least one compound of N-qulnoxalylanilines according to claim 2, wherein R1 is a hydrogen atom.

7. An algicide containing at least one compound of N-qulnoxalylanillnes according to claim 1.

8. An algicide containing at least one compound of N-qulnoxalylanilines according to claim 2.

9. An algicide containing at least one compound of N-quinoxalylanllines according to claim 3.

10. An algicide containing at least one compound of N-qulnoxalylanilines according to claim 4.

11. An algicide containing at least one compound of N-quinoxalylanillnes according to c3.aim 5.

12. An algicide containing at least one compound of N-quinoxalylanllines according to claim 6.

13. An agent for preventing the adhesion of organisms containing 46 33 6 8 ^ at least one compound of N-quinoxalylanilines according to claim 1.

14. An agent for preventing the adhesion of organisms containing at least one compound of N-quinoxalylanilines according to claim 2.

15. An agent for preventing the adhesion of organisms containing at least one compound of N-quinoxalylanilines according to claim 3.

16. An agent for preventing the adhesion of organisms containing at least one compound of N-quinox.alylanilines according to claim 4.

17.An agent for preventing the adhesion of organisms containing at least one compound of N-quinoxalylanilines according to claim 5.

18. An agent for preventing the adhesion of organisms containing at least one compound of N-quinoxalylanilines according to claim 6.

19. An industrial antibacterial/antifungal agent according to claim 1, containing at least one compound substantially as herein described in any one of Synthesis Examples 1-5 or as listed in any one of Tables 1-4.

20. An industrial antibacterial/antifungal agent according to claim 1, substantially as herein described in any one of Formulation Examples 1-3 and/or any one of Examples 1-4.

21. An industrial antibacterial/antifungal agent according to any one of claims 1-6, substantially as herein described.

22. An algicide according to claim 7, containing at least one compound substantially as herein described in any one of Synthesis Examples 1-5 or as listed in any one of Tables 1-4. INTELLECTUAL PROPERTY OFFICE OF N.Z. 47 12 APR 2000 ft826

23. An algicide according to claim 7, substantially as herein described in any one of Formulation Examples 1-3 and/or Example 5 .

24. An algicide according to any one of claims 7-12, substantially as herein described.

25. An agent for preventing the adhesion of organisms according to claim 13, containing at least one compound substantially as herein described in any one of Synthesis Examples 1-5 or as listed in any one of Tables 1-4.

26. An agent for preventing the adhesion of organisms according to claim 13, substantially as herein described in any one of Formulation Examples, Example 6 and/or Example 7.

27. An agent for preventing the adhesion of organisms according to any one of claims 13-18, substantially as herein described. 48 INTELLECTUAL PROPERTY OFFICE OF N.Z. 12 APR 2000 RECEIVED ABSTRACT An industrial antibacterial/antifungal agent, algicide and agent for preventing the adhesion of organisms, containing at least one compound of N-quinoxalylanilines represented by general formula (wherein R1 and R2, each independently represent H, halogen , CF3, Cj-Cj alkyl, Ci-Cj alkoxy, or N02, R3 represents H, halogen, or Cj-Cj alkyl, R4 represents H, Cx-C5 alkyl, Ca-Cs alkenyl, C2-C6 alkynyl, C2-Cs alkylcarbonyl, C^C, alkylsulfonyl, or C^Cj alkylsulfenyl which may be substituted with halogen, X and Y each independently represent N02, CF3 or halogen, Z represents H, halogen, Cl-Cs alkoxy, or a phenoxy group which may be substituted with halogen, N02 or OH, m and n each independently represent 0 or 1 but not m«n«sl, j and k each independently represent 0, 1, 2 or 3 provided that j+ks3). (1) <0)m (1) 48 Ou