CA2278244A1 - Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing n-quinoxalylanilines - Google Patents

Abstract

Industrial antimicrobial/mildew-proofing agents, algicides and antifouling agents containing N-quinoxalylanilines represented by general formula (1), wherein R1 and R2 independently represent each H, halogeno, CF3, C1-5 alkyl, C1-5 alkoxy or NO2; R3 represents H, halogeno or C1-5 alkyl; R4 represents H, C1-5 alkyl, C2-6 alkenyl, C2-6 alkynyl, C2-6 alkylcarbonyl, C1-5 alkylsulfonyl or optionally halogenated C1-5 alkylsulfenyl; X and Y independently represent each NO2, CF3 or halogeno; Z represents H, halogeno, C1-5 alkoxy or optionally halogenated, nitrated or hydroxylated phenoxy; m and n independently represent each 0 or 1 provided that m and n are not 1 at the same time; and j and k independently represent each 0, 1, 2 or 3, provided that j + k is not more than 3.

Description

INDUSTRIAL ANTIMICROBIAL/MILDEW PROOFING AGENTS
ALGICIDES AND ANTIFOULING AGENTS CONTAINING
N-OUINOXALYLANILINES
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
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.
DESCRIPTION OF THE RELATED ART
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.
Agents 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.
The adhesion of the aquatic organisms to ships causes an 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 sea water and fresh water, there have been used antifouling paints containing organic tin compounds such as bistributyltin 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 and their use as. agricultural and horticultural antimicrobial, insecticidal, and acaricidal agents.
However, this publication discloses nothing about the use of the compounds as industrial antibacterial/antifungal agents and algicidal agents as well as agents for preventing the adhesion of organisms.
The above-described organic nitrogen compounds, organic nitrogen-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 tributyltin-containing 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 compounds) (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-quinoxalylanilines as industrial antibacterial/antifungal agents, algicides and agents for preventing the adhesion of organisms.

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 agents) for preventing the adhesion of organisms, characterized by containing at least one compound of N-quinoxalylanilines represented by general formula (1) ~~~m R / N~ R3 Xi R2 \ ~ i _~~iYk 1 N N ~ ~ ( ) ~~~n R4 Z
(wherein Rland 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 ) or a hydroxyl 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 ~+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, l-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-1-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, i-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, i-propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, s-butylsulfonyl, t-butylsulfonyl, 1-pentylsulfonyl, 2-pentylsulfonyl, 3-pentylsulfonyl, i-pentylsulfonyl, 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-quinoxalylanilines 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, SOZMe: 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 Rt / N Ra XI Rt / N R~ XI Rt / N Ra XI
\ I ~ c _I=~/Y t \ I ~ s _I=~iY t \ I ~ s _I~/Y t N N' ~ ~4 N N ~ y ~ N ~ ~s R ~ R~ i a ~ Rs z a Z Z Z
the substituents on the benaene ring R' Rs R4 2 3(Z) 4 5 6 H H H NOz H NOZ H CFs H H H H H NOZ H NOZ

H H H NOz H NOZ H NOZ

H H H NOZ H H H NOZ

H H H NOZ OEt CF3 H NOZ

H H H H Cl CF3 H NOZ

H H H NOZ Br CF3 H NOZ

H H Me NOZ C1 CF3 H NOZ

H Me H NOZ C1 CF3 H NOZ

H Et H NOZ C1 CF3 H NOZ

F H H NOZ H NOZ H CFA

F H H H H NOZ H NOZ

F H H N02 H NOZ H NOz F H H C1 H NOZ H Cl F H H NOz H CF3 H NOZ

F H H NOZ H H H NOZ

F H H N02 OEt CF3 H NOZ

F H H NOZ OPh-OH-m CF3 H NOZ

--, Table 1 (continued) the substituents the benzene on ring R' Re R4 2 3(Z) 4 5 6 F H H NOz OPr-n CF3 H NOZ

F H H NOZ Br CF3 H NOZ

F H Me NOZ CI CFa H NOZ

F H COMB NOz CI CF3 ~H NOz F H SOZMe NOZ CI CF3 H NOZ

F H SCC13 NOZ CI CF3 H NOz F H COEt NOZ CI CF3 H NOZ
~

F Me H NOZ CI CF3 H NOZ

F Et H NOZ CI CF3 H NOZ

CI H H H H NOZ H NOZ

CI H H CI H NOZ H CI

CI. H H NOZ H .CF3H NOZ

CI H H NOZ OEt CF3 H NOZ

CI H H N02 OPh-OH-m CF3 H NOZ

CI H H NOz OPr-n CF3 H NOZ

CI H H NOZ Br CF3 H NOZ

CI H Me NOZ CI CF3 H N02 CI H SOZMe NOZ CI CF3 H NOZ

CI H COEt NOz C1 CF3 H NOZ

CI Me H NOZ CI CF3 H NOZ

CI Et H NOZ CI CF3 H NOZ

Br H H NOZ CI CF3 H NOZ

Br H H NOZ OEt CF3 H NOz Table 1 (continued) the substituentson the benzene ring R' Re R 2 3(Z) 4 5 g Br Me H NOZ CI CF3 H NOZ

I H H NOz Cl CF3 H NOZ

CF3 H H NOz H NOZ H NOZ

CF 'H H NO H H H NO Z

CF3 H H NOZ OEt CF3 H NOZ

CF3 H H H Cl CF3 H NOZ

CF3 H H NOZ Br CF3 H NOZ

CF3 H Me NOZ CI CF3 H NOZ

CF3 Me H NOz CI CF3 H NOZ

CF3 Et H NOZ CI CF3 H OZ
N

CF3 C1 H NOz C1 CF3 H NOZ

H H CHZ =CHCHZNOz H N02 H CFA

H H CH---- H H NO Z H NO z CCHZ
.

=CHCHZ

H H CH---CCHZ NOZ H NOZ H NOZ

H H CHI = CHCHzNOZ CI CFs H NO~

H H CH---CCHZ NOZ OEt CF3 H NOZ

H H CH---CCHz NOZ CI CF3 H NOZ

H Me CHZ = CHCHZNOZ CI CF3 H NOZ

H Et CH--_CCH2 NOZ CI CF3 H NOZ

H C1 CH2 = CHCHZNOZ CI CF3 H NOZ

H H CH--_CCHZ NOZ F CF3 H N02 F H CHZ =CHCHZNOZ H NOZ H CF3 F H CH---CCHZ H H NOZ H NOZ

F H CHz =CHCHZH H NOZ H CF3 F H CH---CCHZ NOZ H NOZ H NOZ

F H CHz = CHCHZN02 CI CF3 H NOZ

F H CH---CCH2 NOZ OEt CF3 H NOZ

F H CH---CCHz NOZ CI CF3 H NOZ

. ~, Table 1 (continued) the substituentson benzene the ring R' R8 R 2 3(Z) 4 5 6 F Me CHZ = CHCHZNOZ CI CF3 H NOZ

F Et CH---CCHz N02 C1 CF3 H NOZ

F CI CHZ = CHCHZNOZ CI CF3 H NOZ

CI H CHZ = CHCHZN02 H NOZ H CF3 C1 H CH-_-_-CCHZH H NOZ H NOZ

C1 H CHZ =CHCHZH H NOZ H CF3 CI H CHy = CHCHZNOZ CI CF3 H NOZ

CI H CH ---- NOZ OEt CF3 H NOZ
CCHz CI H CH_--CCHz NOZ CI CFa H NOz C1 Me CHZ = CHCHzNOZ CI CF3 H NOZ

C1 Et CH -_-_- NOZ CI CF3 H NOZ
CCHZ

CI CI CHZ = CHCHZNOZ CI CF3 H NOZ

CI H CH--_CCHZ NOZ F CF3 H NOZ

Br H CHZ = CHCHZNOZ H NOZ H CF3 B H CH ---- H H NO H NO Z
r CCH Z Z

Br H CHZ =CHCHZH H NOZ H CF3 Br H CH--__CCHZNOZ H NOZ H NOZ

Br H CHZ = CHCHZNOZ CI CF3 H NOZ

Br H CH ---- NOZ OEt CF3 H NOZ
CCHZ

Br H CH---CCHZ NOZ CI CF3 H NOZ

I H CHI =CHCHzNOZ CI CF3 H NOZ
.

I H CH---CCHz NOZ OEt CF3 H NOZ

CFs H CHz = CHCHZNOZ H NOZ H CF3 CF3 H CH_--CCHZ H H NOZ H NOZ

CF3 H CHz =CHCHZH H NOZ H CF3 CF H CH _-- NO H NO H NO Z

CF3 H CHZ = CHCHZNOZ CI CF3 H NOZ

CF3 H CH --_- NOZ OEt CF3 H NOZ
CCHZ

CF3 H CH _-- NOZ CI CF3 H NOZ
CCHZ

Me H H NOZ H NOz H CF3 Me H H H H NOZ H NOZ

Me H H H H NOZ H CF3 Me H H NOZ H NOZ H NOZ

Me H H NOZ CI CF3 H NOZ

Table 1 (continued) the substituentson benzenering the R' Re R' 2 3(Z) 4 5 g Me H H NOZ OEt CFA H N OZ

Me Me H NOZ C1 CF3 H NO2 Me Et H NOZ Cl CF3 H NOZ

Me Cl H NOZ Cl CF3 H NOZ

Me H H NOZ F CF3 H NOZ

Me H Me NOZ C1 CF3 H NOZ

Me H COMB NOZ C1 CF3 H NOZ

Me H SOZMe NOZ Cl CF3 H NOZ

Me H SCC13 NOZ C1 CF3 H NOZ

Me H CHZ = CHCHZNOZ H NOz H CF3 Me H CH = CCH H H NO H NO z Z Z

Me H CHZ =CHCHZH H NOZ H CF3 Me H CH----CCHZNOZ H NO2 H NO2 Me H CHZ = CHCHZNOZ Cl CF3 H NOZ

Me H CH ---- NOz OEt CF3 H NOz CCHZ

Me H CH----CCH2NOZ CI CF3 H NO2 Me0 H H NOa H NOZ H CF3 Me0 H H H H NOZ H N02 Me0 H H H H NOZ H CF3 Me0 H H NOZ H N02 H NOZ

Me0 H H NOZ CI CF3 H NOZ

Me0 H H NOZ OEt CF3 H N02 Me0 Me H NOZ C1 CF3 H NOZ

Me0 Et H NOZ Cl CF3 H NOZ

Me0 Cl H NOZ Cl CF3 H NOZ

Me0 H H NOz F CF3 H NOZ

Me0 H Me NOZ Cl CF3 H NOz Me0 H COMB NOz CI CF3 H NOZ

Me0 H SOZMe NOZ Cl CF3 H N02 Me0 H SCC13 NO2 Cl CF3 H NOZ

Me0 H CHz = CHCHzNOz H NOz H CFs Me0 H CH---CCHZ H H NOZ H NOZ

Me0 H CHZ =CHCHZH H NOZ H CF3 Me0 H CH--_CCHZ NOz H NOz H NOZ

Me0 H CHZ = CHCHZNOZ Cl CF3 H NOZ

Me0 H CH ---- NOZ OEt CF3 H NOZ
CCHZ

Table 1 (continued) the substituentson benzene the ring R1 Re R' 2 3(Z) 4 5 6 Me0 H CH -- CCHZNOZ CI CF3 H NOZ

NOZ H H NOZ OEt CFA H NOZ

NOZ Me H NOZ CI CF3 H NOZ

NOZ Et H NOZ CI CF3 H NOZ

N02 H Me NOZ CI CF3 H NOZ

NOZ H SOZMe NOZ CI CF3 H NOZ

NOZ H SCCIs NO2 CI CF3 H NOZ

NOZ H CHZ= CHCHZNOZ H NOz H CF3 z NO H CH = CHCH H H NO H CF 3 Z

NOZ H CHZ= CHCHZNOZ C1 CF3 H NOZ

NOZ H CH _-- NOZ OEt CF3 H NOZ
CCHZ

CCHZ

- --, Table 2 N R~ X~ / N R~ X~ / N R~ X~
t ~ ( ~ i'~~iYt : ~ ~ ~ c'~'~iYt : ~ ( ~ ~'~~iYt R N N ~ y R N N ~ ~< R ~ N
s , a R i R ~ p R i Z Z Z
the substituents on the benzene ring RZ R$ R' 2 3(Z) 4 5 6 F H H NOZ H NOZ H CFs F H H H H NOZ H NOZ

F H H NOZ H H H NOZ

F H H NOZ OEt CF3 H NOz F H H NOZ OPh-OH-m CF3 H NOZ

F H H NOZ OPr-n CF3 H NOZ

F H H NOz Br CF3 H NOZ

F H Me NOz Cl CF3 H NOz F H SOZMe NOZ C1 CF3 H NOZ

F H COEt NOZ C1 CF3 H NOZ

F Me H NOZ Cl CF3 H N02 F Et H NOZ CI CF3 - H NOZ

F Cl H NOZ H H H NOZ

Cl H H H H NOZ H NOZ

CI H H H H NOz H CF3 C1 H H NOZ H N02 H NOz Table 2 (continued) the substituents the benzene on ring Rz Re R' 2 3(Z) 4 5 6 Cl H H NOZ H CF3 H NOZ

CI H H NOZ H H H NOZ

CI H H NOZ Cl CF3 H NOZ

Cl H H NOz OEt CFs H NOZ

C1 H H NOZ OPh-OH-m CF3 H NOZ

Cl H H H CI CF3 H NOZ

Cl H H N02 OPr-n CF3 H NOz Cl H H NOZ Br CF3 H NOZ

C1 H Me NOz CI CF3 H NOZ

Cl H COMB NOZ CI CF3 H NOZ

C1 H SOZMe NOZ CI CF3 H NOZ

CI H SCC13 NOZ Cl CF3 H NOZ

CI H COEt NOZ C1 CF3 H NOZ

C1 Me H NOZ Cl CF3 H NOZ

C1 Et H NOZ C1 CF3 H NOZ

Cl C1 H NOZ H H H NOZ

Br H H NOZ C1 CF3 H NOZ

Br H H N02 OEt CF3 H NOZ

Br Me H NOZ C1 CF3 H NOZ

I H H NOz C1 CF3 H NOZ

CF3 H H NOz H CF3 H NOa CF3 H H NOZ Cl CF3 H NOZ

CF3 H H NOZ OEt CF3 H NOZ

CF H H H Cl CF3 H NOZ

CF3 H H NOZ Br CF3 H NOZ

CF3 H Me NOZ C1 CF3 H NOZ

CF3 Me H NOZ CI CF3 H N02 CF3 Et H NOz CI CF3 H NOZ

Table 2 (continued) the substituentson benzene the ring RZ R$ R 2 3(Z) 4 5 6 Me H H NOZ H NOZ H CF3 Me H H H H NOZ H NOZ

Me H H H H NOZ H CFa Me H H NOZ H NOZ H NOZ

Me H H CI H NOZ H C1 Me H H NOZ H CF3 H NOz Me H H NO2 H H H NO2 Me H H CF3 H NOZ H CF3 Me H H N02 C1 CF3 H NOZ

Me H H NOZ OEt CF3 H NOZ

Me H H NOZ OPh-OH-m CF3 H NOZ

Me H H H C1 CFa H NOz Me H H NOZ OPr-n CF3 H NOZ

Me H H NOZ Br CF3 H NOZ

Me H Me NOZ C1 CF3 H NOZ

Me H COMB NOZ C1 CF3 H NOZ

Me H SOZMe NOZ C1 CF3 H NOz Me H SCC13 NOZ Cl CF3 H NOZ

Me H COEt NOZ C1 CF3 H NOZ

Me Me H NOz Cl CF3 H NOZ

Me Et H NOZ C1 CF3 H NOZ

Me C1 H NOZ H H H NOZ

Me H H NOz F CFA H NOZ

Me0 H H NOZ H NOZ H CF3 Me0 H H H H NOz H NOZ

Me0 H H H H NOZ H CF3 Me0 H H NOZ H NOZ H NOZ

Me0 H H Cl H NOZ H Cl Me0 H H NOZ H CF3 H NOz Me0 H H NOZ H H H NOZ

Me0 H H CF3 H NOZ H CF3 Me0 H H NOZ CI CF3 H NOz Me0 H H NOZ OEt CF3 H NOZ

Me0 H H NOZ OPh-OH-m CF3 H NOz Me0 H H H C1 CF3 H NOZ

Me0 H H NOZ OPr-n CF3 H NOZ

. ,, Table 2 (continued) the substituentson benz~:ne the ring RZ R$ R' 2 3(Z) 4 5 6 Me0 H H NOZ Br CF3 H NOZ

Me0 H Me NOZ CI CF3 H NOZ

Me0 H COMB NOZ CI CF3 H NOZ

Me0 H SOZMe NOz C1 CF3 H NOZ

Me0 H SCC13 NOZ CI CF3 H NOZ

Me0 H COEt NOZ CI CF3 H NOz Me0 Me H NOZ CI CF3 H NOZ

Me0 Et H NOZ CI CF3 H NOZ

Me0 CI H NOZ H H H NOZ

Me0 H H NOZ F CF3 H NOZ

NOZ H H NOZ H NOZ H NOZ

NOZ H H N0z H CF3 H N02 NOZ H H NOZ H H H NOZ

NOZ H H NOz OEt CF3 H NOZ

NOZ H H NOZ Br CF3 H NOZ

NOZ H Me NOZ CI CF3 H NOZ

NOZ Me H NOz CI CF3 H NOZ

NOZ Et H NOZ C1 CF3 H NOZ

NOZ CI H NOz CI CF3 H NOZ

NOz H H N02 F CF3 H NOZ

F H CHZ= CHCHZNOZ CI CF3 H NOZ

F H CH ---- NOz OEt CF3 H _NOZ
CCHz F H CH ---CCHzNOZ CI CF3 H NOz F Me CHZ= CHCHzNOZ CI CF3 H NOZ

F CI CHZ= CHCHZNOz C1 CF3 H NOZ

F H CH---CCHz NOz F CF3 H NOz CI H CH2= CHCHZNOZ CI CF3 H NOZ

CI H CH N02 OEt CF3 H NOZ
----CCHZ

CI Me CHZ= CHCHZNOZ CI CF3 H NOZ

- -.., Table 2 (continued) the substituentson benzene the ring R2 Re R' 2 3(Z) 4 5 6 C1 CI CHz = CHCHZNOZ CI CF3 H NOZ

Br H CHZ = CHCHZNOZ CI CF3 H NOZ

Br H CH --- CCHZNOz OEt CF3 H NOZ

Br H CH=CCHZ NOZ CI CF3 H NOZ

I H CHZ = CHCHzNOZ CI CF3 H NOZ

I H CH---CCHZ NOz OEt CF3 H NOZ

I H CH--_CCHZ NOZ CI CF3 H NOZ

CF3 H CHz = CHCHZNOZ CI CF3 H NOZ

CF3 H CH --_- NOZ OEt CF3 H NOZ
CCHZ

CF3 H CH = CCHZ NOZ C1 CF3 H NOZ

CF3 Me CHZ = CHCH2NOZ C1 CF3 H NOZ

CF3 CI CHZ = CHCHzNOZ CI CF3 H NOz Me H CHZ = CHCH2NOZ CI CF3 H NOZ

Me H CH ---- NO2 OEt CF3 H NOZ
CCHZ

Me H CH=CCHZ N02 C1 CF3 H NOZ

Me Me CHZ = CHCHZNOZ CI CF3 H NOZ

Me CI CHZ = CHCHZNOZ CI CF3 H NOz Me H CH---CCHZ NOZ F CF3 H NOZ

Me0 H CHZ = CHCHZNOZ CI CF3 H NOZ

Me0 H CH ---- N02 OEt CF3 H NOZ
CCHZ

Me0 H CH ---- NOZ CI CFA H NOZ
CCHZ

Me0 Me CHZ = CHCHZNOZ CI CF3 H NOZ

Me0 C1 CHZ = CHCHZNOZ CI CF3 H NOZ

Me0 H CH---CCHZ NOZ F CF3 . H NOZ

NOZ H CHZ = CHCHZNOZ CI CF3 H NOZ

NOZ H CH --__ NOz OEt CF3 H NOz CCHZ

NOz H CH _-- CCHzNOz C1 CF3 H NOZ

NOZ Me CHZ = CHCHzNOZ CI CF3 H NOZ

NOZ C1 CHZ = CHCHZNOZ CI CFa H NOZ

NOZ H CH---CCHZ NOZ F CF3 H NOz Table 3 R~ / N R~ X~ R~ / N R~ X~ R~ / N R~ X
-I~ Y
\ ( ~ ' I~~Yk : \ I ~ ~-I~iYk R N N ~ ~~ R N N ~ ~t R ~ N
R~ 2 ~ p, i ~ p R~ s Z Z : Z
the substituents on the benzene ring ~' ~2 R$ R 2 3(Z) 4 5 6 F F H H NOZ H NOZ H CFA
.

F F H H H H NOz H NOZ

F F H H NOZ H NOZ H NOZ

F F H H NOZ C1 CF3 H NOz F F H H NOZ OEt CF3 H NOZ

F F Me H NOZ C1 CF3 H N02 F F Et H NOZ Cl CF3 H NOZ

F F C1 H NOz C1 CF3 H NOZ

F F H Me NOZ Cl CF3 H NOz F F H SO~Me NOZ Cl CFA H NOZ

F F H CHz = CHCHZNOZ C1 CF3 H NOZ

F F H CH-_-CCHz NOZ OEt CFs H NOi F F H CH--__CCHZNOZ CI CF3 H NOZ

CI C1 H H H H NOz H N02 CI Cl H H H H NOZ H CF3 Cl Cl H H NOZ H NOZ H NOZ

Cl Cl H H NOZ Cl CF3 H NOZ

C1 C1 H H NOZ OEt CF3 H NOZ

CI Cl Me H NOZ Cl CF3 H NOZ

C1 CI Et H NOz Cl CF3 H NOZ

CI CI Cl H NOz CI CF3 H NOZ

C1 Cl H H NOZ F CF3 H NOZ

C1 CI H Me NOZ CI CF3 H NOZ

. ~, Table 3 (continued) the substituents the benzenering on R' RZ Re R 2 3(Z) 4 5 6 CI CI H SOzMe NOZ CI CF3 H NOZ

CI C1 H CHZ = CHCHZNOZ Cl CF3 H NOZ

C1 CI H CH = CCHZ NOZ OEt CF3 H NOZ

CCHZ

CI NOZ H H H H NOZ H NOZ

CI NOz H H NOZ H N02 H NOZ

C1 NOZ H H NOZ OEt CF3 H NOZ

CI NOZ Me H NOZ CI CFA H NOZ

CI NOZ Et ' H NOZ CI CF9 H NOZ

CI NOZ C1 H NOz CI CF3 H NOZ

C1 NOZ H Me NOZ C1 CF3 H NOZ

CI NOZ H SOZMe N02 CI CF3 H NOZ

CI NOZ H CHZ = CHCHZNOZ CI CF3 H NOZ

CI NOZ H CH ---- NOZ OEt CF3 H NOZ
CCHZ

CCHZ

Me CI H H NOZ H NOZ H CF3 Me C1 H H H H NOZ H NOZ

Me CI H H H H NOz H CF3 Me CI H H NOZ H NOZ H NOZ

Me CI H H NOZ CI CF3 H NOZ

Me CI H H NOz OEt CF3 H NOZ

Me CI Me H NOZ CI CF3 H NOZ

Me CI Et H NOZ CI CF3 H NOz Me CI C1 H NOZ CI CF3 H NOZ

Me CI H H NOZ F CF3 H NOZ

Me CI H Me NOZ CI CF3 H NOZ

Me CI H COMB NOZ CI CF3 H NOZ

Me C1 H SOZMe NOZ CI CF3 H NOZ

Table 3 (continued) the substituents the benzenering on R' R2 Re R 2 3(Z) 4 5 6 Me CI H SCC13 NO2 CI CF3 H NOZ

Me CI H CHZ = CHCHZ NOz C1 CF3 H NOZ

Me CI H CH = CCHZ NOZ OEt CF3 H NOZ

Me CI H CH ---- CCHZNOZ CI CF3 H NOZ

Me0 NOZ H H NOZ H NOz H CF3 Me0 NOZ H H H H NOz H NOz Me0 NOZ H H H H NOZ H CF3 Me0 NOZ H H NOZ H NOZ H NOZ

Me0 NOZ H H NOZ CI CF3 H NOz Me0 NOZ H H NOZ OEt CF3 H NOZ

Me0 N02 Me H NOZ C1 CF3 H N02 Me0 NOZ Et H NOZ- CI CF3 H NOZ

Me0 NOZ CI H NOZ CI CF3 H NOZ

Me0 NOZ H H NOZ F CF3 H NOZ

Me0 NOZ H Me NOZ CI CF3 H NOZ

Me0 NOZ H COMB NOZ C1 CF3 H NOZ

Me0 NOZ H SOZMe NOZ CI CF3 H NOZ

Me0 NOZ H SCC13 NOZ CI CF3 H NOZ

Me0 NO2 H CHz = CHCHZ NOZ CI CF3 H N02 Me0 NOZ H CH ---- CCHZNOZ OEt CF3 H NOZ

Me0 NOZ H CH = CCHZ NOZ CI CF3 H NOZ

The N-quinoxalylanilines 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 Z1, Z2 and Z' 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:

~~)m ~0)m R' N R3 Xj acid R~ N R3 i ~ -~~/Yk acceptor i ~ X~
+ Hal ~ ~ ---~
R N NH2 R2 \ N N ~~/Yk ~~)n Zl (~)n H
Z
In the above-described reaction scheme, Rl, 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 dimethylformamide, 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 Z' 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 ~~)m R' / N~ R3 X~ SC 1 d ' R' / N~ R3 X1 acceptor _ \ ~ ~ -~~/Yk + Zs-H --~- 2 \ ~ ~ ~=~/Yk R (~)n H ~ ~ R N
Z2 ~~)n Za In the above-described reaction scheme, ZZ 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 groups) or a hydroxyl group(s).

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 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):
~~)m (0)m R1 R3 X acid R R3 acceptor R2 N -~~~Yk + R4-Hal -----~
i H ~ ~ R, R
Z Z
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 triethylamine 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, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and m-dichlorobenzene, or aromatic hydrocarbons such as benzene, toluene, and xylene. The reaction 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 isothiocyanate, 2-amino-3-chloro-1,4-naphthoquinone, ethylene-bis-thiocyanate, 2-n-octyl-3-isothiazolone, glutaraldehyde, 5-chloro-2-n-decyl-3-isotiazolone, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, 2-chloro-4-methylamino-6-isopropylamino-s-triazine, 5-chloro-2-methyl-3-isothiazolone, 2,3-dichloro-1,4-naphthoquinone, diiodomethyl-p-tolylsulfone, N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)sulfamide, N-(3,4-dichlorophenyl)-N'-methylurea, N,N-dimethyl-N'-(3,4-dichlorophenyl)urea, zinc dimethyldithiocarbamate, 2,6-dichloro-3,5-dicyano-4-phenylpyridine, 2,4-dichloro-6-(0-chloroanilino)-s-triazine, 4,5-dichloro-2-(4-chlorobenzyl)-3-isothiazolone, 4,5-dichloro-2-(4-chlorophenyl)-3-isothiazolone, 4,5-dichloro-2-n-hexyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone, 1,2-dibromo-2,4-dicyanobutane, 2,2-dibromo-3-nitrilopropionamide, 2-thiocyanomethylthiobenzothiazole, 2-(4-thiazolyl)benzimidazole, thiabendazole, tetrafluoroisophthalonitrile, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, tetraphenylboranepyridine salts, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, tetra-n-butylthiuram disulfide, tetrachloroisophthalonitrile, tetrachlorophthalonitrile, Cu-10~ Ni solid solution alloy, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, 2,3,6-trichloro-4-propylsulfonylpyridine, N-(2,4,6-trichlorophenyl)maleimide, 4,5-trimethylene-2-methyl-3-isothiazolone, 2-pyridinethiol-1-oxide zinc salt, 2,3,3-triiodoallyl alcohol, N-(fluorodichloromethylthio)phthalimide, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, N-phenethyldichloromaleimide, 2-bromo-2-nitropropanediol, 5-bromo-5-nitro-1,3-dioxane, bromochlorodimethylhydantoin, N-benzyldichloromaleimide, 1,2-benzisothiazoline-3-one, 2-(methoxycarbonylamino)benzimidazole, 4-methyl-5-chloro-2-n-octyl-3-isothiazolone, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, N-2-methyl-6-ethylphenyldichloromaleimide, 2-methyl-3-isothiazolone, methylene-bis-thiocyanate, 3-iodo-2-propynylbutyl carbamate, and iodopropargylbutyl carbamate.
Further, the N-quinoxalylanilines 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-quinoxalylanilines .
In the present invention, the N-quinoxalylanilines used as an active ingredient may be added singly to the systems of the above-described applications , or may be 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 powder, an emulsion, a sol agent (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 , f or example , soybean powder , starch, crystalline cellulose and the like, alumina, silicates, sugar polymers ( highly dispersible silicic acid, waxes and the like.
Examples of the liquid carriers include water, alcohols, for example,methyl alcohol,ethyl alcohol,n-propyl alcohol,isopropyl 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, nitriles, for example, acetonitrile, propionitrile, acrylonitrile 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, triethylamine 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 cationic surfactants include alkylamines (laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonium 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, adhesives, latex, and acrylics, slurry products such as starch, pigments, calcium carbonate, and 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, polyurethane, 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 containing N-quinoxalylanilines as an active ingredient can be used, for example, for 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-trifluoromethylaniline (Compound 1) (1) Synthesis of 2-amino-6-chloroquinoxaline 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, recrystallized 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 dimethylformamide 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-dinitrobenzotrifluoride in 15 ml of dimethylformamide 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 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=4/1) to obtain 8.1 g of N-(6-chloro-2-quinoxalyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline (mp 182-187°C).
Synthesis Example 2 Synthesis of N-(6-chloro-2-quinoxalyl)-2,6-dinitro-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-quinoxalyl)-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-quinoxalyl)-2,6-dinitro-3-ethoxy-4-trifluoromethylaniline (mp 150-155°C).
Synthesis Example 3 Synthesis of N-(6-chloro-2-quinoxalyl)-2,4-dinitro-6-trifluoromethylaniline (Compound 3) 2-Amino-6-chloroquinoxaline ( 1 g) was dissolved in 15 ml of dimethylformamide 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-dinitrobenzotrifluoride in 5 ml of dimethylformamide 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 filtration. The crystals were washed with water and dried, and purified by silica gel column chromatography (eluent:
chloroform/ethyl acetate=5/1) 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-quinoxalyl)-2,4,6-trinitroaniline (Compound 4) 2-Amino-6-chloroquinoxaline ( 1 g) was dissolved in 15 ml of dimethylformamide 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-trinitrofluorobenzene in 5 ml of dimethylformamide 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=4/1) to obtain 0.9 g of N-(6-chloro-2-quinoxalyl)-2,4,6-trinitroaniline (mp 120-130°C) .
Synthesis Example 5 Synthesis of N-acetyl-N-(6-chloro-2-quinoxalyl)-2,6-dinitro-3-chloro-4-trifluoromethylaniline (Compound 5) N-(6-Chloro-2-quinoxalyl)-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=4/1) 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 R' / N R' \ ~ ~ s _~~iY k N N
R, z Z
compound the substituents on the benzene ring physical No, value R' R$ R' 2 3(Z) 4 5 6 mp(°C) 6 H H H NOz Cl CF3 H N02 89- 90 9 CF3 H H NOZ OEt CF3 H NOZ 164-166 11 C1 H H NOZ OPh-OH-m CF3 H NOZ 234-242 14 Cl H H H H NOZ H NOZ 232-235 Cl H H H H NOZ H CF3 215-220 16 C1 H H C1 H NOZ H C1 8laSS

17 H Cl H NOz CI CF3 H NOZ 173-174 18 Cl H CH3 NOZ Cl CF3 H NOZ $laSS

19 C1 H SOZCH3NOZ Cl CF3 H NOZ glass C1 H SCC13 NOZ C1 CF3 H NOZ 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 amount of carrier and auxiliaries are not limited thereto.
CI / I N\ 02N CI / I N\ CF3 \ ~ \
N H ~ ~ CF3 N H ~ ~ N02 02N CI p2N
compoud 1 compoud 3 Formulation Example 1 (Emulsion) Component ~ by weight Compound 1 5 Dimethyl sulfoxide 85 Methyl isobutyl ketone 5 Sorpol 800A (Emulsifier 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 Clay 73 The above components were mixed and ground uniformly to obtain a wettable powder containing 20~ of the active ingredient.

- --, Formulation Example 3 (Flowable agent) Component % by weight Compound 1 20 Lauryl sulfate 2 Xanthan gum 2 Hydroxypropyl cellulose 1 Deionized water 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 for 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, . ,., emulsions and the like, the general formulation methods usually employed can be used.
Where the agents for preventing the adhesion of aquatic organisms of the present invention are used in the form of antifouling coatings, the N-quinoxalylaniline 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 channelsfor 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-quinoxalylaniline as the active ingredient so long as a coating film can be formed, but the N-quinoxalylaniline 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.

- ~, Formulation Example 4 Component ~ by weight Compound 1 g VYHH (vinyl-base synthetic 7 resin produced by UCC) Rosin Tricresyl phosphate 3 Talc 20 Barium sulfate 15 Iron red 10 Xylene 20 Methyl isobutyl ketone 10 Formulation Example 5 Component ~ by weight Compound 3 5 CR-10 (chlorinated rubber 13 resin produced by Asahi Denka) Zinc white 20 Talc 20 Plasticizer 2 Iron red 10 Xylene 30 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-quinoxalylaniline 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 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 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 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.
CI / N\ 02N % / I N~ 02N
\ I ~ \
N H ~ ~ NO' CF N H ~ ~ CF3 02N 02N OEt 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 m n ag~rophytes was added to 125m1 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 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. Bacil_1LS sLbtilis was incubated in an incubator at 37'~ for 1 day whereas T_r; chophyton mentag~rophytes 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 subtilis B: Tricho~yton mentagy~y P
+: 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 (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 (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 3711°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 subtilis B: Tricho~yton mentag~phy P
C: StapbylococcLS aureus D: Escherichia coli E: Pseudomonas aeru,g,'_nosa F : As~erg~illus niger G: Pen i ~ ~ i ~m funi ~ o ~m 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 15.6 3 <2.0 <2.0 15.6 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, 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 (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 (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 3711°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: MicrococcLS lutea J: orynebacteri Lm aQuati ~mm K: Alcal i g n . fa a1 i L : Sal movel l a t~hymL_r,'_mm M: Chetomium ~lobosmm N: Rhizonus orvzae O: Rodotorula rubra P: Baccha_romy cerv' ia.~
Table 8 Results of MIC measurement on bacteria (mg/1) Compound Test Bacteria No. I J K L
1 <2.0 <2.0 <2.0 >1,000 Table 9 Results of MIC measurement on fungi (mg/1) Compound Test Fungi No. M N O P
1 <2.0 >500 <2.0 >500 Example 4 (Evaluation of Bactericidal effect on Legionella strain) A 2 , 000 mg/1 solution of the compound of the present invention in dimethyl sulfoxide was prepared 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 [T_.ggrionella pneLmo~hiia, 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 <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 105 cells/ml of a fresh water green alga (Selenastrum ca,p ornmt~,m) 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 2311°C under continuously illuminated conditions all day long.
After 72 hours, the number of cells in the sample was counted 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 Growth inhibition rate () No. 500 ppb 50 ppb 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 105 cells/ml of a sea water diatom (Nitzschia closte_rimm) 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 2311°C under continuously illuminated conditions all day long.
After 72 hours, the cells were collected by centrifugation 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.

Table 12 Compound Growth inhibition rate () No. 500 ppb 50 ppb 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 (MytilLS 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 My ~i~ dul;~ (Kagaku To Seibutu (Chemistry and Biology), Vol.
28 (No. 2), pages 132-138 (1990)).
The results are shown in Table 13.

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-quinoxalylanilines 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.

Claims (18)

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, 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, 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) or a hydroxyl 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.

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-quinoxalylanilines according to claim 2, wherein R2 is a hydrogen atom.

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

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

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

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

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

11. An algicide containing at least one compound of N-quinoxalylanilines according to claim 5.

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

13. An agent for preventing the adhesion of organisms containing 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-quinoxalylanilines 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.