WO1999062335A1 - Phenylhydrazine derivative, and commercial antibacterial and antimycotic agent, algicide and agent for preventing attachment of organism comprising the same - Google Patents

Abstract

A commercial antibacterial and antimycotic agent, an algicide and an agent for preventing attachment of organisms, characterized in that they comprise a phenylhydrazine derivative represented by general formula (1) wherein X and Y independently represent H, a halogen, a C1-5 alkyl group, a halogen-substituted C1-5 alkyl group, a C1-5 alkoxy group, a halogen-substituted C1-5 alkoxy group or a nitro group; and W represents formula (1-1) wherein X?1 and Y1¿ are independently as defined for X and Y respectively, m and n independently represent 0 or 1, or formula (1-2) wherein R?1 and R2¿ independently represent H, a halogen, a C¿1-5? alkyl group or a halogen-substituted C1-5 alkyl group, and R?3¿ represents C¿1-3? alkyl group.

Description

 Satsuki Itoda »Phenylhydrazine derivatives and industrial antibacterial and antifungal agents, algicides and biofouling inhibitors containing these compounds

 The present invention relates to antibacterial and antifungal agents and algicides for industrial products, antibacterial and antifungal agents used in the manufacturing process of industrial products, and water for preventing the attachment of harmful aquatic organisms such as algicides and shellfish. It relates to a biofouling inhibitor. Background art

 Industrial antibacterial and antifungal agents and algicides are used to eliminate various adverse effects of the growth and growth of bacteria, fungi and algae on various industrial products and facilities. Conventionally, as these industrial antibacterial, antifungal and algicidal agents, organic nitrogen compounds, organic nitrogen compounds, organic halogen compounds, nitrogen-containing aliphatic polymers and heavy metal coordination compounds have been used. I have.

 Anti-fouling agents can be found in underwater equipment such as fishing nets, ship bottoms, buoys, marine structures, condenser cooling water systems for thermal or nuclear power plants, heat exchanger cooling water intake channels for the chemical industry, It is used to prevent harmful aquatic organisms such as shellfish from attaching to underwater structures or reservoirs.

 If these aquatic organisms adhere to the cultivation net, the mesh will be clogged and the growth of the cultivated fish will be hindered as the distribution of seawater decreases, leading to frequent occurrence of fish diseases.

 The adhesion of these aquatic organisms to ships causes an increase in fluid resistance, resulting in a decrease in navigation speed, an increase in fuel consumption, and a loss of costs for cleaning the bottom of the ship and costs due to suspension of operation.

In marine facilities, marine and underwater structures, the increase in weight and the inconvenience of handling operations due to the attachment of aquatic organisms cause the adhesion to the intake channel to lower the thermal conductivity and block the intake channel. And problems such as reduced water intake. Conventionally, in order to prevent the adhesion and propagation of these organisms in seawater and freshwater water, antifouling paints containing an organotin compound such as pistribyl tilsoxide and a copper compound such as copper sulfate and cuprous oxide have been used.

 International Patent WO 96/38419 discloses a phenylhydrazine derivative having a pyrazoyl ring, a method for producing the same, and a use as a plant disease controlling agent.

 However, the phenylhydrazine derivative having a virazole ring of the present invention is a novel compound, and is completely different from the compound described in this publication in the bonding position on the pyrazole ring.

 Further, the compounds described in this publication do not describe the use as industrial antibacterial, antifungal, algicidal and biofouling inhibitors.

 Japanese Patent Publication No. Sho 499-111061, Japanese Unexamined Patent Publication No. Hei 2-295952, Japanese Unexamined Patent Publication No. Hei 2-300157, German Patent DE38002175 In the Official Gazette and in European Patent EP 604 798, there are disclosed benzoylphenylhydrazine compounds, phenylcaprate compounds, benzylcarbazete compounds, phenylbenzamide compounds and phenylbenzamide compounds. Disclosed are a hydrhydrazine compound, a method for producing the compound, and a use as a fungicide for agricultural and horticultural use and an insecticide and acaricide.

 However, there is no description of the use of the compounds described in these publications as industrial antibacterial agents, antifungal agents, algicides and biofouling inhibitors. The above-mentioned organic nitrogen-based compounds, organic nitrogen-based compounds, organic halogen-based compounds, nitrogen-containing aliphatic polymers, heavy metal coordination compounds, etc. are irritating drugs that pose a problem in the Labor Safety Act, and the amount of drugs used is large, and It contains chemicals that are problematic from a protection point of view, releases formalin or halogen, and includes chemicals that may affect the human body and cause environmental pollution, and chemicals that may cause environmental pollution by heavy metals. · It cannot be said that antifungals and algicides as a whole consist only of preferred agents.

In addition, the above-mentioned organotin compounds as biofouling inhibitors are effective in preventing the fouling of aquatic organisms, but they are highly toxic, and they cause significant accumulation of fish and shellfish in the body. Is currently being regulated.

 For example, in the United States, the Organotin Antifouling Paint Regulations Act (1987) banned the use of organotin marine paints on ships below 65 feet, and in the UK, the Food Environmental Protection Act (1) 1987), the use of anti-fouling agents containing triptyl tin on ships less than 25 meters and for marine agriculture is prohibited.

 In Japan, triptyl sulphoxide is designated as a Class 1 specified chemical substance by the Chemical Substances Control Law (1990), and triphenyltin compounds and tripriptyl tin compounds are designated as a Class 2 specified chemical substance. Use is prohibited.

 In addition, measures have been taken to curb the use of triptyltin-based bottom paints (Notice of the Ministry of Transport, 1990).

 The above-mentioned copper compounds are widely used in antifouling paints for intake channels and ship bottoms, but contain copper, which is a heavy metal like tin compounds. It cannot be said to be a biofouling control agent in water. Disclosure of the invention

 The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that phenylhydrazine derivatives have a high safety and a wide spectrum with a low dose from the viewpoint of preventing environmental pollution. The present invention was found to be a highly industrial antibacterial and antifungal agent, an algicide and a biofouling inhibitor, and completed the present invention.

 That is, the present invention provides a compound represented by the following general formula (1):

(In the formula, X and Υ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and a carbon atom of 1 Or 5 carbon atoms substituted with a halogen atom Represents an alkoxy group or a divalent group having 1 to 5 children, and W is

(Wherein X ¹ and Y ¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, Represents an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom or a ditro group, and m and n each independently represent 0 or 1.) or

(Wherein, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group of 5 C 1 -C substituted with an alkyl group or a halogen atom having 1 to 5 carbon atoms, R ³ Represents an alkyl group having 1 to 3 carbon atoms. ) An industrial antibacterial and antifungal agent, an algicide and a biofouling inhibitor characterized by containing a phenylhydrazine derivative represented by the formula:

 General formula (2):

 (2)

(In the formula, X and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and a carbon atom of 1 Or 5 carbon atoms substituted with a halogen atom Represents an alkoxy group having 1 to 5 carbon atoms or a nitro group; R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a carbon atom substituted with an alkyl group having 1 to 5 carbon atoms or a halogen atom; R ³ represents an alkyl group having 1 to 5 atoms, and R ³ represents an alkyl group having 1 to 3 carbon atoms. ) Is related to the derivative of phenylhydrazine represented by

 Each substituent represented by the general formula (1) will be specifically described.

 In the present specification, “n” means normal, “i” means iso, “s” means secondary, “t” means unique, and “neo” means neo.

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

 Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl and cyclopropyl.Alkyl groups having 1 to 5 carbon atoms include, in addition to these, , N-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neo-pentyl, t- Examples include a pentyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclobutyl group and a cyclopentyl group.

 Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, S-butoxy, t-butoxy, n -Pentyloxy, 2-pentyloxy, 3-pentyloxy, i-pentyloxy, neo-pentyloxy, t-pentyloxy, cyclopropoxy, trimethylcyclopropoxy, 2-methylcyclopropoxy, cyclobutoxy and And a cyclopentyloxy group.

Examples of the alkyl group having 1 to 5 carbon atoms substituted with a halogen atom include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, sec-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neo-pentyl, t-pentyl, 1-methylcyclopropyl, 2- Fluorine, chlorine, bromine and / or methylcyclopropyl, cyclobutyl and cyclopentyl groups Mono-, di-, tri- and polysubstituted by iodine atoms are included.

 Examples of the alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, i-pentyloxy, neo-pentyloxy, t-pentyloxy, cyclopropoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy And mono-, di-, tri- and poly-substituted groups of a fluorine atom, a chlorine atom, a bromine atom and a Z or iodine atom of the group, cyclobutoxy group and cyclopentoxy group.

 Preferred as X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-group. Monobutyl, n-pentyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, n-pentyloxy, trifluoromethoxy Groups or nitro groups.

Preferred as X ¹ and Y ¹ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, t-butyl group, n-pentyl group, trifluoromethyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, trifluoromethoxy group Or a nitro group.

Desirable R ¹ and R ² each independently include a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group.

Preferred R ³ includes a methyl group, an ethyl group, an n-propyl group and an i-propyl group.

The industrial antibacterial / antifungal agent, algicide and biofouling inhibitor of the present invention may contain the phenylhydrazine derivative represented by the above general formula (1) as an active ingredient. Preferred embodiments of the present invention are described below.

 (1) An industrial antibacterial and antifungal agent characterized by containing a phenylhydrazine derivative represented by the formula (1).

(2) X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t —Butyl, n-pentyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, n-pentyloxy, trifluoromethoxy X ¹ and Y ¹ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, t-butyl group, n-pentyl group, trifluoromethyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n-pe Chiruokishi group, a Torifuruorome butoxy group or a nitro group, R ¹ and R ² are each independently a hydrogen atom, a chlorine atom, a methyl group or preparative Rifuruoromechiru group, R ³ is a methyl group, Echiru group, n- propyl 3. The industrial antibacterial and antifungal agent according to embodiment (1), which comprises the phenylhydrazine derivative according to claim 2, which is a group or i-propyl group.

(3) X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a methoxy group or a nitro group, and X ¹ and Y ¹ are each independently A hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a t-butyl group or a methoxy group, and the hydrazine derivative according to the embodiment (2), wherein R ³ is a methyl group. Industrial antibacterial agent. Drag agent.

 (4) An algicide comprising a phenylhydrazine derivative represented by the formula (1).

 (5) A biofouling inhibitor containing a phenylhydrazine derivative represented by the formula (1).

(6) X and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, t-butyl group, n-pentyl group, trifluoromethyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n- A pentyloxy group, a trifluoromethoxy group or a nitro group; R ¹ and R ² are each independently a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group; and R ³ is a methyl group or an ethyl group A hydrazine derivative represented by the formula (2), which is an n-propyl group or an i-propyl group.

(7) An embodiment in which X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a methoxy group or a nitro group, and R ³ is a methyl group. The phenylhydrazine derivative according to 6). Preferred compounds contained in the active ingredients of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are listed in Tables 1 and 2 below, and the compounds used in the present invention Is not limited to these.

 However, the symbols in the table have the following meanings.

Me: methyl group, Et: ethyl group, Pr—n: normal propyl group, Pr—i: isopropyl group, Bu_n: normal butyl group, Bu—t: Yuichi Sharybutyl group, P en—n: normal pentyl group, OM e: methoxy group, 0Et: ethoxy group, 0Pr_n: normal propoxy group, 0Bu—n: normal butoxy group.

Table 1

A ring B ring

Α ring B ring

Α ring B ring

Substituent on ring A (X ¹ and Y ¹ ) Substituent on ring B (X and Y)

2 3 4 5 6 2 '3' 4, 5, 6 *

H H H H H H H H H H H

F H H H H H H H H H H

H F H H H H H H H H H

H H F H H H H H H H H

 C1 H H H H H H H H H H

H C1 H H H H H H H H H

HH C1 HHHHHHH Table continuation

Substituent on ring A ('and Y ¹ ) Substituent on ring B (X and Y)

3 4 5 6 2 '3, 4, 5' 6

CI C 1 H H H Η Η Η Η Η

C 1 H CI H H Η Η Η Η Η

C1 H H CI H Η Η Η Η Η

C 1 H H H C I Η Η Η Η Η

H C1 CI H H Η Η Η Η Η

H C1 H CI H Η Η Η Η Η

H C1 H H CI Η Η Η Η Η

H Br H H H Η Η Η Η Η

H H I H H Η Η Η Η Η

H F CI H H Η Η Η Η Η

H C1 F H H Η Η Η Η Η

H Br CI H H Η Η Η Η Η

H H H H H F Η Η Η Η

H H H H H Η F Η Η Η

H H H H H Η Η F Η Η

H H H H H C1 Η Η Η Η

H H H H H Η C1 Η Η Η

H H H H H Η Η C1 Η Η

H H H H H C1 C1 Η Η Η

H H H H H C1 Η C1 Η Η

H H H H H C1 Η Η C1 Η

H H H H H C1 Η Η Η C1

H H H H H Η C1 C1 Η Η

H H H H H Η C1 Η C1 Η

H H H H H Η C1 Η Η C1

H H H H H Br Η Η Η Η

H H H H H Η I Η Η Η

H H H H H Η F C1 Η

H H H H H Η C1 F Η Η

H H H H H Η Br C1 Η Η

C1 H H H H C1 Η Η Η Η

C1 H H H H Η C1 Η Η Η

C1 H H H H Η Η C1 Η Η

H CI H H H C1 Η Η Η Η

H CI HHH Η C1 Η Η Η Table continuation

A ring on a substituent (X ¹及Hi Y ¹⁾ B ring on a substituent (X and Y)

2 3 4 5 6 2,3,4,5,6 '

H CI H H H Η H CI H H

H H CI H H CI H H H H

H H CI H H H CI H H H

H H CI H H H H CI H H

 C1 H CI H H CI H H H H

C1 H CI H H H CI H H H

C1 H CI H H H H CI H H

H CI CI H H CI H H H H

H CI CI H H H CI H H H

H CI CI H H H H CI H H

 C1 H H H H CI H CI H H

H CI H H H CI H CI H H

H H CI H H CI H CI H H

 C1 H H H H H CI H CI H

H CI H H H H CI H CI H

H H CI H H H CI H CI H

 Me H H H H H H H H H H

H Me H H H H H H H H H

H H Me H H H H H H H H

Me Me H H H H H H H H H

Me H Me H H H H H H H H

Me H H Me H H H H H H H

Me H H H Me H H H H H

H Me Me H H H H H H H H

H Me H Me H H H H H H

H Me H H Me H H H H H

Et H H H H H H H H H H

H Pr-n H H H H H H H H H

H H Pr-i H H H H H H H H

H Bu-n H H H H H H H H H

H H Bu- t H H H H H H H H

Pen-n H H H H H H H H H H

H H H H H Me H H H H

H H H H H H Me H H H

HHHHHHH Me HH Continued

A ring on a substituent (X ¹ and Y ') B ring on a substituent (X and Y)

2 3 4 5 6 2 3 4 5 '6'

H H H H H Me Me H H H

H H H H H Me H Me H H

H H H H H Me H H Me H

H H H H H Me H H H Me

H H H H H H Me Me H H

H H H H H H Me H Me H

H H H H H H Me H H

 H H H H H H H Ft H H

H H H H H H Pr— n H H H

H H H H H Pr- i H H 11 H H

H H H H H H H H H H

H H H H H H H uu. H

 H H H H H H Π H

 Me H H H H Me H H H

 Me H H H H H Me H H H 11

Me HHHHHH e HH

 H Me H H H H Me H λ H H

H Me H H H H H Me H H

H H Me H H Me H H H H H

H H Me H H H Me H H H

H H Me H H H H Me H H

Me H H H H CI H H H H

Me H H H H H CI H H H

Me H H H H H H Cl H H

H Me H H H CI H H H H

H Me H H H H CI H H H

H Me H H H H H Cl H H

H H Me H H 11 Π 1 n u n H n u n

H H Me H H H Cl H H H

H H Me H H H H Cl H H

CI H H H H Me H H H H

CI H H H H H Me H H H

CI H H H H H H Me H H

H CI HHH Me HHHH Table continuation

Substituent on ring A (X ¹ and Y ¹ ) Substituent on ring B (X and Y)

2 3 4 5 6 2 3 4 '5' 6 '

H C I H H H Η Me Η Η Η

H C I H H H Η Η Me Η Η

H H C I H H Me Η Η Η Η

H H CI H H Η Me Η Η Η

H H C I H H Η Η Me Η Η

H H Bu-t H H C 1 Η Η Η Η

H H Bu-t H H Η C1 Η Η Η

H H Bu-t H H Η Η C1 Η Η

C1 H H H H Η Η Bu-t Η

 H CI H H H Η Η Bu-t Η

 H H C I H H Η Η Bu-t Η

 OMe H H H H Η Η Η Η

 H OMe H H H Η Η Η Η Η

H H OMe H H Η Η Η Η Η

OEt H H H H Η Η Η Η Η

H OPr-n H H H Η Η Η Η Η

H H OBu-n H H Η Η Η Η Η

H H H H H OMe Η Η Η Η

H H H H H Η OMe Η Η Η

H H H H H Η Η OMe Η Η

H H H H H OEt Η Η Η Η

H H H H H Η OPr-n Η Η Η

H H H H H Η Η OBu-n Η Η

OMe H H H H C1 Η Η Η Η

OMe H H H H Η C1 Η Η Η

OMe H H H H Η Η C1 Η Η

H OMe H H H C1 Η Η Η Η

H OMe H H H Η C1 Η Η Η

H OMe H H H Η Η C1 Η Η

H H OMe H H C1 Η Η Η

 H H OMe H H Η C1 Η Η Η

H H OMe H H Η Η C1 Η Η

CI H H H H OMe Η Η Η Η

CI H H H H Η OMe Η Η Η

CI HHHH Η Η OMe Η Η Table continuation

Substituent on ring A (X ¹ and Y ¹ ) Substituent on ring B (X and Y)

2 3 4 5 6 2 '3, 4' 5 '6,

H CI H H H OMe H H H H

H CI H H H H OMe H H H

H CI H H H H H OMe H H

H H CI H H OMe H H H H

H H CI H H H OMe H H H

H H CI H H H H OMe H H

CFs H H H H H H H H H H

H CFs H H H H H H H H H

HH CF ₃ HHHHHHH

CF ₃ HHHH CI HHHH

H CFs H H H H CI H H H

H H CFs H H H H C C I H H

CFs H H H H H Me H H H

H CF ₃ HHH Me HHHH

H H CFs H H H H Me Me H H

H H H H H CFs H H H H

H H H H H H CFs H H H

HHHHHHH CF ₃ HH

CI H H H H CFs H H H H

H CI H H H H CFs H H H

HH CI HHHH CF ₃ HH

Me H H H H H CFs H H H

H Me HHH CF ₃ HHHH

HH Me HHHH CF ₃ HH

OCFs H H H H H H H H H H

H OCFs H H H H CI H H H

H H OCFs H H H H Me H H

H H H H H OCFs H H H H

H H CI H H H OCFs H H

 H Me H H H H H OCFs H H

N0 ₂ HHHHHHHHHH

表続き HH NO 2 HHHH Me HH

Table continuation

Substituent on ring A (X ¹ and Y ¹ ) Substituent on ring B (X and Y)

2 3 4 5 6 2, 3, 4 '5' 6 '

H Me H H H Η Η NO Η Η

CI H H H H Η Η NO Η Η

F H H H F Η Η Η Η Η

F H H H F C1 Η Η Η Η

CI H H H H Η C1 C1 Η Η

H CI H H H Η C1 C1 Η Η

HH CI HH Η C1 C1 Η Η

Table 2

Substituent on benzene ring (X and Y)

R ¹ R ² R ³

2 3 4 5 6

 H H H H H H H Me

C1 H H H H H H Me

H CI H H H H H Me

H H CI H H H H Me

Me H H H H H H Me

H Me H H H H H Me

H H Me H H H H Me

OMe H H H H H H Me

H OMe H H H H H Me

H H OMe H H H H Me

CF ₃ HHHHHH Me

H CF ₃ HHHHH Me

HH CF ₃ HHHH Me

H H H H H H CI Me

F H H H H H CI Me

H F H H H H CI Me

H H F H H H CI Me

CI H H H H H CI Me

H CI H H H H CI Me

H H CI H H H CI Me

CI CI H H H H CI Me

CI H CI H H H CI Me

CI H H CI H H CI Me

CI H H H CI H CI Me

H CI CI H H H CI Me

H CI H CI H H CI Me

H CI H H CI H CI Me

H Br H H H H CI Me

H H I H H H CI Me

HF CI HHH CI Me Table

Substituent on benzene ring (X and Y)

 9 IV

 0 4 5 0

 H CI F H H H CI Me

H Br CI H H H CI Me

C1 H H H H H CI Et

H CI H H H H CI Pr-n

H H CI H H H CI Pr- i

Me H H H H H CI Me

H Me H H H H CI Me

H H Me H H H CI Me

Me Me H H H H CI Me

Me H Me H H H CI Me

Me H H Me H H CI Me

Me H H H Me H CI Me

H Me Me H H H CI Me

H Me H Me H H CI Me

H Me H H Me H CI Me

Et H H H H H CI Me

H Pr-n H H H H CI Me

H H Pr-i H H H CI Me

H Bu-n H H H H CI Me

H H Bu-t H H H CI Me

Pen- -n H H H H H CI Me

Me H H H H H CI Et

H Me H H H H CI Pr-n

H H Me H H H CI Pr-i

OMe H H H H H CI Me

H OMe H H H H CI Me

H H OMe H H H CI Me

OEt H H H H H CI Me

H OPr-r 1 H H H H CI Me

H H OBu-n H H H CI Me

CF ₃ HHHHH CI Me

H CF ₃ HHHH CI Me

_{HH CF 3 HHH CI MeCF 3 HHHHH} CI Me

H OCFs HHHH CI Me Table ¾m

Substituent on benzene ring (X and Y)

Q cr R ¹ R ² R ³ 0 4 0 D

 Η H OCFs H H H CI Me

NO H H H H H CI Me

H NO H H H H CI Me

H H NO H H H CI Me

H H H H H CI H Me

CI H H H H CI H Me

H CI H H H CI H Me

H H CI H H CI H Me

Me H H H H CI H Me

H Me H H H CI H Me

H H Me H H CI H Me

OMe H H H H CI H Me

H OMe H H H CI H Me

H H OMe H H CI H Me

CFs H H H H CI H Me

H CFs H H H CI H Me

HH CF ₃ HH CI H Me

H H H H H Me H Me

CI H H H H Me H Me

H CI H H H Me H Me

H H CI H H Me H Me

Me H H H H Me H Me

H Me H H H Me H Me

H H Me H H Me H Me

OMe H H H H Me H Me

H OMe H H H Me H Me

H H OMe H H Me H Me

CF ₃ HHHH Me H Me

H CF ₃ HHH Me H Me

HH CF ₃ HH Me H Me

H H H H H Me CI Me

CI H H H H Me CI Me

H CI H H H Me CI Me

H H CI H H Me CI Me

CI CI HHH Me CI Me Table; | 9C

Substituent on benzene ring (X and Y)

R ¹ R ² R

2 3 4 5 6

 C1 H C I H H Me C I Me

C1 H H C I H Me C I Me

C1 H H H C I Me C I Me

H CI CI H H Me CI Me

H CI H C I H Me CI Me

H CI H H CI Me C I Me

H Br H H H Me C I Me

H H I H H Me CI Me

Me H H H H Me CI Me

H Me H H H Me CI Me

H H Me H H Me CI Me

Me Me H H H Me CI Me

Me H Me H H Me CI Me

Me H H Me H Me CI Me

Me H H H Me Me CI Me

H Me Me H H Me CI Me

H Me H Me H Me CI Me

H Me H H Me Me CI Me

OMe H H H H Me CI Me

H OMe H H H Me CI Me

H H OMe H H Me CI Me

CFa H H H H Me CI Me

H CFs H H H Me CI Me

HH CF ₃ HH Me CI Me

NO 2 H H H H Me CI Me

H NO 2 H H H Me CI Me

H H NO 2 H H Me CI Me

H H H H H CFs H Me

CI H H H H CFs H Me

H CI H H H CFs H Me

H H CI H H CFs H Me

Me H H H H CFs H Me

H Me HHH CF ₃ H Me

H H Me H H CFs H Me

OMe HHHH CFs H Me Table continuation

Substituent on benzene ring (X and Y)

5 R ¹

2 3 4 6 R ² R

H OMe H H H CFa H Me

HH OMe HH CF ₃ H Me

C1 HHHH CF ₃ CI Me

H CI HHH CF ₃ CI Me

H H CI H H CFs CI Me

H H H H H CI CI Me

C1 H H H H CI CI Me

H CI H H H CI CI Me

H H CI H H CI CI Me

C1 CI H H H CI CI Me

C1 H CI H H CI CI Me

C1 H H CI H CI CI Me

C1 H H H CI CI CI Me

H CI CI H H CI CI Me

H CI H CI H CI CI Me

H CI H H CI CI CI Me

H Br H H H CI CI Me

H H I H H CI CI Me

Me H H H H CI CI Me

H Me H H H CI CI Me

H H Me H H CI CI Me

Me Me H H H CI CI Me

Me H Me H H CI CI Me

Me H H Me H CI CI Me

Me H H H Me CI CI Me

H Me Me H H CI CI Me

H Me H Me H CI CI Me

H Me H H Me CI CI Me

OMe H H H H CI CI Me

H OMe H H H CI CI Me

HH OMe HH CI CI Me The phenylhydrazine derivative of the present invention is disclosed in International Patent Publication No.WO96 / 38419, Japanese Patent Publication No. 491-111061, and Japanese Patent Application Laid-Open No. 2-2955962. It can be produced with reference to Japanese Patent Application Laid-Open No. Hei 2-3030157, Doit Patent DE38021075 and European Patent EP640479.

 Further, among the phenylhydrazine derivatives of the present invention, the phenylhydrazine derivative represented by the general formula (2) can be produced by the following method. That is, a pyrazolecarboxylic acid (a) is converted into a carboxylic acid halide (b) according to a conventional method, and then reacted with various phenylhydrazines (c) to obtain a compound of the present invention represented by the general formula (2). Can be manufactured.

 (2)

(However, in the formula, X, Y, R ¹ , R ² and R ³ represent the same meaning as described above, and Ζ represents a halogen atom such as a chlorine atom or a bromine atom.)

 In the halogenation step of the pyrazole carboxylic acids (a), it is possible to directly add thionyl halide, halogenidine, oxyhalogenated phosphorus, phosgene, etc., but usually in an inert solvent such as chloroform, benzene, and toluene. It is better to carry out at 0 to 120 ° C or the reflux temperature of the solvent.

One of the pyrazolecarboxylic acid halides (b) and phenylhydrazines (c) The step of producing the compound of the present invention represented by the general formula (2) can be performed in a suitable inert solvent. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene and chlorobenzene, halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane, ethers such as diisopropyl ether, tetrahydrofuran and dioxane, and acetonitrile and the like. Examples thereof include polar solvents such as nitriles, dimethyl sulfoxide, and dimethylformamide.

 Further, if necessary, an organic base (eg, pyridine, triethylamine) or an inorganic base (eg, carbon dioxide, hydroxide, sodium hydride) may be added. In this reaction, the reaction temperature is usually preferably from 0 to 50 ° C.

 The compound of the present invention represented by the general formula (2) of the obtained crude product can be used as it is. As the purification of the compound of the present invention, recrystallization, solvent washing, column chromatography or the like can be usually applied.

 Specific examples of the synthesis are shown below, but the present invention is not limited thereto.

 [Synthesis Example 1] (Synthesis of Compound 3)

 Compound 3

0.64 g of 3,5-dichloro-1-1-methyl-4-carboxylic acid chloride was dissolved in 3 O ml of dichloromethane. Under ice cooling and stirring, 0.47 g of 4-chlorophenylhydrazine and then 0.36 g of triethylamine were added to the solution, and the temperature was gradually raised to room temperature.

 After stirring at room temperature for 1 hour, the reaction solution was washed with 100 ml of water, and the dichloromethane layer was dried over anhydrous sodium sulfate.

The solvent is distilled off under reduced pressure, and the residue solid is mixed with n-hexane getyl ether mixed solvent. Then, 0.80 g of the compound 3 of the present invention was obtained. (Melting point: 11.9.-0-192.0 ° C)

 (Synthesis Example 2-5)

 Compound 1, Compound 2, Compound 4 and Compound 5 were synthesized in the same manner as in Synthesis Example 1.

 Compound 1 (melting point 1 31.0-132.0 ° C)

 Compound 2 (melting point 15.9-11.6 ° C)

 Compound 4 (melting point: 132.0-13.3 ° C)

 Compound 5 (melting point 178.0-179.0 ° C)

Compound 1 Compound 2

 'Compound 4 Compound 5 The phenylhydrazine derivative used as an active ingredient in the present invention may be used alone, or when the industrial antibacterial / antifungal agent, algicide and biofouling inhibitor of the present invention are used. If necessary, other known industrial antibacterial and antifungal agents, algicides or biofouling inhibitors can be further contained and used as a mixture.

 Representative examples are listed below, but are not limited thereto.

N-decyl-N-isononyl-Ν, Ν-dimethylammonium chloride, poly [oxy- Quaternary ammonium compounds such as 1,2-ethanediyl (dimethylimino) -1,2-ethanediyl (dimethylimino) -1,2-ethanediyl dichloride];

 Aldehyde compounds such as glutaraldehyde;

 1,2-dibromo- 1,2,4-di-cyanobutane, 2,2—di-butamate 3—di-tri-propionamide, 2-promo 2-di-tropropanediol, 5-promo 5—ditro 1,3-dioxane Halogenated compounds such as;

 N-nitrogen-based compounds such as bromochlorodimethylhydantoin and trichloromouth isocyanuric acid;

 Guanide-based compounds such as poly (hexamethylene biguanide) hydrochloride; zinc dimethyldithiolate zinc rubamate, getyldithi zinc dirubinate zincate, dibutyruditi zinc zinc rubamate, ethyl benzyldithilate zinc salt Zinc acid salt, ethylene bisdithiol zinc salt, propylene bisdithiol zinc salt, bis (dimethyldithiol rubamoyl) ethylene bisdithiol zinc salt, ethylene bisdithiol zinc manganese acid, dimethyldithionate zinc Dithiocarbamate-based metal compounds such as nickel rubamate, nickel dibutyldithiocarbamate, dimethyldithiophene copper rubamate, and dimethyldithiocarbamate iron;

 Copper-based metal powders such as copper powder and copper-nickel alloy powder;

 Copper compounds such as cuprous oxide, cuprous thiocyanate (copper rhodan), basic copper carbonate, copper pyrophosphate, copper naphthenate, copper abietic acid, and copper oxyquinoline;

 Pyrithion-based metal compounds such as zinc salt of 2-pyridinethiol-1-oxide and copper salt of 2-pyridinthiol-toxide;

 Tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetra-n-propylthiuram disulphide, tetraisopropylthiuramdisulfide, tetra-n-butylthiuram disulphide, tetraisobutyl thiuram disulphide Iides, Ν, Ν '— thiuram-based compounds such as ethylenebisthiocarbamoyl sulfide, Ν, Ν'-propylenebisthiocarbamoyl sulfide, Ν, Ν'-butylenebisthiophyrubamyl sulfide;

2— (4-Ithiazolyl) benzi midazole, 2— (Methoxycarbonylamido) No.) Benzi midazo, methyl-1- (ω-cyanopentylcarbamoyl)-2 -benzi midazo, 2 -zinc mercaptobenzi midazo zinc, 2-thiocyanomethylthiobenzi midazole, etc. -Based compounds;

 2-mercaptobenzothiazole, 2- (thiocyanomethylthio) benzothiazol, 2- (thiocyanomethylsulfonyl) benzothiazol, 2-thiothianoethylthio-1 4-cyclobenzotothiazole, 2-thiocyanopropyl Benzothiazole-based compounds such as thio-5,7-dichlorobenzothiazole and 2-thiothianomethylthio-1,4,5,6,7-tetrachloro benzothiazole;

 Ditolyl compounds such as tetrafluoroisophthalonitrile, tetrachloroisophthalonitrile, 5-chloro-1,2,4-difluoro-6-methoxyisophthalonitrile, 2,4,5,6—tetrachloroisophthalonitrile ;

 5 —Chloro-2-methyl-3 —isothiazolone, 5 —Chloro-2-n —decyl —3-isothiazolone, 4,5 —dichloro-2 -— (4-chlorobenzyl) -1-3-isothiazolone, 4,5-dichloro1-2 — (4 —Chlorophenyl) -1-3-isothiazolone, 4,5-Dichloro-2-n-hexyl-3- 3-isothiazolone, 4,5-trimethylene-12-methyl-1-3-isothiazolone, 4-methylthi-5 —Chloro-1-n—octyl-1-3-isothiazolone, 2-methyl-1-isothiazolone, 4,5—dichloro-2-n-octyl-4-4-isothiazolin-1-3-, 2-n—octyl-4- Isothiazoline-based compounds such as isothiazolin-3-one and 1,2-benzoisothiazolin-13-one;

 1 1 [2— (2,4-dichloromethane) 1 4 1-propyl-1 1,3-dioxolanyl-2—methyl] -1 1H—1,2,4-triazole, 4,4-dimethyl 2 (1,2,4-triazole_1-yl) — 1— (4—Trifluoromethyl-2-chlorophenyl) 1 1 1-Penten-2-ol and other triazole compounds

2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,3,6—trichloro-4—propylsulfonylviridine, 2,6-dichloro-1,3,5—dicyanor-4-phenylpyridine Pyridine compounds;

2,4 dicro-mouth 6- (o-chloroanilino) -s-triazine, 2-clo Mouth 4 —Methylamine 6 —Isopropylamine s —Triazine, 2 —Black mouth-4,6 —Bis (ethylamino) 1 s—Triazine, 2 —Black mouth 4,6 —Bis

(Isopropylamino) 1 s — triazine, 2-methylthio 1,4,6 —bis (ethylamino) 1 s — triazine, 2-methylthio 14 -ethylamino 16 -isopropylamino s — triazine, 2-methylthio 14t-butylamino-16-cyclopropylamino s-triazine compound such as triazine;

 N- (3,4-dichlorophenyl) —N'-methylurea, 3— (3,4-dichlorophenyl) 1-1,1-dimethylurea, 3— (3,4-dichlorophenyl) one

1-Methoxy 1 monomethylurea, 1 — (α, α '— dimethylbenzyl) 1-3-methyl-3 phenylurea, 1 — (2 methylcyclohexyl) — 3 — phenyl urine, 3 — ( Urea-based compounds such as 4- (1-isopropylphenyl) -1-1,1-dimethylurea;

 Quinone compounds such as 2,3-dichloro-1,4-naphthoquinone, 2-amino-3-chloro-1,4-naphthoquinone, 2,3-dicyanone 1,4 dithiaanthraquinone;

 N-trichloromethylthiotetrahydrofurophthalimide, N-1,1,2,2—tetrachloroethylthiotetrahydrofurimidate, N-trichloromethylthiophthalimid, N-fluorodichloromethylthiophthalimid Amide, N, N-dimethylamino N'-phenyl N '-(fluorodichloromethylthio) sulfamide, trichloromethylthiomethanesulfone p-chloroanilide, N— (1,1,2,2 —Tetrachloro-2-fluoroethylthio) methanesulfonylanilide, N-fluorodichloromethylthio-1-N—3-chlorophenyl-1-N′-dimethylurea, N—fluorodichloromethylthio-N—3, 4-N-Methylurine, N-Fluoro-N-methylthio-N-Tris-sulfonyl-N-Methylamine Compound;

N-Phenethyldichloromale-mid, N-benzyldichloromale-mid, N- (2-chlorophenyl) male-mid, N— (4-fluorophenyl) male-mid, N- (3,5-dichloro-mouth Phenyl) maleid, N— (2, 4, 6 — triclo mouth Phenyl) maleimide, N—4—tolyl maleimide, N—2,4-xylylmaleimide, 2,3-dichloro-1-N— (2 ′, 6′-Jetylphenyl) maleide, 2 , 3-Dichloro-N- (2'-methyl-6'-getylphenyl)

2,3-Dichloro-N- (2 ', 6'-dimethylphenyl) maleide, 2,3-Dichloro-1-N- (2', 4 ', 6'-trimethylphenyl) maleide Mid compounds;

 3,5-dimethyl-1-tetrahydro-1,3,5,2 (H) -thiadiazine-one-one, 3,3'-ethylenebis (tetrahydro-1,4-dimethyl-2-H-2,1-

3,5-thiadiazin-2-one, 3,5-dimethyl-2-thiotetrahydro-1,3,5-thiadiazine, 3,5-dibenzyltetrahydrodraw 1,3,5-methylthiocyanide, chlorothiocyanate Methyl, thiocyanate, methylene bis thiosinate, chloromethylene bis thiosinate, ethylene bis thiosinate, methyl ethylene bis thiosinate, isobornyl thiocyanate, methyl isothiocyanate, allyl Thiosocyanate compounds such as isothiocyanate, phenylisothiocyanate, and benzylisothiocyanate; alkylphenol compounds such as prill phenol and nonylphenol; tris (octylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonyl) Phenyl) Hosufai bets, bets tris (mono-, di- mixed noni Rufuweniru) Hosufuai alkyl off We alkylsulfonyl phosphine eye preparative compounds such bets;

 Alkyl phenyl phosphate compounds such as tris (octylphenyl) phosphate, tris (nonylphenyl) phosphate, tris (dinonylphenyl) phosphate, and tris (mono and di-mixed nonylphenyl) phosphate;

 0—3—dodium 2-propynyl N-butyl ester, N—3—odo—2-propynyl 0—butyl ester barrate, 2, 3, 3—triiodoaryl alcohol, jod methylpara Iodine compounds such as tolylsulfone;

polysulfide compounds such as n-butyloctyl chloromethyl disulfide; boron compounds such as pyridine triphenylborane; Further, the phenylhydrazine derivative used as an active ingredient in the present invention may be composed of a single compound or a mixture of several types of phenylhydrazine derivatives.

 The phenylhydrazine derivative used as an active ingredient in the present invention may be added alone to the above-mentioned use application system, or as a mixture comprising the active ingredient and, if necessary, an appropriate carrier or solvent, or It may be formulated as an aqueous emulsion or dispersion.

 The formulation of the industrial antibacterial and antifungal agent, the algicide and the biofouling inhibitor of the present invention can be used as an active ingredient in the present invention when outlined in the field of application of the industrial antibacterial and antifungal agent and the algicide. The phenylhydrazine derivative is mixed with a suitable carrier and auxiliary agent, for example, a surfactant, a binder, a stabilizer, etc., and mixed, and then wettable powders, emulsions, sols (floatables), etc. And used in an appropriate dosage form.

 When preparing these preparations, there is no upper limit on the concentration of the active ingredient fuunilhydrazine derivative as long as wettable powders, emulsions, solutions, sols, and other suitable preparations can be prepared. It is blended in an amount of 119 to 90% by weight, preferably 3 to 40% by weight based on the weight.

 As a carrier that can be used, any solid or liquid can be used as long as it is commonly used for industrial antibacterial and antifungal agents and algicides, and it is not limited to a specific one.

 Examples of solid carriers are mineral powders such as lime ore, bentonite, clay, montmorilloite, diatomaceous earth, mica, vermicillaite, gypsum, calcium carbonate, phosphate lime, white limestone, slaked lime, silica sand, Examples include ammonium sulfate, urea, etc., or vegetable powders, for example, soybean powder, starch, crystalline cellulose, etc., alumina, silicates, sugar polymers, highly dispersible silicic acids, waxes, etc.

Examples of liquid carriers include water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, Chlorobenzene, cumene, methylnaphthalene, etc. Are halogenated hydrocarbons, for example, chloroform, dichloromethane, ethylene dichloride, etc., ethers, for example, ethyl ether, dioxane, tetrahydrofuran, etc., ketones, for example, acetone, methylethyl ketone, cyclohexanone, methylisobutyl. Ketones, esters, for example, ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc., nitriles, for example, acetate nitrile, propionitrile, acrylonitrile, etc., sulfoxides, For example, dimethyl sulfoxide, alcohol ethers, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc., amines, for example, triethyl amine, etc., and aliphatic and alicyclic hydrocarbons, for example, n- Ki Down, cyclohexane and the like cyclopropyl, further industrial gasoline (petroleum ether, solvent naphtha, etc.), and petroleum fractions (paraffin acids, kerosene, gas oil, etc.), and the like.

 In the case of preparations such as emulsions, wettable powders, and sols (flowables), surfactants are incorporated for the purpose of emulsification, dispersion, solubilization, wetting, foaming, spreading, and the like. Examples of such a surfactant include the following, but are not limited thereto.

 Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, and sorbitan alkyl ester.

Examples of anionic surface active agents, alkylbenzene Natick DOO, alkyl Rusuru Hosah succinates, alkyl monkey sulfates, polyoxyethylene alkyl Sa Rufuwe DOO, § Li one Rusuruhone preparative and Raurirusarufuwe one preparative, and the like _c Examples of the cationic surfactant include alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.), and the like.

 Examples of the amphoteric surfactant include carboxylic acid (betaine type) sulfate, and the like.

In addition to these, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, gelatin, case , Alginate, tragacanth gum, guar gum, xanthan gum, hydroxypropylcellulose and other thickeners and various adjuvants. Further, if necessary, a suitable amount of a stabilizer such as an antioxidant or an ultraviolet absorber can be added.

 The industrial antibacterial and antifungal agents and algicides of the present invention containing a phenylhydrazine derivative as an active ingredient can be used for the following applications.

 Waterborne paints, adhesives, latex, emulsion products such as acrylics, starches, pigments, slurry products such as calcium carbonate, and growth control of bacteria, fungi and algae in joint cement; construction materials (building materials, civil engineering materials) Preservation of wood for building materials); Preservation of cutting oil; Prevention of surfactants; Vibration control of surfactants; Sterilization and prevention of slime formation in cooling towers, pulp and paper mills in factory manufacturing facilities and building air conditioning; Antibacterial and antifungal treatment by spraying or dipping on leather; Bacteria generated while paint film, especially exterior paint film is exposed to the weather; Protection from attack by fungi and algae; Interior and exterior materials made of polyurethane, polyethylene, polypropylene, silicone, modified silicone, nylon, epoxy, etc. ), Building materials (building materials, civil engineering materials, etc.), antibacterial and antifungal and algicidal products for home appliances, household goods, sports goods, etc .; protection of slime deposits on sugarcane and sugar beet sugar manufacturing equipment; air cleaner Prevention of accumulation and accumulation of microorganisms in scrubber systems and industrial freshwater supply systems; maintenance of sanitary conditions in food factories; deodorization and sterilization of sewage treatment plants, human waste treatment plants, etc. when washing production facilities; Prevent microbial contamination and sedimentation in muddy water and secondary oil recovery processes; Prevent the growth of bacteria and fungi in paper coatings and coatings; Prevent microbial contamination in cosmetics and toiletry products Control algae growth in pools, etc. Prevention of microbial contamination of agricultural formulations, electrodeposition systems, diagnostic and pharmaceutical products, medical equipment, etc .; prevention of microbial accumulation in photographic processing.

An anti-fouling agent containing a phenylhydrazine derivative as an active ingredient, such as fishing nets, the bottom of ships, buoys and other submarine equipment, marine structures, condenser cooling water systems for thermal or nuclear power plants, and heat from the chemical industry Water mussels, mussels, oysters, hydrmes for underwater structures such as water intake channels for exchanger cooling water and auxiliary equipment for dams, and reservoirs It can be used to prevent the adhesion of harmful aquatic organisms such as shellfish such as seaweed, hydra, selbra, sea squirt, bryophytes and snails, and algae such as azaa, honori and shimidro.

 Formulation examples when the phenylhydrazine derivative of the present invention is used as an industrial antibacterial and antifungal agent and an algicide are shown using the compound of the present invention. The compounding ratio of the active ingredient, the type and amount of the carrier and the auxiliary agent are shown. Are not limited to these.

Formulation Example 1 (emulsion)

 Ingredient

 Compound 5 of the present invention

 Dimethyl sulfoxide 8 5

 Methyl isobutyl ketone 5

 Solpole 8 0 0 A 5

 (Emulsifier manufactured by Toho Chemical Co., Ltd.)

 1 0 0

 By mixing and dissolving the above, an emulsion containing 5% of the active ingredient was obtained. Formulation Example 2 (Wettable powder)

 Ingredient

 Compound 20 of the present invention

 Lauryl Sulfate 7

 Cre 1 7 3

 1 0 0

The above was uniformly mixed and pulverized to obtain a wettable powder containing 20% of the active ingredient ₍

Formulation Example 3 (Floable agent)

 Ingredient

 Compound 20 of the present invention

 Lauryl Sulfate 2

 Xanthan gum 2

 Hydroxypropyl cellulose 1

 Distilled water 7 5

 1 0 0

 The above mixture was placed in a ball mill and pulverized and mixed for 12 hours to obtain a flooring agent containing 20% of the active ingredient.

 The formulated industrial antibacterial and antifungal agents and algicides of the present invention can be obtained by diluting various preparations as they are or by diluting them with water or an appropriate organic solvent, and then preparing them in various industrial raw materials or products. To the surface of various industrial raw materials and products, or to spray various industrial raw materials and products in the diluent of the industrial antibacterial, antifungal and algicidal agents of the present invention. It can be used by various methods in accordance with the generally used methods of industrial antibacterial and antifungal agents and algicides, including the method of immersion in water, etc. It is not limited.

 Formulations of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are outlined in the field of application of biofouling inhibitors. The phenylhydrazine derivative used as an active ingredient in the present invention is a paint , Solutions, emulsions and the like. For the preparation of these paints, solutions, emulsions and the like, general recipes usually used can be adopted.

 When the underwater biofouling inhibitor of the present invention is used in the form of an antifouling paint, for example, a paint is prepared by blending a phenylhydrazine derivative, which is an active ingredient, with a film-forming agent, and is used to prepare a ship bottom, marine By applying it to a structure, a cooling water intake pipe or an underwater structure, it is possible to prevent the adhesion and propagation of underwater organisms.

 As a coating film forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.

Further, a solvent, a pigment, or the like may be used as necessary. When preparing a paint, there is no upper limit on the concentration of the phenylhydrazine derivative as an active ingredient as long as a coating film can be formed, but 1 to 50% by weight, preferably 5 to 50% by weight based on the weight of the antifouling paint. It is blended at a ratio of 20% by weight.

 Formulation examples in the case where the underwater biofouling inhibitor of the present invention is used as an antifouling paint are shown using the compound of the present invention, but the present invention is not limited thereto.

Prescription example 4

 Ingredient weight% Compound of the present invention

 VYHH (vinyl synthetic resin, manufactured by UCC) 7

 Rosin 7

 Tricresyl phosphate 3

 Talc 2 0

 Sulfuric acid barrier 1 5

 Red petals 1 0

 Xylene 2 0

 Methylisobutyl ketone 1 0

 1 0 0 Prescription example 5

 Ingredient

 Compound 5 of the present invention

 C R- 10 (chlorinated rubber resin, manufactured by Asahi Denka) 1 3

 Zinc flower 2 0

 Talc 2 0

 Plasticizer 2

 Red petals 1 0

 Xylene 3 0

1 0 0 When the underwater biofouling inhibitor of the present invention is used in the form of a solution, for example, a solution in which a phenylhydrazine derivative, which is an effective component, is dissolved in a solvent together with a film-forming agent is prepared, and the solution is used for aquaculture nets and stationary. By applying it to fishing nets and the like, it is possible to prevent the adhesion and propagation of aquatic organisms.

 Synthetic resins, artificial rubbers, natural resins and the like are used as the film forming agent, and xylene, toluene, cumene, methylethylketone, methylisobutylketone, acetate and the like are used as the solvent.

 Further, an additive such as a plasticizer may be used if necessary. When preparing a solution, there is no upper limit on the concentration of the funinylhydrazine derivative, which is an active ingredient, as long as a solution can be formed, but 1 to 50% by weight, preferably 5 to 30% by weight of the solution is used. It is blended in a ratio.

 Formulation examples when the underwater biofouling inhibitor of the present invention is used as an antifoulant solution are shown using the compounds of the present invention, but are not limited thereto.

Prescription example 6

 Ingredient weight%

 Compound 15 of the present invention

 Acrylic resin (50% xylene liquid) 50

 Xylene 3 5

 1 0 0 Prescription example Ί

 Ingredient

 Compound of the present invention 10

 Acryl resin (50% xylene solution) 40

 Di-tertiary nonyl pentasulfide 5

 Liquid paraffin 5

 Xylene 4 0

1 0 0 When the underwater biofouling inhibitor of the present invention is used in the form of an emulsion, a surfactant is usually added to a solution of the phenylhydrazine derivative as an active ingredient according to the general method for preparing an emulsion, and Can be prepared, and there is no particular limitation on the type of surfactant used.

 The prepared emulsion can be used by kneading it into raw materials such as aquaculture nets and fixed nets used in the ocean or water, for example, polymer resins and the like.

 When an emulsion is prepared, the concentration of the phenylhydrazine derivative as an active ingredient has no upper limit as long as the emulsion can be formed. However, the concentration is 1 to 50% by weight, preferably 3 to 30% by weight based on the weight of the emulsion. In the proportion of

 Further, the above-mentioned solution or emulsion of the present invention can also be used by adding to water or water storage in order to prevent adherent propagation of aquatic organisms in a cooling water intake pipe or a reservoir.

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described more specifically and in detail with reference to Examples using Compounds 1 to 38, but the present invention is not limited thereto.

 (Compounds 6 to 38 are disclosed in JP-B-49-11061, JP-A-2-295692, JP-A-2-300157, Doit patent DE The compound was synthesized according to the methods described in Japanese Patent Application Laid-Open No. 380215/1995 and European Patent No. EP 604 798.) Compound 6 (melting point: 149 ° -150.degree. C.)

Compound 7 (melting point 1570-15.9.C)

Compound 8 (melting point 1620-164.0 ° C)

Compound 9 (solid)

Compound 10 (melting point 1930 0 19,0 ° C)

 Compound 1 1 (melting point: 1550 ° C)

 Compound 1 2 (melting point 1 7 3 5 1 7 5 5 ° C)

 Compound 13 (melting point: 202 ° C)

 Compound 1 4 (melting point 15 3 0 1 5 5 0 ° C)

Compound 15 (solid) Compound 16 (solid)

Compound 17 (melting point 13.9-14.1 ° C) Compound 18 (melting point 13-7.0-13.9 ° C) Compound 19 (melting point 185.0-1) 87.0 ° C) Compound 20 (melting point 148.0-14.9 ° C) Compound 21 (melting point 94.0-96.0 ° C) Compound 22 (melting point 17 6.0-1 78.0 ° C) Compound 23 (melting point 187.0-188.0 ° C) Compound 24 (melting point 17 6.17 8.0 ° C) Compound 2 5 (melting point 19.5.19.7.0 ° C) Compound 26 (melting point 22.6.28.0 ° C) Compound 27 (melting point 15 1.15.20 ° C) Compound 28 (melting point 183.0-185.0 ° C) Compound 29 (melting point 132.0-133.0 ° C) Compound 30 (melting point 91.0-92.2 0.C) Compound 31 (melting point 144.0-14.5 ° C) Compound 32 (melting point 178.0-170 ° C) Compound 33 (melting point 158.0 ° C) Compound 15 (melting point 125.0-120.C) Compound 35 (melting point 152.0-150.C) Compound 36 (melting point 109.C) 0-110 ° C) Compound 37 (melting point 98.0-99.0.C) Compound 38 (melting point 175.0-176.0 ° C)

Compound 6 Compound 7

 Compound 8 Compound 9 Compound 10

Compound 1 3 Compound 1 5

Compound 1 6 Compound 1 7

Compound 1 9

Compound 20 Compound 2 Compound 23

Compound 26 Compound 27

Compound 29

化合物 35 化合物 37

Compound 3 1

Compound 35 Compound 37

 Compound 38

Examples (Evaluation of antibacterial and antifungal activities)

 The compound of the present invention was diluted with dimethyl sulfoxide in a series of dilutions (200 0 0, 1 0 0 0 0 0, 5 0 0 0, 2 5 0 0, 1 2 5 0, 6 2 6, 3 1 3, 1 5, 7, 8, 39, 20, 20, 10, 2.5 mgZl) were prepared. For bacteria, use Sensitivity Medium 1N (Nissui Pharmaceutical) and for fungi, use potato dextrose agar medium (Nissui Pharmaceutical), add 0.5 ml to 9.5 ml of each, mix into petri dishes. The solidified plate was poured.

The concentration of the compound of the present invention in the agar medium was 100, 500, 250, 125, 125, respectively. 62.5, 31.3, 15.6, 7.8, 3.9, 2.0, 1.0, 0.5, 0.25, 0.125 mg / l .

The inoculated bacteria were cultured at 37 ° C for 20 hours in broth for sensitivity measurement (Nissui Pharmaceutical), and the fungi were cultured in potato dextrose agar medium (Nissui Pharmaceutical) for 10 days. A suspension of 10 ^S CFU / ml was prepared.

 The suspension of the test bacterium was streaked using a platinum loop on a drug-mixed agar plate. The bacterium was incubated at 37 ± 1 ° C for 18 to 20 hours, and the fungus was 27. After culturing at C for 7 days, the concentration at which no growth was observed was defined as the minimum inhibitory concentration (MIC). The results are shown in Table 3.

 However, the symbols in the table mean the following.

 A: Rhodotorula mucilaginosa

 B: Trichophyton mentagrophytes Table 3 Activity against bacteria and fungi

 Compound M I C (mg / 1)

 No. A B

 1 15.6

 2 3.9 62.5

 3 15.6 15.6

 4 2.0 2.0

 5 31.3 15.6

 6 7.8 7.8

 7 15.6 15.6

 9 0.125

 1 0 1.0

 1 1 7.8 7.8

 1 2 3.9 3.9

1 7 3.9 Table 3 (continued) Activity against bacteria and fungi

 Compound M I C

 N 0. A B

 1 8 15.6 15.6

 1 9 15.6

 2 0 15.6

 2 1 15.6 7.8

 2 7 7.8

 2 8 15.6

 2 9 7.8 62.5

 3 0 62.5 31.3

 3 1 62.5

 3 2 62.5

 3 3 31.3

 3 4 7.8

 3 5 7.8 62.5

 3 7 7.8

 3 8 15.6 31.3 Example 2 (Evaluation of antibacterial and antifungal activities)

 The compounds of the present invention were diluted with dimethylsulfoxide in a dilution series 56, 78, 39 mg / 1) were prepared. For bacteria, use Sensitivity Medium 1N (Nissui Pharmaceutical) and for fungi use Potato Dextrose Agar Medium (Nissui Pharmaceutical), add 0.5ml to 9.5ml and mix Then, the mixture was poured into a petri dish to form a solidified plate. The concentration of the compound of the present invention in the agar medium was 100,500,250,125,62.5,31.3,15.6,7.8,3. 9, 2. O mg / 1.

The inoculated bacteria were cultured at 37 ° C for 20 hours in a broth for sensitivity measurement (Nissui Pharmaceutical), and the fungi were cultured for 10 days on a potato dextrose agar medium (Nissui Pharmaceutical). The prepared suspension of 1 0 ⁶ CF UZm 1.

 The suspension of the test bacteria was streaked onto a drug-mixed agar plate using a platinum loop, and cultured for 18 to 20 hours at 37 ± 1 ° C for bacteria and 7 days at 27 ° C for fungi. The concentration at which no growth was observed was defined as the minimum inhibitory concentration (MIC).

 The results are shown in Table 4.

 However, the symbols in the table mean the following.

 A: Staphylococcus aureus

 B: Micrococcus lutea

 C: Corvnebacterium aquaticum

D: Alcaligenes Faecalis

 E: Aspergillus niger

 F: Penicillium funiculosum

 G: Chatomium globosum

 H: Rhizopus oryzae

 I: Candida albicans

 J: Saccharomvces cerevisiae Table 4 Activity against bacteria, fungi and yeast (Compound 6)

 M I C (m / 1)

 A B C D E F G H I J

 125 31.3 15.6 15.6 125 125 250 31.3 15.6 63 Example 3 (Evaluation of anti-Regionella activity)

 The compound of the present invention was made into a solution having a concentration of 200 mg / l using dimethyl sulfoxide, and 1 ml of the solution was diluted with 19 ml of sterilized tap water to prepare a solution having a concentration of 100 mg / l.

The sample solution 2 0 m 1 in the test bacterial solution was 0. 1 ml inoculated (legionella New乇Huy La (Legionella pneumophila), 3. 1 x 1 0 8 or Zm 1).

After 24 hours of contact at 30 ° C, the viable cell count after the action was measured. The results are shown in Table 5 ₍ Table 5 Number of viable cells 2 hours after active compound against Legionella bacteria)

 N o. (CFU / m 1)

6 8.0 X 1 0 ¹

9.6 X 10 ⁵ sterilized tap water Example 4 (Evaluation of growth inhibitory activity against freshwater green algae)

 A fixed amount of the compound of the present invention was dissolved in a medium containing 10 V m1 of freshwater green algae (Selenastrum capricornutum) in the logarithmic growth phase, and the concentration of the compound of the present invention in the medium was 50%. Samples of 0 ppb and 50 ppb were prepared, and were incubated at 23 ± 1 ° C for 24 hours under continuous lighting conditions.

 After 72 hours, the proliferation rate was determined by measuring the number of cells using a hemocytometer.

 The growth inhibition rate was calculated by comparison with the untreated group.

 The results are shown in Table 6. Table 6 Activity against freshwater green algae

 Compound growth inhibition rate (%)

 N 0 .500pDb 50ppb

 1 9 6 9 2

 2 9 6 9 3

 3 9 6 9 3

 4 9 4 8 9

 5 9 7 9 5

 6 9 5 8 9

7 9 0 7 3 (Continued) Active compound against freshwater green algae Growth inhibition rate (%)

0 .500ppb 50ppb

 8 9 2

 9 9 6 9 4

1 0 9 4 8 6

1 1 9 6 9 3

1 2 9 6 9 3

1 3 9 4 8 8

1 4 7 5 8 8

1 5 9 4 8 6

1 6 9 3 6 8

1 8 9 6 8 7

1 9 9 5 8 6

2 0 9 3

 2 1 8 8

 2 2 9 5 8 8

2 3 9 4 8 2

2 4 9 4 7 9

2 5 9 3 7 7

2 6 7 8

 2 7 9 5 9 1

2 8 9 6 8 6

2 9 9 2

 3 2 6 9

 3 3 9 3 8 8

3 4 9 6 9 2 Table 6 (continued) Activity against freshwater green algae

 Compound growth inhibition rate (%)

 N o. 500ppb 50ppb

 3 5 9 4 9 2

 3 6 9 2

 3 7 9 8 9 5

 3 8 9 5 9 3 Example 5 (Evaluation of growth inhibitory activity against seawater diatoms)

Seawater diatoms in the logarithmic growth phase (Nitchia Kurosuteriumu, Nitzschia closte rium) 1 0 ⁵ in medium containing Zm 1, were each dissolved in an amount of a compound of the present invention, concentration of each 5 0 of the present compounds in the medium A sample of 0 ppb was prepared, and the culture was allowed to stand at 22 ± 1 ° C for 24 hours under continuous illumination.

 After 72 hours, the cells were collected by centrifugation, and methanol was added to disrupt the cells and chlorophyll was extracted. The amount of chlorophyll was measured from the absorbance using a spectrophotometer to determine the growth rate.

 The growth inhibition rate was calculated by comparison with the untreated group.

 The results are shown in Table 7. Table 7 Activity against seawater diatoms

 Compound growth inhibition rate (%)

 N 0 .500ppb

 1 7 5

 2 6 8

 4 9 1

 1 0 8 5

 1 1 7 8

1 2 7 8 Table 7 (continued) Activity against seawater diatoms

 Compound growth inhibition rate

 500DDb

 1 3 8 2

 1 5 8 6

 1 7 7 0

 3 2 7 6 Example 6 (Evaluation of growth inhibitory activity against freshwater algae)

The medium containing freshwater alga 1 0 ⁵ / m 1 in the logarithmic growth phase, respectively to dissolve the amount of a compound of the present invention, the concentration of the present compound in the medium is at each 5 0 0 ppb and 5 0 ppb Samples were prepared and subjected to shaking culture at 100 rpm for 24 hours at a temperature of 20 ± 2 ° C for freshwater diatoms and 23 ± 2 ° C for other algae species for 24 hours. I got it.

 After 72 and 168 hours, the proliferation rate was determined by measuring the total cell volume using a hemocytometer. The growth inhibition rate was calculated by comparison with the untreated group. The results are shown in Tables 8 to 11. However, the symbols in the table mean the following.

 A: Freshwater green algae (Chlorella pyrenoidosa) B: Freshwater cyanobacteria (Microcystis aeruginosa) C: Freshwater diatom (Diatoma elongatum, Matoma elongatum)

 D: Activity against freshwater green algae (Scenedesmus pannonicus) Table 8 A

 Growth inhibition rate (%)

 Compound 500ppb 50ppb

 N 0. 72hr 168hr 72hr 168hr

 6 77 68

9 85 100 96 69 Table 9 Activity against B

 Growth inhibition rate (%) Compound 500ppb 50ppb N 0.72hr 168hr 72hr 168hr

4 79 81 89 6 80 97 88 98 9 85 97 84 100

1 0 91 1 5 94

Table 10 Activity for C

 Growth inhibition rate (%) Compound 500ppb 50ppb No. 72hr 168hr T2hr 168hr

4 87 87 82

9 77 87 78 82

1 0 73 86 1 65 63

 1 5 82 85 1 8 82 70 2 0 74

2 1 88

Table 11 Activity for D

 Growth inhibition rate (%)

 Compound 500ppb 50ppb

 N o. 72hr 168hr 72hr 168hr

 4 93 66 62

 6 64 75

 1 0 75 85

 1 5 70 84 Example 7 (Evaluation of mussel adhesion prevention activity)

 The compound of the present invention was completely dissolved in 1 ml of acetone and applied uniformly in a 4 cm diameter zone drawn on a test plate. A zone to which only acetone was applied was provided as a blank, and a zone to which 1.0 mg and 0.5 mg of copper sulfate were applied as comparative agents was provided. After drying, blue mussels (Mytilus edulis) having a shell length of about 2-2.5 cm were adhered to the outer periphery of each zone by using 4 pieces of rubber as a splicer. The prepared test plate was immersed in a water tank into which seawater flows, and allowed to stand in a dark place for 3 hours. The adhesion control effect (adhesion repellent activity) was determined in comparison with copper sulfate used as a comparative drug.

 The evaluation method of the adhesion activity is described by Kazuo Ina and Hideo Eto, "A method for retrieving active substances that adhere to marine epiphytes using mussels" (Chemistry and Biology, Vol. 28 (No. 2), 132- : L38 page (1990)).

 The results are shown in Table 12. However, the symbols in the table mean the following.

 + +: Does not adhere to the zone at all, and a strong repellent effect is observed.

 +: Adhesion inside the zone is also observed, but most adhere to the outside of the zone, and repellent effects are observed.

I: Adhered to the same extent inside and outside the zone, and no repellent effect was observed. Table 12 Repellent activity against mussels

 Compound judgment

 N o. (Mg)

 1 1 0 + +

 0 5 + +

 1 0 + 4- 0 5 + +

 Copper sulfate 10 0 +

 0 5

 Blank

Industrial applicability

 The phenylhydrazine derivative represented by the general formula (1) is highly safe, exhibits a wide spectrum at a low dose, and is an industrial antibacterial agent, an antifungal agent, an algicide, and a biofouling inhibitor. Useful as an agent.

Claims

The scope of the claims 1. General formula (1)

(Wherein X and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and a carbon atom of 1 Represents an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a dinitro group substituted with a halogen atom,  W is

(Wherein X ¹ and Y ¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, Represents an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom or a nitro group, and m and n each independently represent 0 or 1.) or

(Wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1-5 carbon atoms, or an alkyl group having 1-5 carbon atoms substituted with a halogen atom. R ³ represents an alkyl group having 1 to 3 carbon atoms. ). An industrial antibacterial and antifungal agent, an algicide and a biofouling inhibitor, characterized by containing a phenylhydrazine derivative represented by the formula:  2. An industrial antibacterial and antifungal agent comprising the phenylhydrazine derivative according to claim 1. 3. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t- Butyl group, n-pentyl group, trifluoromethyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, trifluoromethoxy group or X ¹ and Y ¹ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl, t-butyl, n-pentyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, n — a pentyloxy group, a trifluoromethoxy group or a nitro group; R ¹ and R ² are each independently a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group; R ³ is a methyl group; 3. An industrial antibacterial / antifungal agent comprising the phenylhydrazine derivative according to claim 2, which is an ethyl group, an n-propyl group or an i-propyl group. 4. X and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a methoxy group or a nitro group; X ¹ and Y ¹ each independently represent a hydrogen atom; An industry comprising the phenylhydrazine derivative according to claim ³ , which is an atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a t-butyl group or a methoxy group, and R ³ is a methyl group. For antibacterial and antifungal agents.  5. An algicide comprising the phenylhydrazine derivative according to claim 1. 6. A biofouling inhibitor comprising the phenylhydrazine derivative according to claim 1. 7. General formula (2)

(Wherein X and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and a carbon atom of 1 Represents an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a nitro group substituted with a halogen atom, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 carbon atom. Represents an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and R ³ represents an alkyl group having 1 to 3 carbon atoms.) Hydrazine derivative. 8. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and a t_butyl Group, n-pentyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, n-pentyloxy, trifluoromethoxy or R ¹ and R ² are each independently a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group, and R ³ is a methyl group, an ethyl group, an n-propyl group or an i 8. The phenylhydrazine derivative according to claim 7, which is a propyl group. 9. The method according to claim 7, wherein X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a methoxy group or a nitro group, and R ³ is a methyl group. A hydrazine derivative of