CA1204784A - Substituted benzyl-cycloalkenyl urea derivatives, their intermediates, the processes for their preparation and a use as fungicides for agriculture and horticulture - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The invention relates to a substituted benzyl-cyclo-alkenylamine of the formula (II)

Description

23189-5~29D
This applica~ion is diviaed out of eopending parent application Serial No. 442,342 filed on December 1, 1983. This application relates to new substituted benzyl-cycloalkenyl-amines of formula (II) X

~ - CH2 - NH (II) ll wherein X is a halogen atom or a lower alkyl group, and Rl is a eyeloalkenyl group, and proeesses for the preparation of eompounds of formula (II). Compounds of formula (II) are useful as inter-mediates for preparing novel fungicides of formula (I) as defined hereinafter, which are the subject of the copending parent appli-cation.
The invention of the parent applieation relates to novel substituted benzyl-eyeloalkenylurea derivatives, processes for the produetion of said derivatives, and agrieultural ~r hortieultural fungicides. It is already known that eertain N-(l-eycloalken-l-yl) ureas, respectively thioureas, such as, for example, N-benzyl-N-eyclohexen-l-yl-N'-phenyl urea, N^-cyclohexen-l--yl-N-methyl--N'-phenyl urea, have herbieidal respectively fungieidal properties (compare United States Patents No. 3,701,807 and 3,761,241). The preparation and the use as fungieides of other N-cycloalkyl-N-benzyl-Ni-phenyl urea derivatives are known (compare German Patent No. 2,732,257).
Aecording to one aspecc of the invention of the parent application there is provided new substitu-ted benzyl-cycloalkenyl-Nit-157 ~;

- ~2~7~

urea derivatives of the following formula (I) X Y
~ CH2 - N - C - NH - R2 (I) wherein X represents a halogen atom or a lower alk~-l group; Y
represents an oxygen atom or a sulfur a-tom; Rl represents a cycloalkenyl group, and R2 represents a lower alkyl group, a cycloalkyl group, a benzyl group c,r a phenyl group optionally substituted by 1 to 5 substituents selected from the group consisting of a hydroxyl group or a lower alkoxy group, have been found~
According -to another aspect of the parent application there is provided a process for preparing -the new substituted benzyl-cycloalkenylurea derivatives of the formula (I) X '~
~ CH2 - N -- C - NH -~ R (I) Rl wherein X represents a halogen atom or a lower alkyl group; Y
represents an oxygen a-tom or a sulfur atom; R represents a cycloalkenyi group, and R2 represents a lower alkyl group, a cycloalkyl group, a benzyl group or a phenyl group op-tionally substituted by 1 to 5 substituents selected from the group con-sisting of a hydroxyl group or a lower alkoxy group, which process comprises reacting i) a substituted benzyl-cycloalkenylamine of the formula (II) ~ CH~ - NH (II) ~ 1 1 wherein X and Rl are as defined above, with an isocyanate of the :Eormula (III) R - N = C = Y (III) wherein Y and R are as defined above if appropriate in the presence of a diluent or ii) a carbamoyl halide of the formula (IV) X ~ CH~ - N - C - Hal (IV) wherein X, Y and Rl are as defined above and Hal represents a halogen atom, with an amine of the formula (V) H2N - R (V) wherein R2 is as defined above if appropriate in the presence of a diluent and i~ appropriate in the presence of an acid binder.
It has furthermore been found that the new substituted benzyl-cycloalkenylurea derivatives of the formula (I) have power-ful fungicidal properties. They can be used as agricultural or horticultural fungicides.

~20~

Formula (I) provides a general definition o~ the substituted benzyl-cycloalkenylurea derivatives. Preferred compounds of the formula (I) are those in which X represents a halogen atom or a lower alkyl group with 1 to 6 carbon atoms, Y represents an oxygen atom or a sulfur atom, Rl represents a cycloalkenyl group with 5 to 7 carbon atoms and R represents a lower alkyl group with 1 to 6 carbon atoms, 1~ a cycloalkyl group with 5 to 8 carbon atoms, a benzyl group or a phenyl group optionally substituted by 1 to 5 of the same or different substituents selected from the group consisting of hydroxyl, or an alkoxy group with 1 to 4 carbon atoms.
Particularly preferred compounds of the formula (I) are those in which 7~

X represents fluorine, chlorine, bromine, jodine, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, iso-butyl or tert.-butyl Y represents an oxygen atom or a sulf~lr atom, R1 represents 2-cyclopenten-1-yl, 3-cyclopenten-1-yl,

2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2-cyclohepten-1-yl, 3-cyclohepten-1-yl and R represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, iso-butyl, tert. butyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, benzyl, phenyl optionally substituted by 1 or 2, same or different substituents selected from the groups hydroxyl~
methoxy, ethoxy, n-propoxy or iso-propoxy.

If, for example N-(2-cyclohexen-1-yl)-N-(4-chloro-benzyl)-amine and methylisocyanate are used as starting substances, the course of the reaction in process i) according to the invention can be represented by the following equation:

Cl- ~ CH2 N~H CH3 ~ -CH2-Nl-co-NH CH3 If, for example, N-4-bromobenzyl-N-(2-cyclopenten-1-yl) carbamoyl-chloride and aniline are used as starting substances the course of the reaction in process ii) according to the - Nit-157 ~2047~

invention can be represented by the following equation:

acid binder Br ~ CH2-N-CO-Cl+H2N ~ -HCl > Br ~ CH2-N-CO-NH
1~1 13 The substitued benzyl-cycloalkenylamines of the formula (II) required as starting materials for prosess i) are new. The presen-t invention relates to these new intermediates of the formula (II). These intermediates may be produced, for example, 1~ by the following known processes:
Process a) A process for producing a substituted benzyl--cyclo-alkenylamine of the above formula (II) which is characterized by reacting a substi-tued benzylamine of the formula:

~ CH2 - NH2 (VI) wherein X is as defined above with a compound of the formulao R - Hal (VII) ~2~

wherein R and Hal are as defined above or Process b) A process for producing a substituted benzyl-cyclo-alkenylamine of the above formula (II) which is characterized by reacting a substituted benzyl halide of the formula:

X ~ CH2 - l~al (VIII) wherein X and Hal are as defined above with a cyclo-alkenylamine of the formula:

R1 _ NH2 (IX) ~ wherein R is as defined above. Both processes a) and b) can be carried out if appropriate in presence of a diluent and in the presence of an acid binder at tempera-tures between about - 20C and the boiling point of ~he reaction mixtures preferably between 0C and 100C.

Specific examples of the starting material of the formula (II) are:

Nit-157 N-4-chlorobenzyl-2-cyclopenten-1-ylamine, N-4-bromobenzyl-2-cyclopenten--l-ylamine, N-4-methylbenzyl-2-cyclopenten-1-ylamine, N-4-chlorobenzyl-2-cyclohexen-1-ylamine, N-4-bromobenzyl-2-cyclo-hexen-1-ylamine, N-4-methylbenzyl-2-cyclohexen-1-ylamine, N-4--chlorobenzyl-3-cyclopenten--1-ylamine, N--4-bromobenzyl-3-cyclo-penten-l-ylamine, N~4-chlorobenzyl--3-cyclohexen-1-ylamine, N--4-methylbenzyl-3-cyclohexen-1-ylamine, N-4-chlorobenzyl-2-cyclo-hepten-l--ylamine.
The isocyanates of the formula (III) required as starting materials for process i) are generally well-known compounds.
Specific examples of the starting materials, the isocyanates of the formula tIII) are methyl isocyanate, ethyl isocyanate, propyl isocyanate, n--butyl isocyanate, cyclohexyl isocyana-te, phenyl isocyanate, 3--methoxyphenyl isocyanate, isopropyl isocyanate, ethyl isothiocyana-te, phenyl isothiocyanate, n-butyl isothiocyanate, benzyl isothiocyanate, 3-hydroxyphenyl isocyanate, 4--hydroxyphenyl isocyanate, 4-methoxyphenyl isocyanate.
Formula (IV) provides a general definition of the carbamoyl halides required as starting substances ~or process ii). They can be obtained by known analogy processes.
Specific examples of these starting materials, the carbamoyl halides of the formula (IV) are N-4-chlorobenzyl-N-(2-cyclopenten-1-yl)carbamoyl chloride, N-4--bromobenzyl-N-(2-cyclopenten--1-yl)carbamoyl chloride, N-4-me-thylbenzyl-N-(2-cyclopenten-1-yl)carbamoyl chloride, N-4-chlorobenzyl-N-(2-cyclohexen-1--yl)carbamoyl chloride, 7~

N-4-bromobenzyl-N-(2-cyclohexen-1-yl)carbamoyl chloride, N--4-methylbenzyl-N-(2-cyclohexen-1-yl)carbamoyl chloride, N-4-chlorobenzyl--N-(3-cycloper:-~en-1-yl)carbamoyl chloride, N-4-bromobenzyl-N (3--cyclopenten-1--yl)carbamoyl chloride, N-4-chlorobenzyl-N-(3-cyclohexen-1--yl)carbamoyl chloride, N-4-methylbenzyl-N-(3-cyclohexen-1-yl)carbamoyl chloride, N-4-chlorobenzyl-N-(2-cyclohepten-1--yl)carbamoyl chloride, as well as the bromides corresponding to the above chlorides, and the thiocarbamoyl halides corresponding to the above carbamoyl halides, such as thiocarbamoyl chlorides respectively bromides.
Specific examples of the other well-known starting materials, the amines of the formula (V) required for process ii) are methylamine, ethylamine, propylamine, n-butylamine, cyclohexylamine, aniline, 3-methoxyaniline, isopropylamine, m-aminophenol, p-aminophenol, 4-methoxyaniline.
Possible diluents for the reaction in process i) include water; aliphatic, alicyclic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chloro-benzene etc.; ethers such as diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydroruran etc.; ketones such as acetone, methyl e-thyl ketone, methyl iso-propyl ketone, methyl iso-butyl ketone etc.;
nitriles such as acetonitrile, propionitrile, acrylonitrile etc.;
esters such as ethyl acetate, amyl acetate etc.; acid amides such as dimethylformamide; dimethylacetamide etc.; sulfones and sulfoxides such as dimethylsulfoxide, sulfolane etc.; and bases such as pyridine etc.
The process i) may be practiced over a wide range of temperatures. Generally, it is carried out at a temperature between about -20C and the boiling point of the reaction mixture, preEerably between about 0C and about 100C. Although the reaction is desirably carried ou-t at normal pressure, it is also possible to operate under elevated or reduced pressure.
The process ii) may be practiced employing an inert solvent or diluent similar to the above--mentioned, thereby obtaining the desired product of high purity in a high yield Further, the above reaction ii) may be carried out in the presence of an acid binder. As such an acid binder, there may be mentioned commonly employed hydroxides, carbonates, bicarbonates, alkolates etc., of alkali metals, tertiary amines such as triethylamine, die-thylaniline, pyridine etc.
The above process ii) may be practiced over a wide range of temperatures. Generally, it is carried out at a temperature between abou-t -20C and about the boiling point of the reaction mixture, preferably betwen about 0C and about 100C. Although the reaction is desirably carried out at normal pressure, it is also possible to operate under elevated or reduced pressure~
Where a compound o~ the formula (I) wherein R2 is a hydroxy-substituted phenyl group is desired, the above process i) is preferred ~7~

In the process a) for the production of the new com-pounds of t~e formula ~II) of this invention as illustrated above, specific examples of the starting materials, the substituted known benzylamines of the formula (VI) are 4-chlorobenzylamine, 4-bromobenzylamine, 4-methyl-benzylamine etc.
Specific examples of the other starting materials, the compound of the formula (VII) include 3-chloro(or bromo)-cyclopentene, 3-~hloro (or bromo) cyclohexene, 4-chloro(or bromo)cyclopentene, 4-chlorc (or bromo) cyclo-hexene, 3-chloro(or bromo1cycloheptene etc.
In the process b) for the production of the new compounds of the formula (II) of this invention as illus-trated above, speci~ic examples o~ the starting material, the substituted benzyl halide of the formula (VIII) in-clude 4 chlorobenzyl chloride, 4-bromobenzyl chloride, 4-methylbenzyl chloride etc., as we~l as the bromides correspondin~ to the chlorides. Specific examples of the other starting material, the cylcoalkenylamines of the formula (IX) include 2-cyclopenten-1-ylamine, 2-cyclohexen-1-ylamine, 3-cyclopenten~1-ylamine, 3-cyclohexen-1-yl-amine, 2-cyclohepten-1-ylamine etc.
The above processes a) and ~) may be practiced employing an inert solvent or diluent similar to the above-mentioned in processes i) and ii), thereby ob-taining the desired product of hi~h purity in a high yield.
Furthermore, the abo~e processes a) and b) may be carried out in the presence of an acid binder similar to the above-mentioned.

Nit-157 1~71~

The above processes a) and b) may be practiced over G
wide range of temperatures. Generally, the reaction is carried out a-t a tempera-ture between about -20C and the boiling point of the reaction mixture, preferably between about 0C and about 100C. Although the reaction is desirably carried out at normal pressure, it is also possible to operate under elevated or reduced pressure~
The present inventors have discovered that the sub-stituted benzyl-cycloalkenylurea derivatives of the above formula lG (I) which had not been described in any literature may be produced and that said compounds have excellent agricultural or horticul-tural fungicidal activity.
Furthermore, the compounds of the formula (I) may be easily produced and their structural characteristics resides in that the urea (thiourea) structure is a backbone structure, and to the nitrogen atom at the 1-position are attached a substituted benzyl group and ~ cycloalkenyl group having 5 -- 7 carbon atoms, especially 2-(or 3-)cycloalken-1-yl group, and to ~he nit:rogen atom at the 3-position is a-ttached R2 as defined above. And it has now been discovered that by having the above--described specific structure, these compounds can manifest an agricultural or horticultural fungicidal effect, particularly an extremely remarkable controlling effect on rice sheath blight caused by Pellicularia sasakii.
Furthermore~ it has also been discovered that the compounds of the formula (I) can manifest a satisr`actory con-trolling effect on damping-off of vegetables caused by Rhizoctonia solani. -- 12 -~o~

The active compounds of formula (I) may be effec-~ively employed against pathogenic Eungi parasitizing the above-ground parts of plants, pathogenic fungi attacking plants through soil to cause tracheomycosis, seed-borne causative pathoyenic fungi and soil-borne causative pathogenic fungi.
Further, since these compounds are of only low toxicity to warm-blooded animals and have good compatibility with higher plants, that is, do not show phy-totoxicidty to crop plants at concentrations usually employed, -they may be quite conveniently employed against plant diseases caused by pathogenic fungi as agricultural or horticultural fungicides.
The compounds of the fsrmula (I) may be effectively employed as fungicides against Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes, Fungi Imperfecti etc. as well as various plant diseases caused by other bacteria.
When used as agricultuxal or horticultural fungicides the compounds of formula (I) may be diluted directly with water or processed, by addition of agriculturally acceptable adjuvants, into various preparations using methods commonly emp~oyed in the 2~ field of producing agricultural chemicals. These various prepara-tions may be used as such or after diluting with water to the desired concentration on actual use.
The agriculturally acceptable adjuvants which are herein referred to include, for example, diluents (solvents, fillers and carriers), surfactants (solubilizers, emulsifiers, dispersants and spreaders~, stabilizers, sticker-s, propellants for aerosols ar,d synergists.

7~

Examples of the solvents are water; and organic solvents, for example, hydrocarbons / as n-hexane, petroleum ether, naphtha, petroleum fractions (paraffin wax, kerosene, gas oil, middle oil, heavy oil etc.,), benzene, toluene, x~lenes etc 7, halogenated hydrocarbons /such as chloromethylene, carbon tetrachloride, trichloro-ethylene, ethylene chloride, ethylene dibromide, chloro-benzene, chloroform etc 7, alcohols /such as methyl al-cohol, ethyl alcohol, propyl alcohol, ethylene glycol etc 7, ethers Lsuch as diethyl ether, ethylene oxide, di-oxane etc. 7, alcohol ethers ~such as ethylene glycol mono-methyl ether etc 7, ketones /such as acetone, isophorone etc 7, esters / such as ethyl acetate, amyl acetate etc.7, amides ~such as dimethylformamide, dimethylacetamide etc /, sulfoxides ~such as dimethylsulfoxide etc 7and the like.
Examples of the fillers or carriers include organic pulverulent solids such as slaked lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, cal-cite, diatomite, amorphous silicon dioxide, alumina, zeolite, clay minerals (such as pyrophyllite, talc, mont-morillonite, ~eidellite, vermiculite, kaolinite, mica etc.); vegetable pulverulent solids (such as cereal pow-ders, starches, processed starches, sugar, glucose, plant stem crushed products etc.); synthetic resin pul-verulent solids (such as phenolic resins, urea resins,vinyl chloride resins etc.), and the like.
Examples of the suractants include anionic sur-actants such as alkylsulfates (e.g. sodium laurylsul-fate), arylsulfonic acids (e.g. alkylarylsulfonate salts, sodium alkylnaphthalenesulfonate etc.), succinic acid salts, polyethylene glycol alkyl aryl ether sulfuric acid ester salts.; cationic surfactants suc-h as alkyl-Nit-157 4~

amines (e.g. laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride etc.), polyoxyethylene alkylamines etc.; nonionic surfactants such as polyoxyethylene glycol ethers (e.g. polyoxye-thylene alkyl aryl ether and its condensates, etc.), polyoxyethylene glycol esters (e.g. polyoxy-ethylene fatty acid esters etc.), polyol esters (e.g. polyoxy--ethylene sorbitan monolaurate etc.), amopholitic surfactants and so for-th.
Examples of other adjuvants are stabilizers, stickers [e.g. agricultural soaps, casein line, sodium arginate, polyvinyl alcohol (PVA), vinyl acetate based adhesives, acrylic adhesives etc.], propellants for aerosols [such as -trichlorofluoromethane, dichlorofluoromethane, 1,2,2-trichloro-1,1,2--trifluoroethane, chlorobenzene, LNG, lower ethers etcO]; combustion modifiers (for fumigation) [such as nitrites~ zinc dust, dicyandiamide etc.];
effect-prolonging agents; dispersion stabilizers [such as casein, tragacanth, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA) etc.]; and synergists.
The compounds of formula (I) may be formulated into various preparation forms using methods commonly employed in the field of producing agricultural chemicals. Examples of the preparation forms include emulsifiable concentrates, oil prepara-tions, wettable powders, aqueous solutions, suspensions, powders, granules, pulverulent compositions, fumigants, tablets, aerosols, pastes, capsules etc.
The agricul-trual or horticultural fungicides can contain the aforesaid active ingredients in amoun-ts Gf abou-t 0.1 - about 95 % by weight, preferably about 0.5 - about 90 % by weight.
On actual use, the aetive compound levels in the aforesaid various preparations and ready-to--use preparations ean be appropriately varied, for example, in the range of about 0.0001 -about 20 % by weight, preferably about 0.005 - about 10 % by weight.
The levels of these aetive ingredients may be appropri-ately ehanged depending on the form of the preparation, the method, purpose, time and place of applieation, the severity of the erop diseases e-tc.
The compounds of formula (I) may, if necessary, be used in the co-presence of o-ther agricultural chemicals, such as insecticides, fungicides, acaricides, nematoeides, antiviral agents, herbicides, plant growth regulators, attraetants [for example, organic phosphate compounds, carbamate eompounds, dithio (or thiol) earbamate compounds, organic chlorine compounds, dinitro eompounds, organic sulfur or metal eompounds, antibiotics, substituted diphenyl ether eompounds, urea eompounds, triazine compounds ete.], and/or fertilizers and the like.
The various preparations or ready-to--use prepara-tions eontaining the aforesaid aetive ingredien-ts can be applied using a eommon application method sueh as spraying [for example, liquid spraying, misting, atomizing, dusting, granule-seattering, water surfaee applieation, pouring ete~]; fumigation; soil applieation [for example, ineorporating, sprinkling, vaporing, infusion ete.];
surfaee applieation [for example, eoating, banding, powder eoating, eovering ete.]; impregnation and the like. In addition they ean also be used by the so-ealled ultra-low-volume method. In this ~'~k method, it is possible ior the composition to comprise even 100 %
of the active ingredient.
The dosage applied per unit area is about 0.03 - about 10 kg, preEerably about 0.3 - about 6 kg, calculated as the active compound, per hectare. However, in special cases, it is possible or even sometimes necessary to apply a dosage higher or lo~er than the above range.
Thus agricultural or horticultural fungicidal composi-tions are provided which comprise the active compounds of the above formula (I) as active ingredients and diluents (solvents and/or fillers and/or carriers) and/or surfactants, and, if necessary, e.g. stabilizers, stickers and synergists.
Further there is provided a method for controlling crop diseases which comprises applying the compound of the above formula (I) either alone or in admixture with a diluent (solvent and/or filler and/or carrier) and/or surfactan-t, and, if necessary, e.g~ a stabilizer, a sticker and a synergist.
This invention and that of the copending parent application mentioned above are more particularly described by the following examples but the inventions should in no way be restricted thereto.
A. Preparative Examples Example 1:
[Example of Synthesis of Cornpound of Formula (II) of Invention]

7~

Cl ~ C'!~
' ~
(Compound No. II-1) 35 g of 4-chlorobenzylamine was dissolved in 250 ml of toluene, and while stirring the solution with ice-cooling, a solution of 20 g of 3- bromocyclohexene in 20 ml of toluene was added dropwise. After the addition, the temperature was gradually raised, and stirring was further continued at 50C for about 5 hours. After cooling, the reaction mixture was filtered by suction, and the toluene layer was washed thoroughly with water. The toluene solu-tion was dried on anhydrous sodium sulfate, the toluene was distilled off, and the residue was distilled under reduced pressure to obtain 15 g of the desired product, N-4-chlorobenzyl-2-cyclohexen-1-ylamine.
b.p. 134 - 138C/0.55 mm Hg.
The compounds of the formula (II) (intermediates) of this invention synthesized by procedures similar to those in Example 1 are given in Table 1.

Nit-157

3~4~

Table 1 , . . ~
Co~cund Co~"ound o~ For~ula (II) of Inv~ntlon .~;o. ~Inter~.ediate) ~'-4 ~hlorobenzyl-2-cyclopentenyla-.ine b.p. 13~ - 137C/l. r.L~ ~g II-3 ~4 ~ro.~obenzyl-2-cyclor,en~enylamine b.p. 147 ~- 152C/~.5 F.~. }Ig II-4 N-4-~ethylbenzyl-2-cyclopentenyla~ine b.p. 120 - 121C/105 ~ ~'9 II-5 h-4-~ethylbenzyl-2-cyclchexen~ .ine b.p. 137 - 142C/1.5 ~.~. Hg II 6 ~-4-~rc~.okenzyl-2-cyclohe~enyla,~ine bop~ 157 ~ 160C/0~ mm ~g II-7 N-4-Chlorobenzyl-3-cyclopentenylamine ~ r~-4-3~omobenzyl-3-cyclopentenyla~ine II-9 ~;-4-Chlorobenz~l 3-cyclohexenyla.-,~ine II-10 N-4-~'ethylbenzyl-3-cyclohexenylamine II-ll ':-4-Chlorobenzyl 2-cyclohe~tenyl~.ine Nit-157 7~

Example 2:
[Example of Synthesis of Compound of Formula (I)]

Cl ~ - CH2 - N - C - NH - CH2CH2CH3 (Compound No. 1) 22 g of N-4-chlorobenzyl-2-cyclohexenylamine was dissolved in 400 ml of hexane, and while stirring the solution with ice-cooling, a solu-tion of 9 g of propyl isocyanate in 30 ml of hexane was added dropwise. After the addition, the temperature was gradually raised, and stirring was further continued at 40C for about 3 hours. After cooling, the formed crystals were filtered off by suction, and recrystallized from a mixed solvent of hexane - ethyl alcohol to obtain 26.3 g of the desired product, l-(4-chlorobenzyl)-1-(2--cyclohexenyl)-3-propylurea.
m.p. 80.0 - 83.0C.
Example 3:
[Example of Synthesis of Compound of Formula (I)]

Br ~ CH2 -- N - C - NH - ~

(Compound No. 2) 19 g of aniline was dissolved in 400 ml of toluene, and while stirring the solution with ice-cooling, a solution of 31 CJ of N--4--bromobenzyl--N-(2--cyclopentenyl)carbamoyl chloride in 50 ml of toluene was added dropwlse. After the addition, the temperature was gradually raised, and stirring was further continued at 70 80C for about 10 hours. After cooling, the crystallized aniline hydrochloride was filtered off, and the toluene layer was washed successively with water, a 1 % aqueous sodium carbonate solution, a 1 % aqueous hydrochloric acid and water. After washing, the toluene solution was dried on anhydrous sodium sulfate, the toluene was distilled off; and the residue was recrystallized from a mixed solvent of hexane - ethyl alcohol to obtain 26.7 g of the desired product, 1-(4-bromobenzyl)--1-(2-cyclopen-tenyl)--3-phenylurea.
m.p. 106 0 - lll.O~C.
The compounds of the formula (I) synthesized by procedures similar to those in Examples 2 and 3 are given in Table 2.

Tahle 2 X~- CH2 -- N -- C -- ~H -- R2 . . . .
Co,~pou n~ 1 2 l~io . X R R Y Phy s i ca 1 cons tan t , ............ _ 1~, C
3 4-Cl ~a -CH3 O 82.0 - 88,0

4 4-Cl ~1 C2H; 88.5 - 90.5 4-C1 ~1 -C3H7-n O 71.0 - 76.0 6 4-Cl ~1 -C,~Hg-n O 53 . O - 55 . 5 7 i-C1 ~1 {~ ~ 101.0 - 104.0 4-Cl ~1 OC1~3 O 110.0 - 111.5 4-C1 ~1 ~ O 103.0 - 106.0 4-Br ~1 -CH3 O 7 4 . O - 7 6 .

11 ~-Be ~1 -C2~5 0 83 . 0 - 86 . 0 12 ~-i3r ~1 -C3~7-iso o 63 . O - 68 0 0 13 4 -CH3 ~1 -C 2~5 0 91. 0 93 . O

14 4-CH3 ~1 _C3TI7 n 75.0 - 80.0 ~ _ ~1 -C d~ ~ .~ _ 9 5 . 5 -- 9 6 . 5 Nit-1 57 -~2~7~1 =~DOU nd~~ - -~
~o. ¦ X _ _ _ y I Phys cal con~tant 16 4--Cl V --CH3 O 105.0 -- 106.0 17 4-Cl {> -C 2R 5 o 9 6 , O - 98 . O

18 4-Cl ~ ~ n O 62.0 - 64.0 19 ~-Cl ~ ~ 0 95,0 - 97.0 2~ 4-Cl ~> OC~3 13105 - 132.5 21 4~ C> 4~ ~ 92.Q - g6.0 2 2 4-Br ~ -C3 ~7 -n 07 ~ . 0 - a o . o 2~ 4-Br ~> ~ O13 0 . O - 131 0 0 2~ 4--CF33 ~ C2H5 0 68~0 - 71.0 4-CH3 ~) ~3~7-n OS9 . O - 63 . O

26 4-CH3 ~) OCH~ O9l . O - 9 4 ~ 5 27 4-C~13{> ~ O 100.0 - lO~.0 2~ ~-Cl ~a ~2'~5 S ~ . 5 - lO0 . O

29 4~1 {~ ~ S 130.0 - 133.0 3G 4-~r ~1 __ S 111 o O ~ 11 8 ~ 0 Nit-1 57 Compound I _ Physical cons-tant No. X R R Ymp. ~C
31 4-Br ~ ~ S136.0 - 141.0 32 4-CH3 ~ -C4Hg-n S52.G - 54.0 33 4-Cl ~ -C2H5 S96.0 - 97.5 34 4-Cl ~ ~ S129.0 - 132.5 4-CH3 ~ -C~H5 587.5 - 88.5 Further, the followin~ compounds of the formula (I) were synthesized by procedures similar to those in Example 2:
1-(4-chlorobenzyl)-1-(2-cyclopentenyl)---3-(3-hydroxyphenyl) urea, 1--(4-chlorobenzyl)--1-(2-cyclohexenyl)-3-(4--hydroxyphenyl) urea, 1-(4-chlorobenzyl)-1-(2-cyclohexenyl)-3-(4-methoxyphenyl) urea, 1-(4-chlorobenzyl)-1-(3-cyclopentenyl)-3-phenylurea, 1~(4-chlorobenzyl)-1-(3-cyclohexenyl)--3-propylurea, 1-(4-chlorobenzyl)--1--(2-cycloheptenyl)--3-phenylurea.

- 2~ ---The preparations of the compounds and the biological tests on them are specifically illus-trated by the following examples. Compound Nos. correspond to the above.
B. Formulation Examples Example 4 (Wettable Powder) 15 Parts of Compound No. 1, 80 parts of a 1 : S mixture of powdered diatomite and powdered clay, 2 parts of sodium alkylbenzenesulfonate and 3 parts of a condensate of sodium alkylnaphthalenesulfonate and formalin were ground and mixed together to prepare a wettable powderO It is diluted with water and applied by spraying to pathogenic fungi and/or sites where they are breeding and crop diseases were broken out.
Example 5 (Emulsifiable Concentrate) 30 Parts oE Compound No. 2, 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate were mixed wi-th stirring to prepare an emulsifiable concentrate. It is diluted with water and applied by spraying to pathogenic fungi and/or sites where they are breeding and crop diseases were broken out.
Example ~ (Dust) 2 Parts of Compound No. 3 and 98 parts of powdered clay were ground and mixed together -to prepare a dust. It is dusted over pathogenic fungi and/or sites where they are breedin~ and crop diseases were broken out.

Example 7 (Dust) 1.5 Parts of Compound No. 4, 0.5 part of isopropyl hydrogen phosphate (PAP) and 98 parts of powdered clay were ground and mixed t~gether to prepare a dust. It is dusted over pathogenic fungi and/or sites where they are breeding and crop diseases were broken out.
Example 8 (Granules) 25 Parts of water were added to a mixture of 10 par-ts of Compound No. 5, 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of llgnin sulfonate, intimately kneaded and pelletized using an extruding granulator to obtain granules of 10 - 40 mesh, which were then dried at 40 - 50~C to prepare granules. They are applied by scattering to pathogenic fungi and/or sites where they are breeding and crop diseases were broken out.
Example 9 (Granules) 95 Parts of clay material particles having a particle size distribution of 0.2 - 2 mm were charged into a rotary mixed and

5 parts of Compound No. 6 dissolved in an organic solvent was sprayed over it while rotating to be uniformly absorbed, thereby preparing granules. They are applied by scattering to pathogenic fungi and/or sites where they are breeding and crop diseases were kroken out.

Example 10 (Oil Preparation) 0.5 Part of Compound No. 7 and 99.5 parts of kerosene were mixed with stirring to prepare an oil preparation. This is applied by spraying to pathogenic fungi and/or sites where they are breeding and crop diseases were broken out.
C, Use Exam~
Example 11 Test on Effect to Control Pellicularia sasakii by Spraying (Pot Test) Preparation of Test Formulations Active Compound: 50 parts by weigh-t, Carrier: 45 parts by weight of a 1:5 mixture of diatomite and kaolin, Emulsifier: 5 parts by wieght of polyoxyethylene alkyl phenyl ether.

The above active compound, carrier and emulsifier in amounts specified above were ground and mixed to prepare a wettable powder, and a predetermined amount thereof was diluted with water to prepare a formulation.

Testing Method Rice plants (brand name: Kinmaze) were grown in Wagner pots of 1 a/5000 under the full water conditions, and at the young ear formation stage, the formulation of the active compound prepared above and diluted to the pre-determined con~entration was sprayed at a rate of 100 ml per 3 pots. The following day, the test rice plants were inoculated at the bottom of stems with Pellicularia sasakii which had been cultured in a barley medium for 10 days to form sclerotia, and allowed to infected by maintaining them in a wet chamber at 28 - 30C and a relative humidity of 95 ~ or higher for 10 days, after which the degree of attack and the presence of phytotoxicity were examined. The exa-mination was done by ~easuring the expansion of the lesion from the inoculation site at the root and the degree of damage was expressed by the ~ollowing standard.

3n3 + 2n2 ~ n1 ~ nO
Degree of Damage = _ x 100 wherein N: To~al number of the examined stems nO: Number of stems free from infection Nit-157 ~4~

n1: Number of stems infected up to the first-leaf leave sheath lfrom below) n2: Number of stems infected up to the second-leaf leave sheath (from below) n3: Number of stems infected up to the third-leaf leave sheath or above (from below) in this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following compound No.~ 1, 2, 5, 6, 7, 8, 9, 15, 16, 17, 18, 19, 20, 21, 22, 23, 26, 27, 29, 31, 33 and 34.

Nit 157 Table 3 Co~ oundConcentration o De~ree of . .
~o ~Ac t i ve Ing E ed i en t ~a~nag ~ Phy totox ic i ty _ ~pm % __ ~

6 250 0

7 250 0 ~5 50 O

l~ 50 0 29 5~ 0 31 50 ~
33 25û a . _. . . ___ __ o _ _ X-l 250 - 80~5 (Co,np~r~ t ive Co.TIoound 3 X 2 250 80 . 0 (Co~n2ar ative Compound ) X-3 250 73.5 ~Co~?~rative Co.~ound ) polyo:~ i n ~ 5 2 2 . 5 (CO;ll;~U~ r C i a 1 ~rac;uct C,ontrol) vali ~a.nycin ~ 60 lS
~Co:nnercial Procluct Control) No TrPatlnen t _ 31~5 . _ Nit-1 57 Notes:

1) X-1 (Comparative Compound) S

C~3~ C_2~_c2~5 (Compound described in U.S.
Patent No. 3,701,807 ~ specification) X-2 (Comparative Compound) o c~3-~a-c-~H ~ (Same as above) X-3 lComparative Compound) C~ C-~ ~ (Compound falling in the scope ~=~/ 2 j ~ ~ of the general formula des-cribed in U.S. Patent No.
~ 3,701,807 specification) polyoxin: polyoxin compound zinc salt (2.2 ~ liquid preparation of polyoxin D-Zn) validamycin A: 3 % liquid preparation of vali-damycin A

2~ In the table, the "-" in the Phytotoxicity column means the absence of phytotoxicity.

Nit-157 ~7~

Example 12 Test on Effect to Control Rhizoctonia solani (in Greenhouse) This example shows the results of the test on the effect to controlling soil-borne causative pathogenic fungi, Rhizoctonia solani which causes damping-off of seedlings of various crop plants by soil treatment.

Preparation of Test Formulations 3 Parts by weight of the active compound and 97 parts by weight of talc were ground and mixed together.

Testing Method Infected soil was prepared hy inoculating field soil (clay loam) which had been sterilized in an autoclave, with Rhizoctonia solani which has been cultured in a wheat bran medium for 10 days, and the dust preparation prepared above was incorporated into the soil to the predetermined concentration and well stirred to treat it. This chemical-treated soil and non-treated soil for comparison were packed into plastic containers of 27 x 18 cm2 in area and 9 cm in depth to m~ke nurseries respectively, then seeds of cucumber and egg plant were sown in each box, 50 seeds per box, allowed to germinate by maintaining in usual manner in a greenhouse, and the number of the infected seedings and the phytotoxicity to the germination and growth were examined at the predetermined intervals. According to the test results on the day 25, Compounds Nos. 1, 2, 20, 23 and 26 manifested a controlling effect of nearly 100% against damping-off o~ cucumber and egg plant at a concentration of the active ingredient of 25 ppm.

Nit-157

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A substituted benzyl-cycloalkenylamine of the formula (II) (II) in which X is a halogen atom or a lower alkyl group; and R1 is a cycloalkenyl group.

2. A substituted benzyl-cycloalkenylamine according to claim 1, in which X is a halogen atom or a lower alkyl group with 1 to 6 carbon atoms, and R1 is a cycloalkenyl group with 5 to 7 carbon atoms.

3. A substituted benzyl-cycloalkenylamine according to claim 1, in which X is a fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl, and R1 is 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2-cyclohepten-1-yl or 3-cyclohepten-1-yl.

4. A compound of formula (II) as defined in claim 1, wherein X is chlorine, bromine or methyl and R1 is cyclohexenyl or cyclopentenyl.

5. A process for preparing a compound of formula (II) as defined in claim 1, which process comprises:

a) reacting a substituted benzylamine of the formula:

(VI) wherein X is as defined in claim 1 with a compound of the formula:

R1 - Hal (VII) wherein R1 is as defined in claim 1 and Hal is a halogen atom; or b) reacting a substituted benzyl halide of the formula:

(VIII ) wherein X and Hal are as defined above with a cycloalkenylamine of the formula:
R1 - NH2 (IX) wherein R1 is as defined above.

6. A process according to claim 5, wherein reaction a) or b) is effected with a diluent, an acid binder at a temperature of from -20°C to the boiling point of the reaction mixture.

7. A process according to claim 5 or 6, wherein in the starting materials X is a halogen atom or a lower alkyl group with 1 to 6 carbon atoms, and R1 is a cycloalkenyl group with 5 to 7 carbon atoms.

8. A process according to claim 5 or 6, wherein in the starting materials X is a fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl, and R1 is 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2-cyclohepten-1-yl or 3-cyclohepten-1-yl.

9. A process according to claim 5 or 6, wherein in the starting materials X is chlorine, bromine or methyl and R1 is cyclohexenyl or cyclopentenyl.

10. The compound N-4-chlorobenzyl-2-cyclopenten-1-ylamine.

11. The compound N-4-chlorobenzyl-2-cyclohexen-1-ylamine.

12. The compound N-4-bromobenzyl-2-cyclohexen-1-ylamine.

13. The compound N-4-methylbenzyl-2-cyclohexen-1-ylamine.