1,2,6-Triphenyl-4(1H)-pyridinone derivatives, and their use as fungicides

Abstract

New substituted derivatives of 1,2,6-triphenyl-4(1H)-pyridone are now provided, which are useful as fungicidal agent having practically valuable and improved fungicidal activities against a variety of phyto-pathogenic microorganisms, especially fungi and which show low toxicity to animals, including humans. These new compounds may be produced by different processes.

Description

SUMMARY OF THE INVENTION:

This invention relates to new 4(1H)-pyridinone derivatives, and more particularly, new 1,2,6-triphenyl-substituted 4(1H)-pyridinone derivatives which are useful as new compounds or agents having improved fungicidal activities. This invention also relates to a fungicidal composition containing said new 4(1H)-pyridinone derivatives as active ingredient. This invention further relates to processes for the production of said new 4(1H)-pyridinone derivatives.

An article of the "Synthetic Communications" 13(5), 411-417 (1983) describes a process for the production of 1,2,6-triphenyl-substituted 4(1H)-pyridinone derivatives by reactions between ketimines and ethyl phenylpropionate, and this article discloses some examples of the 1,2,6-triphenyl-substituted 4(1H)-pyridinone derivatives produced, which are merely described there to be interesting as intermediate compounds for synthetic production of other, final products. On the other hand, Japanese patent application first publication "Kokai" No. 65871/81 discloses 1-phenyl-2,6-dimethyl-4(1H)-pyridinone derivatives. It also contains a disclosure to the effect that these derivatives are not only effective for cucumber powdery mildew (Sphaerotheca fuliginea) but also useful as slime control agents. Similarly, Japanese patent application first publication "Kokai" No. 102504/80 discloses 2,6-diphenyl-4(1H)-pyridinone and contains a description to the effect that this compound is effective for rice blast (Pyricularia oryzae) and cucumber anthracnose (Colletotrichum lagenarium). 3-Substituted phenyl- or 3,5-disubstituted phenyl-4 -pyridinone derivatives are also disclosed in Japanese patent application second publication "Kokoku" No. 350/85 and No. 351/85, and these compounds have activities as herbicides but no description is given there as to their fungicidal effects.

The above article in the "Synthetic Communication" does not describe anything about the biological activities of the compounds disclosed there. In order to provide a novel, agricultural and horticultural fungicide more useful than the known compounds described in the above-mentioned publications, we, the present inventors, have paid our attention on the 1,2,6-triphenyl-substituted 4(1H)-pyridinone derivatives and its skeleton structure and have carried out extensive investigations to provide their new 3-substituted derivatives. As a result, we have now succeeded to synthesize new compounds of this invention. It has also been found that the new compounds of this invention have improved and excellent activities as agricultural and horticultural fungicides, leading to completion of this invention.

DETAILED DESCRIPTION OF THE INVENTION

According to a first and broadest aspect of this invention, there is provided as new compounds 4(1H)-pyridinone derivatives represented by the general formula: ##STR1## wherein X, Y and Z are the same or different and are independently a halogen atom, a nitro group, a cyano group, a hydroxy group, aldehyde group (--CHO), an alkyl group, a halogen-substituted alkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a halogen-substituted alkoxy group, an alkoxyalkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an alkanoyl group, preferably formyl or acetyl, an alkanoyloxy group, preferably acetyloxy, a phenyl group, a phenoxy group, a carbamoyl group, an alkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or an alkyl group, or a substituted or unsubstituted amino group of the formula ##STR2## where R.sup.2 and R.sup.3 are the same or different and are each a hydrogen atom, a lower alkyl group, preferably methyl, or an alkanoyl group; or X, Y and Z are independently a group of the formula --(O).sub.p --S--R.sup.4 where R.sup.4 is an alkyl group and p is an integer of 0 to 3; or X, Y and Z are independently a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the benzene ring to which X, Y or Z is linking so that X, y or Z taken together with said two adjacent two carbon atoms of the benzene ring forms a 5-membered ring.

l, m and n are independently an integer of 0 to 5, R is a halogen atom, a cyano group, an alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, a phenyl group, a benzyl group, a trimethylsilylethynyl group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is as defined above, or a substituted methyl group of the formula --CH.sub.2 OR.sup.5 wherein R.sup.5 is a hydrogen atom, an alkyl group or a benzoyl group,

A is an oxygen atom or a sulfur atom, provided that when R is methyl and A is an oxygen atom, l, m and n do not denote zero simultaneously; and provided that when R and X are each a methyl group, A is an oxygen atom and l is l, m and n do not denote zero simultaneously, and a salt of the compound of the formula (I) above.

The compound of the formula (I) according to this invention may also be converted into their salts with an acid or a cation.

Further, the compounds of this invention may be in the form of such a tautomer as indicated below. ##STR3##

In the compounds of formula (I) according to this invention, R may preferably be an alkyl group, particularly a (C.sub.1 -C.sub.6) alkyl group, or a halogen atom, a cyano group or a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or an alkyl group. More preferably, R is a (C.sub.1 -C.sub.4) alkyl group, a chlorine atom or a bromine atom.

In the compounds of formula (I), X, Y and Z may preferably be the same or different and are independently an alkyl group, an alkoxy group, a halogen-substituted alkyl group, an alkoxy group, a halogen-substituted alkoxy group, a halogen group, nitro group, cyano group, an alkenyl group, an alkenyloxy group, an alkynyl group or an alkynyloxy group, or X, Y and Z are independently a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the benzene ring to which X, Y or Z is linking so that, X, Y or Z taken together with said two carbon atoms of the benzene ring forms a 5-membered ring; l, m and n are independently an integer of 0 to 5; and A is an oxygen atom or a sulfur atom.

In the compounds of formula (I), it is preferred that the sum of l, m and n is equal to 2 or greater than 2.

In the compounds of formula (I), two or more groups may be present for each of the groups X, Y and X and they are the same or different from each other in their nature.

In the compounds of formula (I), it is preferred that X is a halogen atom or an alkoxy group or a combination of halogen atom(s) and alkoxy group(s); Y is a halogen atom or an alkoxy group or a combination of halogen atom(s) and alkoxy group(s); and Z is a halogen atom or an alkoxy group or a combination of halogen atom(s) and alkoxy group(s).

In the compounds of formula (I), one, two or three groups for X may be present therein and may preferably be positioned at the 2-position, the 3-position, the 2- and 4-positions, the 2- and 5-positions, the 3- and 5-positions or the 2-, 3- and 5-positions of the benzene ring to which the group(s) X is or are linking.

In the compound of the general formula (I) according to this invention, an alkyl group as represented by the substitutents X, Y, Z, R, R.sup.1, R.sup.4 and R.sup.5, as well as a cycloalkyl group occasionally present in theses substituents X, Y, Z and others may be an alkyl group containing 1 to 6 carbon atoms, preferably an alkyl group containing 1 to 4 carbon atoms. The alkyl group may include a cycloalkyl group such as cyclopentyl. Suitable examples of an alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl. The halogen group includes bromine, chlorine, flourine and iodine.

According to particular embodiments of the first aspect of this invention, there are provided the following four types of the compounds:

(A) A compound represented by the general formula (Ia): ##STR4## wherein X.sup.a is a halogen atom, a nitro group, a cyano group, a hydroxy group, an alkyl group, a halogen-substituted alkyl group, a cyanoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a halogen-substituted alkoxy group, an alkoxyalkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an alkanoyl group, an alkanoyloxy group, a phenyl group a phenoxy group, a carbamoyl group, an alkylcarbamoyloxy group, a carboxyl or carbooxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or an alkyl group, or a substituted or unsubstituted amino group of the formula ##STR5## where R.sup.2 and R.sup.3 are the same or different and are each a hydrogen atom, a lower alkyl group, or an alkanoyl group; or X.sup.a is a group of the formula --(O).sub.p --S--R.sup.4 where R.sup.4 is an alkyl group an p is an integer of 0 to 3; or X.sup.a is a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the benzene ring to which X.sup.a is linking so that X.sup.a taken together with said two adjacent two carbon atoms of the benzene ring forms a 5-membered ring;

Y.sup.a is a halogen atom, a nitro group, a cyano group, a hydroxy group, an alkyl group, a halogen-substituted alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a halogen-substituted alkoxy group, an alkoxyalkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an alkanoyl group, an alkanoyloxy group, a carbamoyl group, an alkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or an alkyl group, or Y.sup.a is a group of the formula --(O).sub.p --S--R.sup.4 where R.sup.4 is an alkyl group and p is an integer of 0 to 3; or Y.sup.a is a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the benzene ring to which Y.sup.a is linking so that Y.sup.a taken together with said two adjacent two carbon atoms of the benzene ring forms a 5-membered ring, Z.sup.a is a halogen atom, a nitro group, a cyano group, a hydroxy group, aldehyde group (--CHO), an alkyl group, a halogen-substituted alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a halogen-substituted alkoxy group, an alkoxyalkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an alkanoyl group, an alkanoyloxy group, preferably acetyloxy, a carbamoyl group, an alkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or an alkyl group, or Z.sup.a is a group of the formula --(O).sub.p --S--R.sup.4 is an alkyl group and p is an integer of 0 to 3; or Z.sup.a is a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the benzene ring to which Z.sup.a is linking so that Z.sup.a taken together with said two adjacent two carbon atoms of the benzene ring forms a 5-membered ring, s is an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; and r is zero, 1 or 2. R.sup.a is a halogen atom, a cyano group, an alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, a phenyl group, a benzyl group, a trimethylsilylethynyl group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is as defined above, or a substituted methyl group of the formula --CH.sub.2 OR.sup.5 wherein R.sup.5 is a hydrogen atom, an alkyl group or a benzoyl group, provided that when R.sup.a is methyl, s, t and r do not denote zero simultaneously.

(B) A compound represented by the general formula ##STR6## wherein X.sup.b is a halogen atom or an alkoxy group or a combination of halogen atom(s) and alkoxy group(s); Y.sup.b is a halogen atom, especially chlorine or flourine, or an alkoxy group and Z.sup.b is a halogen atom, especially flourine,

s is an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; and r is an integer of zero, 1 or 2. R.sup.b is an alkyl group or a halogen atom, especially chlorine or flourine, provided that when R.sup.b is methyl, s, t, and r do not denote zero simultaneously.

(C) A compound represented by the general formula ##STR7## wherein X, Y and Z are the same or different and are independently a halogen atom, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group or an alkynyloxy group,

l, m and n are independently an integer of 0 to 5, R is an alkyl group or a halogen-substituted alkyl group.

(D) A compound represented by the general formula ##STR8## wherein X.sup.c is an alkyl group; Y.sup.c is a halogen atom, especially chlorine or flourine, an alkyl group, or an alkoxy group; and Z.sup.c is a halogen atom, especially flourine,

s in an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; and r is an integer of zero, 1 or 2. R.sup.c is an alkyl group or a halogen atom, especially chlorine or flourine, provided that when R.sup.c is methyl, s, t, and r do not denote zero simultaneously, and provided that t and r do not denote zero simultaneously.

Particular examples of the compounds of this invention represented by the general formula (I) will next be shown in Table 1a-Table 1d below. Compound numbers given in these Tables will be referred to in the subsequent descriptions.

TABLE 1a__________________________________________________________________________ ##STR9##Com-pound MeltingNo. Xl Ym Zn A R point(.degree.C.)__________________________________________________________________________1 2-Cl H H O CH.sub.3 228-2312 2-Cl " " " " 229-2313 3-Cl " " " " 219-2214 4-Cl " " " " 268-2705 2-F " " " " 221-2256 3-F " " " " 243-2467 4-F " " " " 256-2598 2-Br " " " " 201-2039 2-I " " " " 219-22210 2-C.sub.2 H.sub.5 " " " " 230-23411 2-C.sub.3 H.sub.7i " " " " 233-23612 4-C.sub.3 H.sub.7i " " " " 282-28413 4-C.sub.4 H.sub.9n " " " " 150-15114 4-C.sub.4 H.sub.9t " " " " 255-25715 2-OCH.sub.3 " " " " 179-18116 3-OCH.sub.3 " " " " 183-18517 4-OCH.sub.3 H H O CH.sub.3 237-23918 2-OC.sub.2 H.sub.5 " " " " 179-18219 3-OC.sub.2 H.sub.5 " " " " 206-20920 4-OC.sub.2 H.sub.5 " " " " 205-20821 2-OC.sub.3 H.sub.7i " " " " 177-18022 3-OC.sub.3 H.sub.7i " " " " 152-15423 4-OC.sub.3 H.sub.7i " " " " 222-22524 2-COOCH.sub. 3 " " " " 227-22925 2-COOC.sub.2 H.sub.5 " " " " 208-21126 3-COOC.sub.2 H.sub.5 " " " " 196-19827 4-COOC.sub.2 H.sub.5 " " " " 202-20428 2-OH " " " " >30029 3-OH " " " " >30030 4-OH " " " " >30031 ##STR10## " " " " 199-20332 2-NO.sub.2 " " " " 223-22533 3-NO.sub.2 " " " " 260-26234 4-NO.sub.2 " " " " 271-27335 2-CN " " " " 218-22236 3-CN " " " " 257-25937 4-CN " " " " 285-29138 2-NH.sub.2 " " " " >30039 3-NH.sub.2 " " " " 273-27740 4-NH.sub.2 " " " " >30041 2-NHCH.sub.3 H H O CH.sub.3 291-29342 ##STR11## " " " " 228-23343 2-SCH.sub.3 " " " " 228-23144 3-SCH.sub.3 " " " " 198-20145 4-SCH.sub.3 " " " " 237-23846 ##STR12## " " " 250-25347 ##STR13## " " " " No measurable48 ##STR14## " " " " 242-24449 2-SO.sub.2 CH.sub.3 " " " " 279-28150 3-SO.sub.2 CH.sub.3 " " " " 246-24851 4-SO.sub.2 CH.sub.3 " " " " 222-22552 2-CH.sub.2 CHCH.sub.2 " " " " 201-20453 2-CF.sub.3 " " " " 259-26154 3-CF.sub.3 " " " " 235-23755 4-CF.sub.3 " " " " 234-23756 3-CH.sub.2 OCH.sub.3 " " " " 155-15657 2-COCH.sub.3 " " " " ##STR15##58 3-COCH.sub.3 " " " " 201-20359 2-OCH.sub.2 CHCH.sub.2 " " " " 152-15560 3-OCH.sub.2 CHCH.sub.2 " " " " 170-17161 4-OCH.sub.2 CHCH.sub.2 " " " " 197-19862 2-CCH H H O CH.sub.3 187-19063 3-C CH " " " " 241-24564 4-CCH " " " " >30065 2-OCHF.sub.2 " " " " 196-20066 3-OCHF.sub.2 " " " " 167-16967 2-OC.sub.4 H.sub.9n " " " " 141-14468 3-OC.sub.4 H.sub.9n " " " " 121-12369 4-OC.sub.4 H.sub.9n " " " " 130-13470 2-CH.sub.2 CN " " " " >30071 4-OCF.sub.3 " " " " 235-23772 4-OCF.sub.2 CF.sub.2 H " " " " 151-15473 ##STR16## " " " " 236.5-23774 ##STR17## " " " " 234-23575 3-OCH.sub.2 CCH " " " " 166-16976 2,3-Cl.sub.2 " " " " ##STR18##77 2,4-Cl.sub.2 " " " " 257-26078 2,5-Cl.sub.2 " " " " 269-27179 2,6-Cl.sub.2 " " " " 232-23580 3,4-Cl.sub.2 " " " " 233-23581 3,5-Cl.sub.2 " " " " 253-25582 2,3-(CH.sub.3).sub.2 " " " " 212-21483 2,4-(CH.sub.3).sub.2 " " " " 217-22084 2,5-(CH.sub.3).sub.2 " " " " 268-26985 2,6-(CH.sub.3).sub.2 " " " " 197-20086 3,4-(CH.sub.3).sub.2 H H O CH.sub.3 222-22587 3,5-(CH.sub.3).sub. 2 " " " " 268-27188 2,3-(OCH.sub.3).sub.2 " " " " 198-19989 2,4-(OCH.sub.3).sub.2 " " " " 222-22590 2,5-(OCH.sub.3).sub.2 " " " " 197-19991 2,6-(OCH.sub.3).sub.2 " " " " 185-18792 3,4-(OCH.sub.3).sub.2 " " " " 230-23293 3,5-(OCH.sub.3).sub.2 " " " " 232-23694 2,3-F.sub.2 " " " " 210-21295 2,4-F.sub.2 " " " " 260-26196 2,5-F.sub.2 " " " " 216-21897 2,6-F.sub.2 " " " " 219-22198 3,4-F.sub.2 " " " " 228-22999 3,5-F.sub.2 " " " " 268-269100 2,3-Br.sub.2 " " " " --101 2,4-Br.sub.2 " " " " 256-259102 2,5-Br.sub.2 " " " " 285-287103 2,6-Br.sub.2 " " " " --104 2-Cl,6-CH.sub.3 " " " " 189-191105 2-Cl,4-NO.sub.2 " " " " 212-214106 2-Cl,5-NO.sub.2 " " " " 277-279107 2-Cl,4-Br " " " " 252-255108 2-Cl,5-CF.sub.3 " " " " 256-258109 2-Cl,5-CH.sub.3 " " " " 240-240.5110 2-CH.sub.3,3-Cl " " " " 244-246111 2-CH.sub.3,4-Cl H H O CH.sub.3 240-242112 2-CH.sub.3,5-Cl " " " " >300113 2-CH.sub.3,4-Br " " " " 235-237114 2-CH.sub.3,5-F " " " " 277.5-278115 2-NO.sub.2,4-Cl " " " " 220-223116 2-Br,4-CH.sub.3 " " " " 226-229117 2-F,5-NO.sub.2 " " " " 220-222118 2-OCH.sub.3,5-Cl " " " " 229-232119 2-OCH.sub.3,5-CH.sub.3 " " " " 215-216120 2-CF.sub.3,4-Cl " " " " 241-243121 2-CN,4-Cl " " " " ##STR19##122 3-Cl,4-CH.sub.3 " " " " 226-228123 3-Cl,4-F " " " " 224-225124 3-NO.sub.2,4-F " " " " 225-227125 3-NO.sub.2,4-Cl " " " " 247-248126 3-CF.sub.3,4-Cl " " " " 231-232127 3-CF.sub.3,4-OCH.sub.3 " " " " 205-208128 3-CH.sub.3,4-Br " " " " 225-227129 2-CH.sub.3,5-OCH.sub.3 " " " " 228-229130 2-CH.sub.3,3-OCH.sub.3 " " " " 231-233131 2-CH.sub.3,4-NO.sub.2 " " " " 248-249132 2-OCH.sub.3,4-NO.sub.2 " " " " 229-231133 2-OCH.sub.3,5-NO.sub.2 " " " " 224-225134 2-NO.sub.2,4-OCH.sub.3 " " " " 209-210135 2-Cl,5-OCH.sub.3 " " " " 224-225136 2-OCH.sub.3,6-CH.sub.3 H H O CH.sub.3 163-165137 2-CH.sub.3,3-F " " " " 267-268138 2-NO.sub.2,4-CH.sub.3 " " " " 253-255139 2-NO.sub.2,5-Cl " " " " 212-214140 2-CH.sub.3,5-NO.sub.2 " " " " >300141 3,5-(OH).sub.2 " " " " >300142 3,5-(OCHF.sub.2).sub.2 " " " " 179-181143 3,5-(OC.sub.2 H.sub.5).sub.2 " " " " 156-158144 3,5-(On-C.sub.3 H.sub. 7).sub.2 " " " " 156-158145 2-CH.sub.3,4-OCH.sub.3 " " " " 195-197146 2-OCH.sub.3,4-CH.sub.3 " " " " 217-219147 2-Cl,4-CH.sub.3 " " " " 222-224148 2-Cl,3-OCH.sub.3 " " " " 226-227149 2,4-Cl.sub.2,3-CH.sub.3 " " " " 237-238150 3,4,5-(OCH.sub.3).sub.3 " " " " 254-255151 2,4-Cl.sub.2,5-OC.sub.3 H.sub.7i " " " " 205-206152 2,3,4-Cl.sub.3 " " " " 257-258153 2,4-F.sub.2,3,5-Cl.sub.2 " " " " 243-245154 2-Cl,3,5-(OCH.sub.3).sub.2 " " " " 262-263155 2,3,4,5,6-F.sub.5 " " " " 192-194156 2,3,4,5-Cl.sub.4 " " " " 294-296157 2,3,4,6-Cl.sub.4 " " " " --158 2,3,5,6-F.sub.4 " " " " 220-222159 2-Cl " " " C.sub.2 H.sub.5 163-166160 " " " " Cl 230-233161 2-Br H H O Cl 238-241162 3-Cl " " " " 276-279163 4-Cl " " " " >300164 2-F " " " " 227-229165 2-I " " " " 238-239166 2-CH.sub.3 " " " " 266-268167 3-CH.sub.3 " " " " 271-273168 4-CH.sub.3 " " " " 292-296169 2-OCH.sub.3 " " " " 208-209170 3-OCH.sub.3 " " " " 250-251171 4-OCH.sub.3 " " " " 266-267172 2-NO.sub.2 " " " " 250-252173 3,5-(OCH.sub.3).sub.2 " " " " 275-276174 " " " " C.sub.2 H.sub.5 166-167175 2-Cl,5-OCH.sub.3 " " " " 175-176176 H 2-Cl " " CH.sub.3 221-225177 " 3-Cl " " " 225-227178 " 4-Cl " " " 209-212179 " 2-F " " " 177-180180 " 3-F " " " 226-228181 " 4-F " " " 239-244182 " 2-Br " " " 240-241183 " 2-Br " " " 236-238 (hydrochloride)184 " 3-Br " " " 237-239185 " 4-Br " " " 203-206186 H 2-I H O CH.sub.3 239-241187 " 2-CH.sub.3 " " " 194-196188 " 3-CH.sub.3 " " " 209-211189 " 4-CH.sub.3 " " " 243-246190 " 2-C.sub.3 H.sub.7i " " " 206-209191 " 4-C.sub.3 H.sub.7i " " " 194-197192 " 2-OCH.sub.3 " " " 200-202193 " 3-OCH.sub.3 " " " 201-204194 " 4-OCH.sub.3 " " " 183-185195 " 3-OC.sub.2 H.sub.5 " " " 146-149196 " 4-OC.sub.2 H.sub.5 " " " 189-193197 " 3-OC.sub.3 H.sub.7n " " " 137-139198 " 4-OC.sub.3 H.sub.7n " " " 165-168199 " 2-OC.sub.3 H.sub.7i " " " 212-214200 " 3-OC.sub.3 H.sub.7i " " " 161-163201 " 4-OC.sub.3 H.sub.7i " " " 198-201202 " 3-COOC.sub.2 H.sub.5 " " " 141-144203 " 4-COOC.sub.2 H.sub.5 " " " 99-103204 " 2-OH " " " >300205 " 3-OH " " " >300206 " 4-OH " " " >300207 " ##STR20## " " " 182-184208 " ##STR21## " " " 213-216209 " 3-CN " " " 262-265210 H 4-CN H O CH.sub.3 240-243211 " 2-SCH.sub.3 " " " 199-202212 " 4-SCH.sub.3 " " " 200-203213 " 2-CF.sub.3 " " " 238-241214 " 3-CF.sub.3 " " " 221-223215 " 4-CF.sub.3 " " " 209-211216 " 2-OCH.sub.2 CHCH.sub.2 " " " 145-148217 " 4-OCH.sub.2 CHCH.sub.2 " " " 196-199218 " 2-OCH.sub.2 CCH " " " 211-213219 " 4-OCH.sub.2 CCH " " " 168-170220 " 2-OCHF.sub.2 " " " 162-164221 " 3-COOH " " " 291-294222 " 2-C.sub.2 H.sub.5 " " " --223 " 2-C.sub.3 H.sub.7n " " " --224 " 4-OCH.sub.2 OCH.sub.3 " " " 188-190225 " 2,3-Cl.sub.2 " " " 274-278226 " 2,4-Cl.sub.2 " " " 183-185227 " 2,5-Cl.sub.2 " " " 264-267228 " 2,6-Cl.sub.2 " " " --229 " 3,4-Cl.sub.2 " " " 188-191230 " 3,5-Cl.sub.2 " " " 274-277231 " 2,3-(CH.sub.3).sub.2 " " " 250-254232 " 2,4-(CH.sub.3).sub.2 " " " 134-136233 " 2,5-(CH.sub.3).sub.2 " " " 215-217234 " 2,6-(CH.sub.3).sub.2 " " " --235 H 3,4-(CH.sub.3).sub.2 H O CH.sub.3 165-166236 " 3,5-(CH.sub.3).sub.2 " " " 237-239237 " 2,3-(OCH.sub.3).sub.2 " " " 230-235238 " 2,4-(OCH.sub.3).sub.2 " " " 192-194239 " 2,5-(OCH.sub.3).sub.2 " " " 242-244240 " 2,6-(OCH.sub.3).sub.2 " " " --241 " 3,4-(OCH.sub.3).sub.2 " " " 210-214242 " 3,5-(OCH.sub.3).sub.2 " " " 212-214243 " 2,3-F.sub.2 " " " 165-167244 " 2,4-F.sub.2 " " " 213-214245 " 2,5-F.sub.2 " " " 222-224246 " 2,6-F.sub.2 " " " 221-222247 " 3,4-F.sub.2 " " " 202-203248 " 3,5-F.sub.2 " " " 205-206249 " 4-OCHF.sub.2 " " " 165-166250 " ##STR22## " " " 232-235251 " 2-Cl,4-OCH.sub.3 " " " 205-206252 " H 2-Cl " " 201-204253 " " 3-Cl " " 234-236254 " " 4-Cl " " 173-175255 " " 2-F " " 219-222256 " " 3-F " " 204-206257 " " 4-F " " 184-186258 " " 2-Br " " 206-209259 H H 2-I O CH.sub.3 226-229260 " " 2-CH.sub.3 " " 188-191261 " " 3-CH.sub.3 " " 236-238262 " " 4-CH.sub.3 " " 212-215263 " " 2-C.sub.2 H.sub.5 " " --264 " " 2-C.sub.3 H.sub.7i " " 224-228265 " " 2-C.sub.4 H.sub.9n " " --266 " " 2-OCH.sub.3 " " 192-194267 " " 3-OCH.sub.3 " " 201-204268 " " 4-OCH.sub.3 " " 185-188269 " " 2-OC.sub.2 H.sub.5 " " 175-179270 " " 2-OC.sub.3 H.sub.7n " " 166-171271 " " 2-OC.sub.3 H.sub.7i " " 165-168272 " " 3-COOC.sub.2 H.sub.5 " " no measurable273 " " 4-COOC.sub.2 H.sub.5 " " 161-165274 " " 2-OH " " >300275 " " 3-OH " " >300276 " " 4-OH " " 262-268277 " " ##STR23## " " 115-122278 " " 3-NO.sub.2 " " 210-211279 " " 4-NO.sub.2 " " 213-216280 " " 2-CN " " 261-266281 " " 3-CN " " 211-214282 " " 4-CN " " 229-233283 H H 2-SCH.sub.3 O CH.sub.3 189-195284 " " 2-CH.sub.2 Cl " " 167-170285 " " 2-CF.sub.3 " " 200-205286 " " 3-CF.sub.3 " " 212-215287 " " 2-CH.sub.2 OCH.sub.3 " " 172-176288 " " 2-CH.sub.2 OC.sub.2 H.sub.5 " " 121-124289 " " 2-OCH.sub.2 CF.sub.3 " " 191-194290 " " 2-COCH.sub.3 " " --291 " " 2-OCH.sub.2 CHCH.sub.2 " " 171-174292 " " 2-OCH.sub.2 CCH " " 182-185293 " " 2-OCHF.sub.2 " " 163-165294 " " 2-COOH " " --295 " " 3-COOH " " >300296 " " 4-COOH " " >293297 " " 2-CH.sub.2 OH " " 254-257298 " " 2-CHO " " 169-173299 " " 2-SO.sub.2 CH.sub.3 " " >300300 " " ##STR24## " " 272-275301 " " 2-OSO.sub.2 CH.sub. 3 " " 209-214302 " " 2-O.sub.2 CNHCH.sub.3 " " >300303 " " 2-OCH.sub.2 OCH.sub.3 " " 178-181304 " " 2,3-Cl.sub.2 " " 183-191305 " " 2,4-Cl.sub.2 " " 218-221306 " " 2,5-Cl.sub.2 " " >300307 " " 2,6-Cl.sub.2 " " 151-154308 H H 3,4-Cl.sub.2 O CH.sub.3 234-236309 " " 2,3-(CH.sub.3).sub.2 " " 206-208310 " " 2,4-(CH.sub.3).sub.2 " " 175-178311 " " 2,5-(CH.sub.3).sub.2 " " 231-235312 " " 2,6-(CH.sub.3).sub.2 " " --313 " " 3,4-(CH.sub.3).sub.2 " " 212-215314 " " 3,5-(CH.sub.3).sub.2 " " 283-286315 " " 2,3-F.sub.2 " " 196-197316 " " 2,4-F.sub.2 " " 206-207317 " " 2,5-F.sub.2 " " 244-247318 " " 2,6-F.sub.2 " " 235-238319 " " 3,4-F.sub.2 " " 188-189320 " " 3,5-F.sub.2 " " 234-236321 " " 3,5-(OCH.sub.3).sub.2 " " 205-206322 " " 2,4-(OCH.sub.3).sub.2 " " 253-257323 " " 3,4-(OCH.sub.3).sub.2 " " 212-215324 " " 2-OC.sub.2 H.sub.5,4-F " " 236-237325 " " 2-OCH.sub.3,5-Cl " " 192-197326 " " 3,5-Cl.sub.2 " " >300327 " " 2-F,3-OCH.sub.3 " " 169-172328 " " 2-OCH.sub.3,5-F " " 185-186329 " " 2,6-(OCH.sub.3).sub.2 " " 206-210330 " " 2,3-(OCH.sub.3).sub.2 " " 239-243331 " " 3,4-(OH).sub.2 " " >300332 " " 3,5-(OH).sub.2 " " >300333 H H 3,4-(OCHF.sub.2).sub.2 O CH.sub.3 178-180334 " " 2,5-(OCH.sub.3).sub.2 " " 242-245335 2-Cl 2-Cl H " " 205-207336 " " " " " 232-234337 2-CH.sub.3 " " " " 197-200338 " " " " " 227-229339 " " " " " 222-225340 2-Cl 4-OCH.sub.3 " " " 184-188341 2-CH.sub.3 3-OCH.sub.3 " " " 212-213342 3-CH.sub.3 " " " " 195-196343 4-CH.sub.3 " " " " 182-183344 2-OCH.sub.3 " " " " 167-169345 3-OCH.sub.3 " " " " 153-155346 4-OCH.sub.3 " " " " 184-186347 2-CH.sub.3 3-Cl " " " 274-275348 3-CH.sub.3 " " " " 219-221349 4-CH.sub.3 " " " " 206-208350 2-OCH.sub.3 " " " " 231-233351 3-OCH.sub.3 " " " " 197-198352 4-OCH.sub.3 " " " " 206-207353 2-Cl 3-OCH.sub.3 " " " 212-213354 3-Cl " " " " 187-188355 4-Cl " " " " 189-191356 3-Cl 2-Cl " " " 196-198357 4-Cl " " " " 233-236358 3-CH.sub.3 2-Cl H O CH.sub.3 206-209359 4-CH.sub.3 " " " " 210-211360 2-OCH.sub.3 " " " " 173-176361 3-OCH.sub.3 " " " " 166-170362 4-OCH.sub.3 " " " " 186-188363 2-COOCH.sub.3 " " " " 180-182364 2-F " " " " 207-208365 " " " " " 201-203366 2-Br " " " " 117-120367 " " " " " 192-195368 2-NO.sub.2 " " " " 241-242369 " " " " " 233-235370 3-Cl 4-OCH.sub.3 " " " 199-203371 4-Cl " " " " 232-234372 2-CH.sub.3 " " " " 191-193373 3-CH.sub.3 " " " " 187-189374 4-CH.sub.3 " " " " 184-186375 2-OCH.sub.3 " " " " 248-260376 3-OCH.sub.3 " " " " 207-209377 4-OCH.sub.3 " " " " 212-214378 2-NO.sub.2 " " " " 235-237379 4-NO.sub.2 2-Cl " " " >300380 3-NO.sub.2 " " " " 193-195381 3-OCH.sub.3 2-CH.sub.3 " " " 145-148382 2-Cl " " " " 193-195383 4-CH.sub.3 2-CH.sub.3 H O CH.sub.3 203-204384 2-NO.sub.2 " " " " 246-248385 2,5-F.sub.2 2-Cl " " " 189-191386 2,3-Cl.sub.2 " " " " 237-239387 3,5-Cl.sub.2 " " " " 221-223388 3,5-(OCH.sub.3).sub.2 " " " " 226-229389 3,5-(OC.sub.2 H.sub.5).sub.2 " " " " 195-198390 3,5-(OCHF.sub.2).sub.2 " " " " 129-130391 3,5-(OH).sub.2 " " " " >300392 3,5-(OCH.sub.3).sub.2 4-OCH.sub.3 " " " 181-183393 " 3-Cl " " " 209-211394 2,5-F.sub.2 2-CH.sub.3 " " " 182-184395 2-CH.sub.3,3-Cl " " " " 230-231396 2,3-Cl.sub.2 " " " " 139-141397 3,5-(OCH.sub.3).sub.2 " " " " 202-203398 " 3-OCH.sub.3 " " " 207-209399 2-NO.sub.2 " " " " 204-208400 3,5-(OCH.sub.3).sub.2 2-OCH.sub.3 " " " 196-198401 3-OCH.sub.3 " " " " 170-172402 4-OCH.sub.3 " " " " 225-227403 4-CH.sub.3 " " " " 225-227404 2-Cl " " " " 223-226405 3-NO.sub.2 " " " " 180-184406 " 3-OCH.sub.3 " " " 240-244407 " 4-OCH.sub.3 " " " 255-260408 2,5-F.sub.2 4-OCH.sub.3 H O CH.sub.3 220-222409 2-Cl,5-OCH.sub.3 " " " " 225-236410 3-Cl 3-Cl " " " 243-244411 4-Cl " " " " 299-300412 2,5-F.sub.2 " " " " 230-233413 2-NO.sub.2 " " " " 273-275414 3-NO.sub.2 " " " " >300415 2-Cl 2-Br " " " 218-220416 " " " " " 225-227417 3-Cl " " " " 214-216418 4-CH.sub.3 " " " " 226-229419 3-CH.sub.3 " " " " 227-228420 2-CH.sub.3 " " " " 197-199421 4-Cl " " " " 224-226422 2-OCH.sub.3 " " " " 153-156423 3-OCH.sub.3 " " " " 147-150424 4-OCH.sub.3 " " " " 216-218425 3,5-(OCH.sub.3).sub.2 " " " " 224-226426 2,5-F.sub.2 " " " " 211-214427 " " " " " 211-213428 2-NO.sub.2 " " " " 220-224429 " " " " " 201-204430 3-NO.sub.2 " " " " 192-196431 2-Cl 2,4-F.sub.2 " " " 120-121432 " " " " " 198-199433 3,5-(OCH.sub.3).sub.2 2,4-F.sub.2 H O CH.sub.3 180-182434 " 3,4-F.sub.2 " " " 217-218435 2-Cl 4-CH.sub.3 " " " 230-233436 3-OCH.sub.3 " " " " 230-231437 3,5-(OCH.sub.3).sub.2 " " " " 223-225438 2-CH.sub.3 2-OCH.sub.3 " " " 188-191439 3-CH.sub.3 " " " " 183-185440 2-OCH.sub.3 " " " " 194-197441 2-NO.sub.2 " " " " 243-245442 3-Cl " " " " 213-215443 4-Cl " " " " 245-248444 2-Cl 4-Cl " " " 218-220445 2-Cl,3-OCH.sub.3 4-OCH.sub.3 " " " 222-223446 3,5-(OCH.sub.3).sub.2 " " " " 202-204447 2-F 2-Br " " " 220-223448 " " " " " 177-179449 2,3-Cl.sub.2 " " " " 249-251450 2-Cl,5-OCH.sub.3 " " " " 232-235451 2-Cl 2-F " " " 199-200452 " " " " " 203-204453 2-F " " " " 190-191454 " " " " " 188- 189455 3,5-(OCH.sub.3).sub.2 " " " " 218-219456 3-Cl 4-Cl " " " 239-241457 4-Cl " " " " 238-240458 2-CH.sub.3 4-Cl H O CH.sub.3 254-256459 3-CH.sub.3 " " " " 189-190460 4-CH.sub.3 " " " " 194-195461 2-OCH.sub.3 " " " " 226-228462 3-OCH.sub.3 " " " " 257-259463 4-OCH.sub.3 " " " " 261-266464 2-NO.sub.2 " " " " 238-239465 3-NO.sub.2 " " " " 228-229466 3,5-(OCH.sub.3).sub.2 2-Cl,4-OCH.sub.3 " " " 223-224467 2-CH.sub.3,5-OCH.sub.3 4-OCH.sub.3 " " " 229-231468 2-CH.sub.3,3-OCH.sub.3 " " " " 216-218469 3,5-(OCH.sub.3).sub.2 " " " C.sub.2 H.sub.5 170-171470 2-Cl,5-OCH.sub.3 " " " " 185-187471 2-Cl H 2-Cl " CH.sub.3 164-167472 " " 2-F " " 228-231473 " " 2-OCH.sub.3 " " 208-210474 2,6-F.sub.2 " 2-Cl " " 213-215475 3-Cl " " " " 234-237476 4-Cl " " " " 229-230477 2-CH.sub.3 " " " " 187-190478 3-CH.sub.3 " " " " 215-217479 4-CH.sub.3 " " " " 204-205480 2-OCH.sub.3 " " " " 184-189481 3-OCH.sub.3 " " " " 182-186482 4-OCH.sub.3 " " " " 197-200483 2-F H 2-Cl O CH.sub.3 188-190484 2-CN " " " " 217-219485 2-Cl " 3-NO.sub.2 " " 291-293486 2-NO.sub.2 " 2-Cl " " 217-219487 3-NO.sub.2 " " " " 195-196488 4-NO.sub.2 " " " " 290-295489 2,5-F.sub.2 " " " " 231-233490 3,5-(OCH.sub.3).sub.2 " " " " 239-241491 3-Cl " 2-F " " 224-226492 4-Cl " " " " 255-257493 2-CH.sub.3 " " " " 183-185494 3-CH.sub.3 " " " " 213-214495 4-CH.sub.3 " " " " 204-205496 2-OCH.sub.3 " " " " 201-202497 3-OCH.sub.3 " " " " 206-207498 4-OCH.sub.3 " " " " 225-226499 3,5-(OCH.sub.3).sub.2 " " " " 226-227500 2-Cl " 4-CH.sub.3 " " 232-233501 3-OCH.sub.3 " " " " 199-201502 2,5-F.sub.2 " 2-F " " 211-212503 2-Cl,5-OCH.sub.3 " " " " 191-192504 2-Br " " " " 218-219505 2-F " " " " 212-213506 2-Cl " 3-CH.sub.3 " " 213-215507 3,5-(OCH.sub.3).sub.2 " " " " 201-203508 2-F H 3-CH.sub.3 O CH.sub.3 211-214509 2,3-Cl.sub.2 " 2-F " " 217-218510 2-NO.sub.2 " " " " 213-214511 H 2-Cl 2-Cl " " 215-218512 " 4-OCH.sub.3 " " " 244-246513 " " 2-F " " 228-231514 2-Cl 2-Cl 2-Cl " " 205-207515 2-NO.sub.2 " " " " 189-193516 " " " " " 237-245517 2-Cl 4-OCH.sub.3 " " " 216-217518 3,5-(OCH.sub. 3).sub.2 " " " " 185-186519 2,5-F.sub.2 " " " " 206-209520 2-Cl " 2-F " " 204-207521 3,5-(OCH.sub.3).sub.2 " " " " 176-178522 H H H " Cl 285-287523 " " " " Br 274-277524 " " " " I 275-277525 " " " " C.sub.2 H.sub.5 173-176526 " " " " C.sub.3 Hn 158-160527 " " " " C.sub.4 H.sub.9n 101-103528 " " " " C.sub.3 H.sub.7i 181-184529 " " " " CH.sub.2 Cl 214-216530 " " " " CH.sub.2 Br no measurable531 " " " " CH.sub.2 OCH.sub.3 176-180532 " " " " CH.sub.2 OH 196-199533 H H H O COOH 257-259534 " " " " CN >300535 " " " " OCH.sub.3 188-191536 " " " " CF.sub.3 222-225537 " " " " COOC.sub.2 H.sub.5 184-187538 " " " " CH.sub.2 CHCH.sub.2 157-159539 " " " " ##STR25## 161-164540 " " " " ##STR26## 210-213541 " " " " ##STR27## 194-196542 2-Cl " " S CH.sub.3 271-275543 H " " " " 264-266__________________________________________________________________________ TABLE 1b__________________________________________________________________________Compound MeltingNo. Xl Ym Zn A R point (.degree.C.)__________________________________________________________________________544 2-Cl,5-OCH.sub.3 H 3-CH.sub.3 O CH.sub.3 202-205545 2-Cl 4-F H " " 235-242546 2-F " " " " 247-249547 3,5-(OCH.sub.3).sub.2 " " " " 202-204548 2-Cl, 5-OCH.sub.3 " " " " 203-206549 " 2,4-F.sub.2 " " " 184-186550 2-CH.sub.3, 4-OCH.sub.3 4-OCH.sub.3 " " " 179-182551 2-Cl, 3,5-(OCH.sub.3).sub.2 " " " " 230-232552 2-Cl ##STR28## " " " 237-239553 3,5-(OCH.sub.3).sub.2 " " " " 247-248554 H H 2-CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.3 " " 118-122555 2-Cl, 5-OCH.sub.3 " 2-CH.sub.2 OCH.sub.2 CH.sub.3 " " 183-184556 " 2-F H " " 223-224557 2-Cl, 3,5-(OCH.sub.3).sub.2 H 2-F " " 237-238558 3,5-(OCH.sub.3).sub.2 2-F " " " 193-194559 2-Cl, 5-OCH.sub.3 3-CH.sub.3 H " " 212-215560 " 2-Cl, 4-OCH.sub.3 " " " 209-211561 " " " " " 205-206562 " 4-CH.sub.3 " " " 238-239563 2,5-F.sub.2 " " " " 240-243564 2,3-Cl.sub.2 2,4-F.sub.2 " " " 165-167565 2,3-Cl.sub.2 2,4-F.sub.2 H O CH.sub.3 225-227566 2,5-F.sub.2 " " " " 216-218567 " " " " " 212-215568 2-Cl 3-Cl " " " 256-260569 2,3-Cl.sub.2 " " " " 253-255570 2-F " " " " 246-248571 3,5-(OCH.sub.2 CCH).sub.2 H " " " 157-159572 2-F 4-Cl " " " 235-238573 3,5-(OCH.sub.3).sub.2 " " " " ##STR29##574 2-Cl, 5-OCH.sub.3 2-Cl " " " ##STR30##575 " " " " " 229-230576 2-Cl, 3,5-(OCH.sub.3).sub.2 " " " " 256-258577 " " " " " 256-258578 2-CH.sub.3, 3-OCH.sub.3 " " " " 217-219579 2-CH.sub.3, 5-OCH.sub.3 " " " " 218-221580 4-Br, 3,5-(OCH.sub.3).sub.2 H " " " >300__________________________________________________________________________ TABLE lc__________________________________________________________________________Compound MeltingNo. Xl Ym Zn A R point(.degree.C.)__________________________________________________________________________581 H 2-F,4-OCH.sub.3 H O CH.sub.3 210-212582 " 2-CH.sub.3,4-OCH.sub.3 " " " 180-182583 " 2-Cl 2-F " " 177-179584 " 4-F " " " 229-232585 " 2-Cl,4-OCH.sub.3 " " " 206-209586 2-Cl,4-OCH.sub.3 H H " " 213-215587 2-F,5-OCH.sub.3 " " " " 191-193588 2-Br,3,5-(OCH.sub.3).sub.2 " " " " 264-265589 2,3,4-F.sub.3 " " " " 209-210590 2-Cl,3,5-(OCH.sub.3).sub.2 " " " C.sub.2 H.sub.5 168-170591 2-F,5-OCH.sub.3 " 2-F " CH.sub.3 173-176 206-210592 2-Br,3,5-(OCH.sub.3).sub. 2 " " " " 234-237593 2-Cl,5-OCH.sub.3 " 2-Cl " " 186-188594 2-Cl,3-OCH.sub.3 2-Cl H " " 270.5-271.5595 " " " " " 238-240596 2-Br,3,5-(OCH.sub.3).sub.2 " " " " 243.5-245.5597 " " " " " 227-230598 3-O--C.sub.3 H.sub.7 -i " " " " 162-164599 2-F,5-OCH.sub.3 " " " " 185-188600 " " " " " 169-174601 2-Cl,5-OCH.sub.3 2-Br " " " 185-194602 2-Cl,3-OCH.sub.3 4-Cl H O CH.sub.3 212-215603 2-Cl,5-OCH.sub.3 " " " " 243-245604 2-Cl,3,5-(OCH.sub.3).sub.2 " " " " 245-247 240-243605 " 2-F " " " 247-250606 " " " " " 242-243 242-246607 " 4-F " " " 250-253608 2-F 4-OC.sub.2 H.sub.5 " " " 186-188609 3-OCH.sub.3 " " " " 180-184610 2-Cl " " " " 168-170611 3,5-(OCH.sub.3).sub.2 " " " " 168-171612 2-Cl,5-OCH.sub.3 " " " " 179-182613 2-Br,3,5-(OCH.sub.3).sub.2 4-OCH.sub.3 " " " 248-250614 2-F 4-OCH.sub.2 C.tbd.CH " " " 158-161615 3-OCH.sub.3 " " " " 173-175616 3,5-(OCH.sub.3).sub.2 " " " " 170-171617 2-Cl,3,5-(OCH.sub.3 ).sub.2 2,4-F.sub.2 " " " 226-230618 " " " " " 216-218619 " 2-Cl,4-OCH.sub.3 " " " 240-243620 " " " " " 233-235621 2-CH.sub.3,3-OCH.sub.3 " " " " 266-269622 " " " " " 205-207623 3,5-(OCH.sub.3).sub.2 2-CH.sub.3,4-OCH.sub.3 " " " 215-217624 " 2-F,4-OCH.sub.3 " " " 162-163625 2-Cl,3,5-(OCH.sub.3).sub.2 4-OCH.sub.3 2-F " " 232-235626 2-Cl,5-OCH.sub.3 4-OCH.sub.3 2-F O CH.sub.3 243-247627 2-Cl,3,5-(OCH.sub.3).sub.2 2-Cl " " " 256-257 213-215628 " " " " " 235-236629 2-Cl,5-OCH.sub.3 " " " " 200-201630 " " " " " 207-208631 2-Br,3,5-(OCH.sub.3).sub.2 " " " " 237-239632 " " " " " 245-247633 3,5-(OCH.sub.3).sub.2 " " " " 184-185634 2-Cl,3,5-(OCH.sub.3).sub.2 2-F " " " 252-254635 " " " " " 251-253636 2-Cl,5-OCH.sub.3 " " " " 200-201637 " " " " " 184-186638 " 4-F " " " 194-198639 3,5-(OCH.sub.3).sub.2 " " " " 195-200640 2-Cl,5-OCH.sub.3 2,4-F.sub.2 " " " 183-185641 " " " " " 169-174642 3,5-(OCH.sub.3).sub.2 " " " " 170-171643 2-Cl,5-OCH.sub.3 2-Cl,4-OCH.sub.3 " " " 252-256644 " " " " " 210-212645 3,5-(0CH.sub.3).sub.2 " " " " 210-214646 2-Cl,3,5-(OCH.sub.3).sub.2 2,4-F.sub.2 " " " 238-240647 " " " " " 229-232__________________________________________________________________________ TABLE 1d__________________________________________________________________________Compound MeltingNo. Xl Ym Zn A R point (.degree.C.)__________________________________________________________________________648 H 2-Cl H O C.sub.2 H.sub.5 191-194649 " 4-OCHF.sub.2 " " CH.sub.3 165-166650 2-Cl, 5-OCH.sub.3 2,4-F.sub.2 " " " 184-186651 2-Cl, 3,5-(OCH.sub.3).sub.2 4-OCH.sub.3 " " " 230-232652 3,5-(OCH.sub.3).sub.2 H 2-CH.sub.2 OC.sub.2 H.sub.5 " " 159-160653 2-Cl 3-CH.sub.3 " " " 247-251654 2-F " " " " 228-231655 3,5-(OCH.sub.3).sub.2 " " " " 210-211656 H H 4-CH.sub.2 OCH.sub.3 " " 145-146657 ##STR31## " H " " >300658 2-F 4-OCH.sub.2 CCH " " " 158-161659 3,5-(OCH.sub.3).sub.2 2-F, 4-OCH.sub.3 2-F " " 103-105660 H 2-F " " " 180-183661 3-C.sub.3 H.sub.7 i H H " " 189-191662 ##STR32## " " " " 177-179663 3,5-(OCH.sub.3).sub.2 2,3-F.sub.2 " " " 227-229664 " 3,5-(CH.sub.3).sub.2 " " " 242-244665 " 2-F 2-F S " 226-228666 " 4-OC.sub.3 H.sub.7 H O " 149-150667 2-Cl, 5-OCH.sub.3 " " " " 189-190668 " H 3-F " " 236-239669 " " H " Cl 255-256670 " " 2-F S CH.sub.3 243-245671 ##STR33## " H O " ##STR34##672 ##STR35## " " " " 233-237673 2-Cl, 5-OCH.sub.3 H H S CH.sub.3 251-253674 H ##STR36## " O " 253-254675 3,5-(OCH.sub.3).sub.2 " " " " 195-196676 2-Cl,3,5-(OCH.sub.3).sub.2 " " " " 208-209677 " H 2-F S " 209-211678 3,5-(OCH.sub.3).sub.2 " " " " 241-243679 " 2,4-F.sub.2 " " " 216-217680 " H H " " 259-261681 2-Cl,5-OCH.sub.3 4-OCH.sub.2 CCH " O " 192-193682 H 4-OC.sub.4 H.sub.9 " O " 150-151683 2-Cl, 5-OCH.sub.3 " " " " 179-183684 3,5-(OCH.sub.3).sub.2 " " " " 118-119685 2-CH.sub.3, 3-OCH.sub.3 2,4-F.sub.2 " " " 208- 209686 H 2,4-F.sub.2 2-F " " 213-214687 " 2-F 2-Cl " " 196-200688 2-F, 4-Cl H H " " 216-218689 2-Cl, 4-F " " " " 268-269690 3,5-(OCH.sub.3).sub.2 " 2,3-F.sub.2 " " 218-219691 H " H " CCH 250-253692 " " " " CCSi 202-203 (CH.sub.3).sub.3693 3,5-(OCH.sub.3).sub.2 2-F 2-F " Cl 236-238694 ##STR37## H H " CH.sub.3 157-159695 2-NO.sub.2, 3,5-(OCH.sub.3).sub.2 " " " " ##STR38##696 2-Cl, 5-OCH.sub.3 2-Cl " S " 269-271697 2-Cl, 5-OCH.sub.3 2-Cl H S CH.sub.3 251-253698 2-Cl, 3,5-(OCH.sub. 3).sub.2 H " " " 255-258699 ##STR39## " " O " >300700 H 2,4-F.sub.2 2-Cl " " 193-194701 " H 2-F, 3-Cl " " 199-200702 " 2-F 2,4-F.sub.2 " " 182-183703 ##STR40## H H " " 283-284704 ##STR41## " " " " ##STR42##705 ##STR43## " " " " 188-189706 ##STR44## " " " " >300707 3-NHCH.sub.3 " " " " 282-283708 4-NHCH.sub.3 " " " " 248-249709 H ##STR45## " " " 262- 265710 3,5-(OCH.sub.3).sub.2 ##STR46## " " " 211-212711 H H ##STR47## " " 209-210712 " 2-Cl 2-F S " 196-199713 3,5-(OCH.sub.3).sub.2 4-OCH.sub.3 H " " 227-232714 " 2-Cl " " " 245-249715 H ##STR48## " O " >300716 H 2-F, 3-Cl H O CH.sub.3 216-217717 " 3,5-F.sub.2 " " " 205-206718 " 2-F 2-F " Cl 219.5-220719 3,5-F.sub.2 H H " CH.sub.3 268-269720 2-OCH.sub.2 CCH " " " " 165-167721 2-Cl, 5-NH.sub.2 " " " " >300722 ##STR49## " " " " >300723 ##STR50## " " " " 239-240724 2-Cl, 5-NHCH.sub.3 " " " " 235-237725 ##STR51## " " " " 203-205726 H " ##STR52## " " 181-183727 2-Cl, 5-OCH.sub.3 " " " " 183-185728 3,5-(OCH.sub.3).sub.2 " " " " 228-229729 H 2,3-(CH.sub.3).sub.2 H " " 250-254730 2-Cl H 2-CH.sub.3 " " 194-197731 2-Cl, 5-OCH.sub.3 " " " " 194-197732 3,5-(OCH.sub.3).sub.2 " " " " 215-217733 3-OCH.sub.3 2-F H " " 161-163734 " " 2-F " " 194-195735 3,5-(OCH.sub.3).sub. 2 " 2,4-F.sub.2 " " 210-212736 H 4-CH.sub.2 OCH.sub.3 H " " 174-175737 " 4-I " " " 253-255738 3-OCH.sub.3 2-F 2,4-F.sub.2 O CH.sub.3 169-171739 " 2-Cl 2-F " " 173-174740 2-Cl H 4-CH.sub.2 OCH.sub.3 " " 177-179741 2-Cl, 5-OCH.sub.3 " " " " 184-185742 3,5-(OCH.sub.3).sub.2 " " " " 160-162.5743 H 2-Cl 2-F " " 223-224744 ##STR53## H H " " 219-221745 2-Cl " ##STR54## " " 237-240746 H " 3-F, 4-OCH.sub.3 " " 180-181747 " 2,6-F.sub.2, 4-Br H " " 189-190748 H 2-Cl 2,4-F.sub.2 " " 165-168749 3,5-(OCH.sub.3).sub.2 " " " " 205-206750 H H 3,5-F.sub.2 " " 234-236751 " " 2,6-F.sub.2, 4-Br " " 210-215752 2, Cl, 4-NO.sub.2 4-F H " " 114-120753 ##STR55## H " " " 197-199754 ##STR56## " " " " 193-195755 2-Cl, 5-OCH.sub.3 ##STR57## " " " 244-246756 4-OCH.sub.2 CCH H " " " 263-265757 4-OC.sub.3 H.sub.7 " " " " 189-190758 ##STR58## " " " " 265-268759 H " 3,4-F.sub.2 " " 188-189760 H 2-F 2,3-F.sub.2 O CH.sub.3 151-153761 " 2-Cl " " " 206-207762 2-F, 5-NH.sub.2 H H " " 290-292763 2-CH.sub.3, 3-NO.sub.2 " " " " 241-242 5-OCH.sub.3764 H ##STR59## " " " 162-164765 2-Cl " " " " 156-160766 3,5-(OCH.sub.3).sub.2 " " " " 164-165767 H H 2-Cl, " " 235-236 3,5-(OCH.sub.3).sub.2768 2-Cl " " " " ##STR60##769 2-Cl, 5-OCH.sub.3 " " " " ##STR61##770 3,5-(OCH.sub.3).sub.2 " " " " 222-223771772 H 2-NO.sub.2 H " " 242-243773 " 3-NO.sub.2 " " " 244- 246774 " 4-NO.sub.2 " " " 206-207775 " H 2-NO.sub.2 " " 161-164776 2-Cl " " " " ##STR62##777 3,5-(OCH.sub.3).sub.2 " " " " 256-258778 H 2-Cl " " "779 " 2-F " " "780 2-Cl 2-NO.sub.2 H " "781 3,5-(OCH.sub.3).sub.2 2-NO.sub.2 H O CH.sub.3782 2-Cl 3-NO.sub.2 " " "783 3,5-(OCH.sub.3).sub.2 " " " "784 2-Cl 4-NO.sub.2 " " "785 3,5-(OCH.sub.3).sub.2 " " " "786 H 2-NO.sub.2 2-Cl " "787 " " 2-F " "788 3-OCH.sub.3 2-Cl 2,4-F.sub.2 " " 159-160789 3-OCH.sub.3 2,4-F.sub.2 H " " 168-169790 " " 2-F " " 136.5-138791 " " 2,4-F.sub.2 " " 137-138792 2,5-Cl.sub.2 H H " " 245-255 3-CF.sub.3793 3,5-(OCH.sub.3).sub.2 2-F 2-F " CH.sub.2 OC.sub.2 H.sub.5 189-191794 3,5-(OCH.sub.3).sub.2 " " " ##STR63## 88-91795 " " " " CH.sub.2 OH 162-164796 ##STR64## H H " CH.sub.3 252-253797 H H H " CH.sub.2 F 180-181__________________________________________________________________________

In Table 1a-Table 1d, when "H" is given in the columns of "X.sub.l ", "Y.sub.m " and/or "Z.sub.n ", this means that the value of l, m and/or n is or are zero, respectively.

In Table 1a, Compound 2 is a salt with 1/3 HCl, Compound 308 a salt with 1/2 HCl, and Compound 446 a salt with ##STR65##

Further, pairs of Compound 335 and Compound 336; Compound 338 and Compound 339; Compound 365 and Compound 364; Compound 366 and Compound 367; Compound 368 and Compound 369; Compound 415 and Compound 416; Compound 426 and Compound 427; Compound 428 and Compound 429; Compound 431 and Compound 432; Compound 451 and Compound 452; Compound 453 and Compound 454; and Compound 515 and Compound 516 are respectively in the relationship of atrop-isomers. Compound 337 is a mixture of isomers.

In Table 1b, pairs of Compound 560 and Compound 561; Compound 564 and Compound 565; Compound 566 and Compound 567; Compound 574 and Compound 575; and Compound 576 and Compound 577 are respectively in the relationship of atrop-isomers. Compound 580 showed the following spectrum peaks:-

IR spectrum (KBr, cm.sup.-1): 1620, 1230, 1020,

NMR spectrum (CDCl.sub.3, 8 ppm): 6.00 (2H, s), 6.58(1H, s), 7.00-7.40(10H, m).

In Table 1c, Compound 610 is a hydrate with 1/2 H.sub.2 O.

Further, pairs of Compound 594 and Compound 595; Compound 596 and Compound 597; Compound 599 and Compound 600; Compound 605 and Compound 606; Compound 617 and Compound 618; Compound 619 and Compound 620; Compound 621 and Compound 622; Compound 627 and Compound 628; Compound 629 and Compound 630; Compound 631 and Compound 632; Compound 634 and Compound 635; Compound 636 and Compound 637; Compound 640 and Compound 641; Compound 643 and Compound 644; and Compound 646 and Compound 647 are respectively in the relationship of atrop-isomers.

In Table 1d, a pair of Compound 696 and compound 697 is in the relationship of atrop-isomers. Further, Compound 695Compound 704 and Compound 776 include different crystalline forms, respectively.

Amongst the compounds of formula (I) according to this invention, the compounds of the formulae listed below are most preferred: ##STR66##

Next, some examples of the compounds of formula (I) of this invention were examined by certain analytical instruments to investigate their characteristic absorptions of the infrared absorption spectrum (IR spectrum) and nuclear magnetic resonance absorption spectrum (NMR spectrum). The results obtained are summarized in Table 2 below.

TABLE 2______________________________________Compound AnalyticalNo. method Characteristics______________________________________ IR-spectrum 2900- 2300, 1615 (KBr, cm.sup.-1)28 NMR-spectrum Not measurable due to insolubility in solvents IR-spectrum 2800- 2300, 1610 (KBr, cm.sup.-1)29 NMR-spectrum 1.73(3H,s), 6.30-6.85(6H,m), (DMSO--d.sub.6, .delta. ppm) 7.67(10H,s) IR-spectrum 1615, 1275, 1240 (KBr, cm.sup.-1)30 NMR-spectrum Not measurable due to insolubility in volvents Mass-spectrum 353 (M.sup.+) (m/z) IR-spectrum 1620 (KBr, cm.sup.-1) NMR-spectrum 1.63(3H,s), 5.20(2H.bs)38 (DMSO--d.sub.6, .delta. ppm) 5.90-6.90(5H,m), 7.00-7.63(10H,m) Mass-spectrum 352 (M.sup.+) (m/z) IR-spectrum 3420, 3300, 1620, 1275 (KBr, cm.sup.-1)40 NMR-spectrum Not measurable due to insolubility in solvents IR-spectrum 1610, 1050 (KBr, cm.sup.-1)47 NMR-spectrum 1.93(3H,s), 2.27(3H,s), (CDCl.sub.3, .delta. ppm) 6.57(1H,s), 6.90-7.30(14H,m) IR-spectrum 3200, 1620 (KBr, cm.sup.-1)64 NMR-spectrum 1.87(3H,s), 2.98(1H,s), (CDCl.sub.3, .delta. ppm) 6.49(1H,s), 6.60-7.20(14H,m) IR-spectrum 1625 (KBr, cm.sup.-1)112 NMR-spectrum Not measurable due to insolubility in solvents Mass-spectrum 385 (M.sup.+) (m/z) IR-spectrum 1625, 1520, 1350, 850 (KBr, cm.sup.-1)140 NMR-spectrum Not measurable due to insolubility in solvents Mass-spectrum 396 (M.sup.+) (m/z) IR-spectrum 3150, 1605, 1600-1440, (KBr, cm.sup.-1) 1160, 765, 700141 NMR-spectrum Not measurable due to insolubility in solvents IR-spectrum 1620 (KBr, cm.sup.-1)163 NMR-spectrum 6.70(1H,s), 6.80-7.47 (CDCl.sub.3, .delta. ppm) (14H,m) IR-spectrum 3500-3200, 1620 (KBr, cm.sup.-1)204 NMR-spectrum 1.77(3H,s), 6.23(1H,s), (CDCl.sub.3 /DMSO-d.sub. 6, 6.50-7.40(14H,m) .delta. ppm) IR-spectrum 3050, 1600, 1585-1480, (KBr, cm.sup.-1) 1290, 770, 700205 NMR-spectrum 1.90(3H,s), 6.50-7.50(16H,m) (CDCl.sub.3 /DMSO-d.sub. 6, .delta. ppm) IR-spectrum 3400, 1605 (KBr, cm.sup.-1)206 NMR-spectrum 1.76(3H,s), 6.24(1H,s), (DMSO-d.sub. 6, 6.40-7.50(14H,m) .delta. ppm) IR-spectrum 3120, 2980, 1720, 1615, (KBr, cm.sup.-1) 1270, 750272 NMR-spectrum 1.33(3H,t), 2.00(3H,s), 4.33 (CDCl.sub.3, .delta. ppm) (2H,q), 7.00-7.95(15H,m) IR-spectrum 3050, 1600, 1590-1440, (KBr, cm.sup.-1) 1280, 750, 690274 NMR-spectrum 1.80(3H,s), 6.30-7.30(16H,m) (CDCl.sub.3, .delta. ppm) IR-spectrum 3800-2200, 1620, 1295, 760 (KBr, cm.sup.-1)275 NMR-spectrum 1.66(3H,s), 6.30(1H,s), (DMSO-d.sub. 6, 6.50-7.40(15H,m) .delta. ppm) IR-spectrum 3050, 3000-2200, 1700, (KBr, cm.sup.-1) 1610, 770295 NMR-spectrum 1.90(3H,s), 6.90-7.90(16H,m) (DMSO-d.sub. 6, .delta. ppm) IR-spectrum 3400, 3200-1800, 1705, (KBr, cm.sup.-1) 1610, 1230296 NMR-spectrum 1.75(3H,s), 6.33(1H,s), (CDCl.sub.3 /DMSO-d.sub. 6, 7.00-8.20(15H,m) .delta. ppm) IR-spectrum 1620, 1305, 1150 (KBr, cm.sup.-1)299 NMR-spectrum 1.90(3H,s), 3.10(3H,s), (CDCl.sub.3, .delta. ppm) 6.80-8.00(14H,m), 8.40(1H,s) IR-spectrum 1615 (KBr, cm.sup.-1)306 NMR-spectrum 1.89(3H,s), 6.42(1H,s), (CDCl.sub.3 , .delta. ppm) 6.67-7.33(13H,m) IR-spectrumrm 1627 (KBr, cm.sup.-1)326 NMR-spectrum 1.87(3H,s), 6.45(1H,s), (CDCl.sub.3, .delta. ppm) 6.65-7.33(13H,m) IR-spectrum 3450, 1610 (KBr, cm.sup.-1)331 NMR-spectrum 1.76(3H,s), 6.25(1H,s), (DMSO-d.sub. 6, 6.40-7.50(13H,m) .delta. ppm) IR-spectrum 3300, 1600 (KBr, cm.sup.-1)332 NMR-spectrum 1.76(3H,s), 6.00(1H, bs), (CD.sub.3 OD/DMSO-d.sub. 6 6.25(1H,s), 6.80-7.20(10H,m) .delta. ppm) IR-spectrum 1620, 1550, 1350 (KBr, cm.sup.-1)379 NMR-spectrum 1.80(3H,s), 6.50(1H,s) (CDCl.sub.3, .delta. ppm) 6.80-7.80(13H,m) IR-spectrumn 3050, 1605, 1580-1430, (KBr, cm.sup.-1) 1150, 760, 700391 NMR-spectrum Not measurable due to insolubility in solvents IR-spectrum 1625, 1530, 1350, 855 (KBr, cm.sup.-1)414 NMR-spectrum Not measurable due to insolubility in solvents Mass-spectrum 416 (M.sup.+) (m/z) IR-spectrum 1620 (KBr, cm.sup.-1)530 NMR-spectrum 4.03(2H,s), 6.30(1H,s), (CDCl.sub.3, .delta. ppm) 6.60-7.90(15H,m) Mass-spectrum 415 (M.sup.+) (m/z) IR-spectrum 2230, 1630 (KBr, cm.sup.-1)534 Mass-spectrum 348 (M.sup.+), 320 (m/z)______________________________________

Descriptions will next be made of the production of the compounds of formula (I) according to this invention.

PROCESS (a)

The compounds of this invention may each be produced by reacting a 1,5-diphenylpentanetrions derivative represented by the general formula (II): ##STR67## wherein Y, Z, R, m and n have the same meanings as defined above, or a tautomer thereof, with an aniline derivative represented by the general formula (III): ##STR68## wherein X and l have the same meanings as defined above.

The tautomers of the above compound (II) are represented by the following formulae: ##STR69##

The trione derivative of the formula (II) above can usually be prepared by condensing a 1-benzoyl-1-methylacetone derivative with a benzoic ester derivative in a suitable solvent, for example, tetrahydrofuran, diethyl ether or dimethoxyethane in the presence of a base such as sodium hydride or sodium methylate added thereto.

For example, 1,5-diphenyl-2-methylpentane-1,3,5-trione can be prepared from 1-benzoyl-1-methylacetone and methyl benzoate. It is also possible to prepare 1-(2-chlorophenyl)-2-methyl-5-phenylpentane-1,3,5-trione from 1-(2-chlorobenzoyl)-1-methylacetone and methyl benzoate; 5-(2-chlorophenyl)-1-(4-methoxyphenyl)-3-methylpentane-1,3,5-trione from 1-(4-methoxybenzoyl)-1-methylacetone and methyl 2-chlorobenzoate; and 2-benzyl-1,5-diphenylpentane-1,3,5-trione from 1-benzoyl-1-benzylacetone and methyl benzoate.

In the Process (a), the reaction between the pentanetrione of the formula (II) or its tautomer and the aniline derivative of the formula (III) may be conducted generally by dissolving or suspending both the reactants in a suitable solvent, for example, a hydrocarbon such as benzene, toluene or xylene, a halogenated hydrocarbon such as chlorobenzene, methylene chloride or chloroform, an ether such as diisopropyl ether, tetrahydrofuran or dioxane, a ketone such as acetone, methyl ethyl ketone or cyclohexanone, an ester such as ethyl acetate, a nitrile such as acetonitrile, an amide such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, dimethylsulfoxide, acetic acid, or the like. As an alternative, the reaction may also be conducted without any solvent. It is however preferable to carry out the reaction by dissolving the reactants in xylene or chlorobenzene. Here, the reaction may be allowed to proceed with or without addition of one or more suitable reaction aids. As usable reaction aids, may be mentioned suitable acids, for example, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluene-sulfonic acid and triflouromethanesulfonic acid, and Lewis acids such as boron triflouride, aluminum chloride and titanium tetrachloride. In addition, the reaction may also be allowed to proceed while collecting the resultant water in a Dean-Stark trap.

Depending on the kinds of an acid and a solvent to be employed, the reaction may also be conducted in the presence of a dehydrating agent such as molecular sieve. When p-toluenesulfonic acid is used in dimethylsulfoxide, for instance, Molecular Sieves 5-A may be used. The molecular sieve can be used generally in an amount of 2-200 g, preferably, 50-200 g per 0.1 mole of the 1,5-diphenylpentanetrione derivative (II). The reaction may be carried out at a desired temperature between the solidifying point of the solvent and its boiling point, preferably, at a temperature in a range of from 10.degree. C. to the boiling point of the solvent.

After completion of the reaction, the acid or molecular sieve is removed respectively by washing it with water and an alkali solution or by filtration or the like. Upon removal of the solvent by distillation subsequent to extraction of the reaction product with chloroform, the compound of this invention can be obtained. The compound of this invention may be purified by recrystallizing same from acetone, methanol, ethanol, benzene, toluene, diisopropyl ether, ethyl acetate, chloroform, hexane or the like, or subjecting same to chromatography on a silica gel column if necessary.

PROCESS (b)

The compounds of this invention may also be produced by cyclizing a 5-anilino-1,5-diphenyl-4-pentene-1,3-dione derivative represented by the general formula (IV) or (V): ##STR70## wherein X, Y, Z, R, l, m and n have the same meanings as defined above, or ##STR71## wherein X, Y, Z, R, l, m and n have the same meanings as defined above, or a tautomer thereof in the presence of an acid catalyst.

The tautomers of the above compound (IV) are represented by the geneal formulae: ##STR72##

The cyclizing or ring-closing reaction of the 5-anilino-1,5-diphenyl-4-pentene-1,3-dione derivative of the formula (IV) or (V) or its tautomer may be conducted generally by dissolving or suspending the derivative (IV) or (V) or its tautomer in a suitable solvent, for example, a hydrocarbon such as benzene toluene or xylene, a halogenated hydrocarbon such as chlorobenzene, methylene chloride or chloroform, an ether such as diisopropyl ether, tetrahydrofuran or dioxane, a ketone such as acetone or methyl ethyl ketone, a nitrile such as acetonitrile, an amide such as N,N-dimethylformamide or N,N-dimethylacetamide, dimethylsulfoxide, acetic acid, or the like. As an alternative, the cyclization reaction may also be conducted without any solvent. As illustrative examples of the acid catalyst, may be mentioned polyphosphoric acid, sulfuric acid, p-toluenesulfonic acid, aluminum chloride, etc. The reaction may be carried out at a desired temperature between the solidifying point of the solvent and its boiling point, preferably, at a temperature in a range of from 10.degree. C. to the boiling point of the solvent.

After completion of the reaction, ice water is added to the reaction mixture, followed by extraction with chloroform. After washing the solution in chloroform with water and drying same, the solvent is distilled off to afford the compound (I) of this invention. The compound of this invention may be purified by its recrystallization from acetone, methanol, ethanol, benzene, toluene, diisopropyl ether, ethyl acetate, chloroform, hexane or the like or its chromatography on a silica gel column if necessary.

PROCESS (c)

The compound of this invention can also be produced by reacting a phenylpropiolic ester derivative represented by the general formula (VI): ##STR73## wherein Z and n have the same meanings as defined above, with an N-phenyl-1-phenylethaneimine derivative represented by the general formula (VII): ##STR74## wherein X, Y, Z, R, l and m have the same meanings as defined above, in the presence of a Lewis acid such as aluminum chloride or titanium tetrachloride.

Upon conducting the reaction in accordance with the Process (c), the phenylpropiolic ester derivative of the formula (VI) and the N-phenyl-1-phenylethaneimine derivative of the formula (VII) are dissolved or suspended in a suitable solvent, for example, benzene, toluene, xylene, chlorobenzene, dimethylsulfoxide or the like. The reaction may also be carried out without any solvent. It is however preferable to dissolve both the reactants in toluene and then to add 0.5-5 equivalents of a Lewis acid as a reaction aid. As the Lewis acid, may be used aluminum chloride, titanium tetrachloride, boron triflouride, boron trichloride or the like. It is preferable to add 1 equivalent of aluminum chloride.

After completion of the reaction, the reaction mixture is washed successively with an aqueous solution of hydrochloric acid, water and an alkali solution. After extraction with chloroform, the resultant chloroform solution is dried and the solvent is then distilled off to obtain the compound of this invention. If necessary, the compound of this invention can be purified by subjecting it to chromatography on a silica gel column for its crystallization and then recrystallizing same from acetone, methanol, benzene, ethyl acetate, chloroform or the like. When the reaction mixture is washed only with dilute hydrochloric acid and water and is not washed with an aqueous alkali solution subsequent to the completion of the reaction, the compound of the present invention is obtained in the form of its hydrochloric acid salt. For instance, in the case of 2-(2-bromophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone as obtained without washing the reaction mixture with an aqueous alkali solution, this product showed it NMR spectrum, of which the peak corresponding to the C-5 proton shifted to a lower magnetic field as compared with usual pyridinone derivatives, and the elemental analysis indicated the inclusion of 1/2 HC1. From this, it was confirmed that the product was the hydrochloride salt.

PROCESS (d)

Using as starting compound such a 4(1H)-pyridinone derivatives which have been prepared in the above-described procedures, other 4-(1H)-pyridinone derivatives can also be produced therefrom.

For example, when 2-(4-methoxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone is either dissolved or suspended in a suitable solvent, e.g., methylene chloride, benzene or chloroform, and a Lewis acid such as boron tribromide, boron trichloride or the like is then added to the resulting solution to conduct a reaction, 2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone is produced.

Further, upon dissolution of the 2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone as above in a suitable solvent, for example, dimethylsulfoxide, dimethylacetamide, dimethylformamide or acetone, followed by reaction with an alkyl halide, alkoxyalkyl halide, an alkenyl halide or the like, the correspondingly substituted 4(1H)-pyridinone derivative is produced.

For example, the reaction with ethyl iodine gives 2-(4-ethoxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone, and the reaction with methoxymethyl chloride provides the 2-(4-methoxymethoxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone.

Furthermore when 1-(2-nitrophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone is reduced with hydrogen, ammonium formate or the like in the presence of a palladium black catalyst, 1-(2-aminophenyl)-3-methyl-2,6-diphenyl-4-(1H)-pyridinone can be prepared.

Moreover, by reacting 3-methyl-1-(4methylthiophenyl)-2,6-diphenyl-4(1H)-pyridinone with a suitable oxidizing agent, for example, m-chloroperbenzoic acid or Oxone in a suitable solvent such as methylene chloride or an aqueous solution of chloroform-methanol, 1-(4-methanesulfinylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone or 1-(4-methanesulfonylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone can be produced correspondingly.

PROCESS (e)

The 4(1H)-pyridinone derivatives of formula (I) where A is the sulfur atom can be produced by dissolving or suspending the corresponding 4(1H)-pyridinone derivative of formula (I) where A is the oxygen atom, in a suitable solvent, for example, pyridinone, xylene or toluene, and then reacting it with phosphorus pentasulfide, silicon disulfide, boron sulfide or the like under the refluxing temperature conditions.

According to a further aspect of this invention, therefore, there is provided a process for the production of a compound of the general formula (I) as described hereinbefore, which process comprises the step of:

either (i) reacting a 1,5-diphenylpentanetrione derivative represented by the general formula (II): ##STR75## wherein Y, Z, R, m and n have the same meaning as defined above, or a tautomer thereof, with an aniline derivative represented by the general formula (III): ##STR76## wherein X and l have the same meanings as defined above, in an inert organic solvent, or

(ii) cyclizing a 5-anilino-1,5-diphenyl-4-pentene-1,3-dione derivative represented by the general formula (IV) or (V): ##STR77## wherein X, Y, Z, R, l, m and n have the same meanings as defined above, or ##STR78## wherein X, Y, Z, R, l, m and n have the same meanings as defined above, or a tautomer thereof in or without an inert organic solvent in the presence of an acid catalyst, or

(iii) reacting a phenylpropionic ester derivative represented by the general formula (VI): ##STR79## wherein X and n have the same meanings as defined above, with an N-phenyl-1-phenylethaneimine derivative represented by the general formula (VII): ##STR80## wherein X, Y, R, l and m have the same meaning as defined above, in or without an inert organic solvent, in the presence of a Lewis acid such as aluminum chloride or titanium tetrachloride, or

(iv) reacting a 4(1H)-pyridinone derivative represented by the general formula ##STR81## wherein X, Y, Z, R, m, n and l are defined above, with phosphorus pentasulfide, silicon disulfide, boron sulfide or other equivalent sulfurizing agent in an inert organic solvent under the refluxing temperature to convert the oxygen atom at the 4-position of the compound of the formula (I') into a sulfur atom which is a value of the group A in the compound of the formula (I).

Incidentally, when at least one phenyl group among the three phenyl groups at the 1-, 2-, and 6-positions of the compounds of this invention as produced in the above-described processes is containing at least one substituent at each of the ortho- or meta-positions thereof, the atrop-isomers exist. The atrop-isomers can be isolated from each other by chromatography on a silica gel column except for enantiomers.

Production of the compounds of this invention will now be illustrated with reference to the following Examples 1-33. Examples 1-10 and 30-32 are illustrative of the Process (a), Examples 11 illustrative of the Process (b), Examples 12-21 and 33 illustrative of the Process (c), Examples 22-26 and 28-29 illustrative of the Process (d), and Example 27 is illustrative of the Process (e).

EXAMPLE 1

Synthesis of 1-(3,5-dimethoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

to 170 ml of chlorobenzene were added 4.2 g (0.015 mole) of 2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 11.5 g (0.075 mole) of 3,5-dimethoxyaniline, 5.2 g (0.027 mole) of para-toluenesulfonic acid and 35.0 g of Molecular Sieves 5A, followed by refluxing the resulting mixture for 2 hours. After cooling the reaction mixture, solid matter was removed from the reaction mixture, followed by addition of 200 ml of chloroform thereto. The organic layer was washed first with 200 ml of 10% hydrochloric acid and then with 200 ml of a 10% aqueous solution of sodium hydroxide. The organic layer was washed further with water and was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate by filtration, the solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate). Upon recrystallization of the resultant crystals from a 2:1 mixed solvent of acetone and hexane, 2.0 g of 1-(3,5-dimethoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 232.degree.-236.degree. C. was obtained.

EXAMPLE 2

Synthesis of 1-(2,6-diflourophenyl)-b 3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 150 ml of xylene were added 2.8 g (0.010 mole) of 2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 12.9 g (0.010 mole) of 2,6-diflouroaniline, 3.0 g (0.016 mole) of para-toluenesulfonic acid and 30.0 g of Molecular Sieves 5A, followed by refluxing the resulting mixture for 3 hours. After cooling the reaction mixture, solid matter was filtered off and the filtrate was washed successively with 50 ml of 10% hydrochloric acid, 50 ml of 10% aqueous solution of sodium hydroxide and water. The filtrate was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate by filtration, the solvent was distilled off and the residue was crystallized from a 2:1 mixed solvent of acetone and hexane to give 0.7 g of 1-(2,6-diflourophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 219.degree.-221.degree. C.

EXAMPLE 3

Synthesis of 1-(2-chloro-5-nitrophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 170ml of chlorobenzene were added 3.4 g (0.012 mole) of 2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 10.4 g (0.060 mole) of 2-chloro-5-nitroaniline, 4.1 g (0.022 mole) of para-toluenesulfonic acid and 35.0 g of Molecular Sieves 5A, followed by refluxing for 2 hours. After cooling the reaction mixture, solid matter was removed from the reaction mixture, followed by addition of 200 ml of chloroform. The resultant mixture was washed first with 100 ml of 10% hydrochloric acid and then with 100 ml of a 10% aqueous solution of sodium hydroxide. The mixture was washed further with water and was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate). Upon recrystallization of the resultant crystals from a 2:1 mixed solvent of acetone and hexane, 1.9 g of 1-(2-chloro-5-nitrophenyl)-3-methyl-2,6 -diphenyl-4(1H)-pyridinone having a melting point of 277.degree.-279.degree. C. was obtained.

EXAMPLE 4

Synthesis of 1-2(2,4-dichloro-3-methylphenyl-3-methyl-2,6-diphenyl-4(1H)-pyridinone

In 170 ml of chlorobenzene were dissolved 3.4 g (0.012 mole) of 2-methyl-1,5-diphenyl-1,3,5-pentanetrione and 10.6 g (0.06 mole) of 2,4-dichloro-3-methylaniline, followed by further addition of 4.1 g (0.022 mole) of para-toluenesulfonic acid and 35.0 g of Molecular Sieves 5A to the solution. After heating the reaction mixture under reflux for 2 hours, solid matter was removed from the reaction mixture, followed by an addition of 200 ml of chloroform. The resultant mixture was washed first with 100 ml of 10% hydrochloric acid and then with 100 ml of a 10% aqueous solution of sodium hydroxide. The mixture was washed further with water and was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate). Upon recrystallization of the resultant crystals from a 2:1 mixed solvent of acetone and hexane, 0.7 g of 1-(2,4-dichloro-3-methylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 237.degree.-238.degree. C. was obtained.

EXAMPLE 5

Synthesis of 2-(3-ethoxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone

In 500 ml of xylene were dissolved 15.0 g (0.046 mole) of 1-(3-ethoxyphenyl)-2-methyl-5-phenyl-1,3,5-pentanetrione, 43.0 g (0.47 mole) of aniline and 8.8 g (0.092 mole) of methanesulfonic acid. The reaction mixture was heated under reflux for 30 minutes in a reactor fitted with a Dean-Stark apparatus. After cooling, the reaction mixture was filtered to remove solid matter, followed by removal of the solvent by distillation. The residue was extracted with chloroform and the resultant solution in chloroform (the extract) was washed first with 100 ml of 10% hydrochloric acid and then with 100 ml of a 10% aqueous solution of sodium hydroxide. The chloroform solution was washed further with water and was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate). Upon recrystallization of the resultant crystals from acetone, 5.3 g of 2-(3-ethoxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone having a melting point of 146.degree.-149.degree. C. was obtained.

EXAMPLE 6

Synthesis of 6-(4-cyanophenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone

In 400 ml of xylene were dissolved 10.0 g (0.033 mole) of 5-(4-cyanophenyl)-2-methyl-1-phenyl-1,3,5-pentanetrione, 25.0 g (0.26 mole) of aniline and 7.0 g (0.073 mole) of methanesulfonic acid. The solution obtained was heated under reflux for 30 minutes in a reactor fitted with a Dean-Stark apparatus. After cooling, 6.5 g (0.043 mole) of trifluoromethanesulfonic acid was added further to the reaction mixture and the resultant mixture was similarly heated under reflux for 30 minutes. After cooling, solid matter was removed from the reaction mixture, followed by concentration under pressure. The concentrate was extracted with dichloromethane. The organic layer was washed successively with 100 ml of 10% hydrochloric acid, 100 ml of a 10% aqueous solution of sodium hydroxide and water. The organic layer was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate). The resultant crystals were washed with acetone to afford 2.4 g of 6-(4-cyanophenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone having a melting point of 229.degree.-233.degree. C.

EXAMPLE 7

Synthesis of 2-(2-chlorophenyl)-3-methyl-1-(2-methylphenyl)-phenyl-4(1H)-pyridinone

In 500 ml of xylene were dissolved 37.7 g (0.012 mole) of 1-(2-chlorophenyl)-2-methyl-5-phenyl-1,3,5-pentanetrione, 38.6 g (0.36 mole) of 2-methylaniline, 22.8 g (0.12 mole) of para-toluenesulfonic acid and 30 g of Molecular Sieves 5A, followed by refluxing the resulting mixture for 8 hours. After cooling, solid matter was filtered off and the organic layer was washed first with 100 ml of 10% hydrochloric acid and then with 100 ml of a 10% aqueous solution of sodium hydroxide. After washing the organic layer further with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate). As result, two atrop-isomers of 2-(2-chlorophenyl)-3-methyl-1-(2-methylphenyl)-6-phenyl-4(1H)-pyridinone, namely, Compound 338 and Compound 339 were obtained in yields of 1.2 g and 0.8 g, respectively. Their melting points were 227.degree.-229.degree. C. and 222.degree.-225.degree. C., respectively.

EXAMPLE 8

Synthesis of 1,2,6-tris(2-chlorophenyl)-3-methyl-4(1H)-pyridinone

To 200 ml of xylene were added 6.9 g (0.020 mole) of 1,5-bis(2-chlorophenyl)-2-methyl-1,3,5-pentanetrione, 25.5 g (0.20 mole) of 2-chloroaniline and 20.0 g of Molecular Sieves 5A. After heating the reaction mixture under reflux for 2 hours, the reaction mixture was poured into ice water, followed by addition of 200 ml of chloroform thereto and vigorous stirring of the resultant mixture. One hour later, the reaction mixture was filtered to remove solid matter. The organic layer was washed first with 50 ml of 10% hydrochloric acid and then with 50 ml of a 10% aqueous solution of sodium hydroxide. The mixture was washed further with water and was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off. The residue was purified by chromatography on a silica gel column (eluent: ethyl acetate) and then recrystallization from acetone to give 1.4 g of 1,2,6-tris(2-chlorophenyl)-3-methyl-4(1H)-pyridinone having a melting point of 205.degree.-207.degree. C.

EXAMPLE 9

Synthesis of 6-(2-chlorophenyl)-1-(2,6-difluorophenyl)-3-methyl-2-phenyl-4(1H)-pyridinone

In 200 ml of xylene were dissolved 6.3 g (0.020 mole) of 5-(2-chlorophenyl)-2-methyl-1-phenyl-1,3,5-pentanetrione, 20.0 g (0.155 mole) of 2,6-difluoroaniline, 4,6 g (0.024 mole) of para-toluenesulfonic acid and 50.0 g of Molecular Sieves 5A, followed by reflux for 8 hours. Solid matter was filtered off from the reaction mixture and 300 ml of chloroform was added to the filtrate. The mixture obtained was washed first with 50 ml of 10% aqueous solution of sodium hydroxide. After washing the chloroform layer further with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to column chromatography (eluent: ethyl acetate) to afford crystals. The crystals were recrystallized from a 2:1 mixed solvent of acetone and hexane, thereby yielding 2.0 g of 6-(2-chlorophenyl)-1-(2,6-difluorophenyl)-3-methyl-2-phenyl-4(1H)-pyridinone having a melting point of 213.degree.-215.degree. C.

EXAMPLE 10

Synthesis of 3-methyl-1-(2,3,4,5,6-pentafluorophenyl)-2,6-diphenyl-4(1H)-pyridinone

In 110 ml of xylene were dissolved 3.1 g (0.011 mole) of 2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 20.0 g (0.11 mole) of 2,3,4,5,6-pentafluoroaniline, 3.1 g (0.016 mole) of paratoluenesulfonic acid and 22.0 g of Molecular Sieves 5A, followed by reflux for 1 hours. After cooling the reaction mixture, solid matter was removed by filtration and the filtrate was then concentrated. After 200 ml of chloroform was added, the resultant solution in chloroform was washed first with 50 ml of 10% hydrochloric acid and then with 50 ml of a 10% aqueous solution of sodium hydroxide. After washing the solution in chloroform further with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to column chromatography (eluent: 50.1 mixed solvent of chloroform and methanol). The resulting crystals were recrystallized from a 1:1 mixed solvent of acetone and hexane, thereby affording 1.3 g of 3-methyl-1-(2,3,4,5,6-pentafluorophenyl)-2,6-diphenyl-4(1H)-pyridinone having a melting point of 192.degree.-194.degree. C.

EXAMPLE 11

Synthesis of 1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 17.8 g (0.050 mole) of 5-(2-chloroanilino)-2-methyl-1,5-diphenyl-4-pentene-1,3-dione, 200 ml of xylene and 100 g of polyphosphoric acid were added. The resultant mixture was heated under reflux for 30 minutes. After cooling the reaction mixture, the solvent was removed by decantation and the remaining solid matter was added with 200 ml of chloroform and 200 ml of water. The resultant mixture was then stirred vigorously for 2 hours. Thereafter, the organic layer was washed with water and then dried over anhydrous sodium sulfate. After removal of the sodium sulfate, the solvent was distilled off and the residue was recrystallized from acetone, thereby affording 2.8 g of 1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 228.degree.-231.degree. C.

EXAMPLE 12

Synthesis of 1-(4-fluorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 300 ml of toluene were added 9.1 g (0.040 mole) of N-(4fluorophenyl)-1-phenylpropaneimine, 4.7 g (0.035 mole) of aluminum chloride and 5.2 g (0.030 mole) of ethyl phenylpropiolate, followed by refluxing the resultant mixture for 5 hours. Thereafter, the reaction mixture was poured into 500 ml of 2N sulfuric acid which had been ice-cooled, followed by extraction with chloroform. After washing the organic layer with water, the organic layer wad dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: 1:50 mixed solvent of methanol and chloroform). The resultant crystals were recrystallized from 1:1 mixed solvent of acetone and hexane to give 1.0 g of 1-(4-fluorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 256.degree.-259.degree. C.

EXAMPLE 13

Synthesis of 1-(3-methoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

Added to 300 ml of benzene were 8.0 g (0.033 mole) of N-(3-methoxyphenyl)-1-phenylpropaneimine and 4.7 g (0.035 mole) of aluminum chloride, followed by dropwise addition of 5.2 g (0.030 mole) of ethyl phenylpropiolate at room temperature.

After heating the reaction mixture under reflux for 30 hours under a nitrogen atmosphere, the reaction mixture was poured into 500 ml of 2N sulfuric acid which had been ice-cooled, followed by extraction with chloroform. After washing the organic layer with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate). The crystals obtained were recrystallized from a 2:1 mixed solvent of ethyl acetate and hexane to obtain 0.8 g of 1-(3-methoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 183.degree.-185.degree. C.

EXAMPLE 14

Synthesis of 2-(3,4-dichlorophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone

To 500 ml of toluene were added 6.2 g (0.022 mole) of 1-(3,4-dichlorophenyl)-N-phenylpropaneimine and 3.9 g (0.022 mole) of ethyl phenylpropiolate, followed by addition of 3.6 g (0.023 mole) of aluminum chloride. After heating the reaction mixture with stirring at 60.degree.-70.degree. C. for 4 days under a nitrogen atmosphere, the reaction mixture was poured into 400 ml of 2N sulfuric acid which had been ice-cooled, followed by extraction with dichloromethane. After washing the organic layer with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate). The resulting crystals were recrystallized from a 2:1 mixed solvent of acetone and hexane to afford 1.9 g of 2-(3,4-dichlorophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone having a melting point of 188.degree.-191.degree. C.

EXAMPLE 15

Synthesis of 6-(2-methylphenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone

To 300 ml of toluene were added 7.5 g (0.036 mole) of N-phenyl-1-phenylpropaneimine, 5.8 g (0.031 mole) of ethyl 2-methylphenylpropiolate and 6.0 g (0.045 mole) of aluminum chloride. The reaction mixture was stirred with heating at 60.degree. C. for 3 days in a nitrogen atmosphere. After cooling, the reaction mixture was poured into 500 ml of 2N sulfuric acid, followed by extraction with chloroform. After washing the organic layer with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate). The resultant crystals were washed with a 2:1 mixed solvent of acetone and hexane to obtain 0.4 g of 6-(2-methyl-phenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone having a melting point of 188.degree.-191.degree. C.

EXAMPLE 16

Synthesis of 1,2-bis(2-chlorophenyl)-3-methyl-6-phenyl-4(1H)-pyridinone

To 300 ml of toluene were added 6.2 g (0.022 mole) of N,1-bis(2-chlorophenyl)propaneimine, 3.9 g (0.022 mole) of ethyl phenylpropiolate and 3.6 g (0.027 mole) of aluminum chloride. After heating the reaction mixture with stirring at 60.degree. C. for 4 days, the reaction mixture was poured into 500 ml of 2N sulfuric acid, followed by extraction with dichloromethane. After washing the organic layer with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to column chromatography (eluent: ethyl acetate) to obtain two types of atrop-isomers of 1,2-bis(2-chlorophenyl)-3-methyl-6-phenyl-4(1H)-pyridinone, namely, 0.6 g of Compound 335 and 0.2 g of Compound 336, of which the melting points were 205.degree.-207.degree. C. and 232.degree.-234.degree. C., respectively.

EXAMPLE 17

Synthesis of 1-(2-chlorophenyl)-2-(4 -methyoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinone

To 300 ml of toluene were added 6.3 g (0.023 mole) of N-(2-chlorophenyl)1-(4-methoxyphenyl)propaneimine, 4.0 g (0.023 mole) of ethyl phenylpropiolate and 3.7 g of aluminum chloride. The reaction mixture was heated with stirring at 60.degree. C. for 4 days. After cooling, the reaction mixture was poured into 500 ml of 2N sulfuric acid, followed by extraction with dichloromethane. After washing the organic layer with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate). The crystals thus-obtained were recrystallized from a 2:1 mixed solvent of acetone and hexane to give 1.0 g of 1-(2-chlorophenyl)-2-(4-methoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinone.

EXAMPLE 18

Synthesis of 1-(2-chlorophenyl)-3-ethyl-2,6-diphenyl-4(1H)-pyridinone

To 300 of toluene were added 10.3 g (0.040 mole) of N-(2-chlorophenyl)-1-phenylbutaneimine, 5.2 g (0.030 mole) of ethyl phenylpropiolate and 5.3 g (0.040 mole) of aluminum chloride. After heating the reaction mixture under reflux for 20 hours under a nitrogen atmosphere, the reaction mixture was poured into 500 ml of 2N sulfuric acid which had been ice-cooled, followed by extraction with chloroform. After washing the organic layer with 50 ml of a 10% aqueous solution of sodium hydroxide and then with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate) so that 2.0 g of 1-(2-chlorophenyl)-3-ethyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 165.degree.-166.degree. C. was obtained.

EXAMPLE 19

Synthesis of 3-chloro-1-(2-chlorophenyl)-2,6-diphenyl-4(1H)-pyridinone

To 300 ml of toluene were added 7.4 g (0.030 mole) of 2-chloro-N-(2-chlorophenyl)-1-phenylethaneimine, 5.2 g (0.030 mole) of ethyl phenylpropiolate and 6.7 g (0.050 mole) of aluminum chloride. The reaction mixture was then heated under reflux for 20 hours under nitrogen atmosphere. After cooling, the reaction mixture was poured into 500 ml of 2N sulfuric acid, followed by extraction with chloroform. After washing the organic layer with 50 ml of a 10% aqueous solution of sodium hydroxide and then with water, it was dried with anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate) to yield 3-chloro-1-(2-chlorophenyl)-2,6-diphenyl-4(1H)-pyridinone having a melting point of 230.degree.-233.degree. C.

EXAMPLE 20

Synthesis of 2-(2-bromophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone hydrochloride

to 300 ml of toluene were added 6.4 g (0.022 mole) of 1-(2-bromophenyl)-N-phenylpropaneimine, 3.9 g (0.022 mole) of ethyl phenylpropiolate and 3.6 g (0.027 mole) of aluminum chloride. The reaction mixture was then heated at 60.degree. C. hours. After cooling, the reaction mixture was poured into 500 ml of 2N sulfuric acid, followed by extraction with methylene chloride. After washing the organic layer (the extract) with water, the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate). The resultant crystals were then recrystallized from a 2:1 mixed solvent of acetone and hexane to obtain 1.3 g of 2-(2-bromophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone hemihydrochloride having a melting point of 236.degree.-238.degree. C.

Elemental analysis: Calculated for C.sub.24 H.sub.18 BrNO.multidot.1/2HCl: C, 66.34; H, 4.29; N, 3.19%. Found: C, 66.64; H, 4.52; N, 3.22%.

EXAMPLE 21

Synthesis of 1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone hydrochloride

Added to 700 ml of toluene were 73.1 g (0.30 mole) of N-(2-chlorophenyl)-1-phenylpropaneimine, 34.8 g (0.20 mole) of ethyl phenylpropiolate and 40.0 g (0.30 mole) of aluminum chloride. The reaction mixture was then heated with stirring as 60.degree. C. for 3 days. After cooling, the reaction mixture was poured into 1000 ml of 2N sulfuric acid, followed by extraction with chloroform. After washing the organic layer with water, the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was purified by chromatography on a silica gel column (eluent: ethyl acetate). The crystals obtained were then recrystallized from a 1:2 mixed solvent of chloroform and hexane to give 17.0 g of 1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone. 1/5HCl having a melting point of 229.degree.-231.degree. C.

Elemental analysis: Calculated for C.sub.24 H.sub.18 C NO.multidot.1/5HCl: C, 76.03; H, 4.83; N, 3.69%. Found: C, 75.56; H, 4.91; n, 3.72%.

EXAMPLE 22

Synthesis of 2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone

To 300 ml of a solution of 18.7 g (0.051 mole) of 2-(4-methoxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone in methylene chloride, 25.0 g (0.010 mole) of boron tribromide was added dropwise. After stirring the resultant mixture at room temperature for 15 hours, the reaction mixture was poured into water, followed by neutralization with sodium hydrogen carbonate. Deposited crystals were collected by filtration and washed with aceton, thereby affording 16.9 g of 2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone having a melting point of not lower than 300.degree. C.

EXAMPLE 23

Synthesis of 3-methyl-1,6-diphenyl-2-(4-propoxyphenyl)-4(1H)-pyridinone

To 50 ml of a suspension of 0.36 g (0.018 mole) of sodium hydride in DMSO, 1.7 g (0.0048 mole) of 2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone was added, followed by further dropwise addition of 1.0 g (0.0058 mole) of propyl iodide. The reaction mixture was then stirred at room temperature for 6 hours. The reaction mixture was thereafter poured into ice water, followed by extraction with chloroform. After washing the organic layer with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off, followed by recrystallization from a 2:1 mixed solvent of acetone and hexane to obtain 1.6 g of 3-methyl-1,6-diphenyl-2-(4-propoxyphenyl)-4(1H)-pyridinone having a melting point of 165.degree.-168.degree. C.

EXAMPLE 24

Synthesis of 1-(2-aminophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 50 ml of a suspension of 1.8 g (0.0050 mole) of 3-methyl-1-(2-nitrophenyl)-2,6-diphenyl-4(1H)-pyridinone and 0.2 g of 10% Pd-C in methanol, 1.5 g (0.023 mole) of ammonium formate (as a reducing agent) was added. After heating the resultant mixture under reflux for 3 hours under a nitrogen gas stream, solid matter was filtered off from the reaction mixture and the solvent was distilled off. The residue was then extracted with chloroform and the organic layer (the extract) was washed with 50 ml of a 10% aqueous solution of sodium hydroxide. After washing the organic layer with water, it was dried with anhydrous sodium sulfate and the solvent was then distilled off. The crystals thus-obtained were washed with acetone to give 0.9 g of 1-(2-aminophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of not lower than 300.degree. C.

EXAMPLE 25

Synthesis of 1-(4-methanesulfinylphenyl)-3-methyl-2,6-diphenyl- 4(1H)-pyridinone

Dissolved in 30 ml of methylene chloride was 1.1 g (0.0029 mole) of 3-methyl-1-(4-methylthiophenyl)-2,6-diphenyl-4(1H)-pyridinone, followed by addition of 0.6 g (0.0034 mole) of m-chloroperbenzoic acid (as oxidizing agent). After stirring the reaction mixture for 15 minutes, it was poured into water, followed by extraction with methylene chloride. The organic layer (the extract) was washed with 20 ml of a saturated aqueous solution of sodium hydrogen carbonate and then with water. The organic layer was thereafter dried over anhydrous sodium sulfate. The solvent was distilled off and the resulting crystals were recrystallized form a 2:1 mixed solvent of acetone and hexane, affording 1.1 g of 1-(4-methanesulfinylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 242.degree.-244.degree. C.

EXAMPLE 26

Synthesis of 1-(3-methanesulfonylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

In 5 ml of water was dissolved 1.2 g (0.0019 mole) of Oxone. The resulting solution was then added dropwise to 5 ml of a methanol solution of 0.5 g (0.0013 mole) of 1-(3-methanesulfinylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone. After stirring the reaction mixture for 2 hours, it was poured into water, followed by extraction with chloroform. The organic layer was washed with water and was thereafter dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was crystallized form a 2:1 mixed solvent of acetone and hexane, affording 0.4 g of 1-(3-methanesulfonylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having a melting point of 246.degree.-248.degree. C.

EXAMPLE 27

Synthesis of 1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinethione

To 40 ml of pyridine were added 1.3 g (0.0035 mole) of 1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone and 0.9 g (0.0042 mole) of phosphorus pentasulfide, followed by refluxing the resultant mixture for 3 hours. After cooling, the reaction mixture was poured into water and the resulting crystals were collected by filtration. The crystals were dissolved in 100 ml of chloroform, and washed first with 30 ml of 2N hydrochloric acid and then with 30 ml of a saturated aqueous solution of sodium hydrogencarbonate. After washing the chloroform solution further with water, it was dried over anhydrous sodium sulfate. After removal of sodium sulfate, the solvent was distilled off to obtain crystals. The crystals were recrystallized from a 1:1 mixture of acetone and hexane, thereby obtaining 1.1 g of 1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinethione having a melting point of 271.degree.-275.degree. C.

EXAMPLE 28

Synthesis of 1,2,6-triphenyl-3-trifluoromethyl-4(1H)-pyridinone

To 40 ml of 1-methyl-2-pyrrolidinone were added 2.0 g (0.0050 mole) of 3-bromo-1,2,6-triphenyl-4(1H)-pyridinone, 2.7 g (0.020 mole) of sodium trifluoroacetate and 1.9 g (0.010 mole) of cuprous iodide. The reaction mixture was then heated at 160.degree. C. for 5 hours in a nitrogen atmosphere. After allowing the reaction mixture to cool down, it was poured into water, followed by extraction with ethyl ether. The organic layer (the extract) was washed with 50 ml of a saturated aqueous solution of sodium hydrogen carbonate. After washing the organic layer further with water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off, and the residue was crystallized from a 1:3 mixed solvent of ethyl acetate and hexane to yield 0.4 g of 1,2,6-triphenyl-3-trifluoromethyl-4(1H)-pyridinone having a melting point of 222.degree.-225.degree. C.

EXAMPLE 29

Synthesis of 3-methyl-2,6 -diphenyl-1-(3-propargyloxyphenyl)-4(1H)-pyridinone

To 50 ml of a suspension of 0.72 g (0.03 mole) of sodium hydride in DMSO, 3.5 g (0.01 mole) of 1-(3-hydroxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone was added, followed by further dropwise addition of 1.4 g (0.012 mole) of propargyl bromide. The reaction mixture was thereafter poured into ice water, followed by extraction with chloroform. After washing the organic layer (the extract) with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off, followed by recrystallization from a 2:1 mixed solvent of acetone and hexane to obtain 1.5 g of 3-methyl-2,6-diphenyl-1-(3-propargyloxyphenyl)-4-(1H)-pyridinone having a melting point of 166.degree.-169.degree. C.

EXAMPLE 30

Synthesis of 1-(3,5-dimethoxyphenyl)-2-(4-methoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinone p-toluenesulfonate

To 200 ml of chlorobenzene were added 3.1 g (0.01 mole) of 1-(4-methoxyphenyl)-2-methyl-5-phenyl-1,3,5-pentanetrione, 2.3 g (1.5 mole) of 3,5-dimethoxyaniline, 2.9 g (0.015 mole) of para-toluenesulfonic acid and 10 g of Molecular Sieves 5A, followed by refluxing the resulting mixture for 2 hours. After cooling the reaction mixture, solid matter was removed from the reaction mixture, followed by addition of 500 ml of chloroform thereto. The organic layer was washed first with 200 ml of 10% hydrochloric acid and then with water. The organic layer was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate by filtration, the solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate). Upon washing the resultant crystals with ethyl acetate, 3.3 g of 1-(3,5-dimethoxyphenyl)-2-(4-methoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinone p-toluenesulfonate having a melting point of 202.degree.-204.degree. C. was obtained.

EXAMPLE 31

Synthesis of 1-(2-fluorophenyl)-3-methyl-6-(3-methylphenyl)-2-phenyl-4(1H)-pyridinone

To 30 ml of xylene were added 2.0 g (0.0068 mole) of 2-methyl-5-(3-methylphenyl)-1-phenyl-1,3,5-pentanetrione, 7.6 g (0.068 mole) of 2-fluoroaniline, 2.0 g (0.012 mole) of para-toluenesulfonic acid and 14.0 g of Molecular Sieves 5A, followed by refluxing the resulting mixture for 1 hour. After cooling the reaction mixture, solid matter was filtered off and the filtrate was mixed with 100 ml of chloroform and then washed successively with 50 ml of 10% hydrochloric acid, 50 ml of a 10% aqueous solution of sodium hyroxide and water. The filtrate was then dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was crystallized from a 1:3 mixed solvent of chloroform and hexane to give 1.3 g of 1-(2-fluorophenyl)-3-methyl-6-(3-methylphenyl)-2-phenyl-4-(1H)-pyridinone having a melting point of 211.degree.-214.degree. C.

EXAMPLE 32

Synthesis of 2-(2-chlorophenyl)-6-(2-fluorophenyl)-3-methyl-1-phenyl-4(1H)-pyridinone

In 450 ml of xylene were suspended 15.3 g of 1-(2-chlorophenyl)-2-methyl-5-(2-fluoro-phenyl)-1,3,5-pentanetrione, 6.4 g of aniline, 6.6 g of para-toluenesulfonic acid and 85 g of Molecular Sieves 5A, followed by refluxing the resultant mixture for 8 hours. Xylene was distilled off from the reaction mixture and 300 ml of chloroform was added to the residue. The mixture obtained was filtered and the filtrate was washed first with 10% hydrochloric acid and then with a 10% aqueous solution of sodium hydroxide. After washing the chloroform phase further with water, the solution in chloroform was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was purified by column chromatography (eluent: ethyl acetate-n-hexane, 1:3) to afford crude crystals. The crystals were recrystallized from ethyl acetate, yielding 4.5 g of 2-(2-chlorophenyl)-6(2fluorophenyl)-3-methyl-1-phenyl-4(1H)-pyridinone having a melting point of 182.degree.-183.degree. C.

EXAMPLE 33

Synthesis of 2-(2,4-difluorophenyl)-6-(2-fluorophenyl)-1-(3,5-dimethoxyphenyl)-3-methyl-4(1H)-pyridinone

In 3 l of toluene were dissolved 54.9 g (0.18 mol) of N-(3,5-dimethoxyphenyl)-1-(2,4-difluorophenyl)propanimine and 27.5 g (0.14 mole) of ethyl (2-fluorophenyl) propionate, and the resultant solution was placed under a nitrogen atmosphere and then admixed with 23.8 g (0.18 mol) of aluminum chloride, followed by refluxing the resultant mixture for 16 hours. After cooling, the reaction mixture was poured into 2N sulfuric acid, followed by extraction with chloroform. After washing the organic layer with 5% aqueous sodium hydroxide, and water, it was dried over anhydrous sodium sulfate. Subsequent to removal of the sodium sulfate, the solvent was distilled off and the residue was subjected to chromatography on a silica gel column (eluent: ethyl acetate-N-hexane, 1:1). The crystals thus-obtained were recrystallized from ethyl acetate to afford 7.3 g of 2-(2,4-difluorophenyl)-6-(2-fluorophenyl)-1-(3,5-dimethoxyphenyl)-3-methyl-4(1H)-pyridinone having a melting point of 171.degree.-173.degree. C.

The new compounds of the formula (I) according to this invention may be formulated into a fungicidal composition by mixing with a liquid or solid carrier or vehicle which is conventionally used in the art. According to another aspect of this invention, therefore, there is provided a fungicidal composition for agricultural and horticultural utilities, which comprises a compound of the general formula (I) as defined hereinbefore or a salt thereof as the active ingredient, n combination with a carrier for the active ingredient.

Although the new compound of this invention may be applied alone, it may usually be admixed with a carrier, optionally together with surfactant, dispersant or auxiliary agent and then formulated in a known manner, for example, into a dust, a wettable powder, an emulsifiable concentrate, fine particles or granules.

As suitable examples of the carriers, may be mentioned solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, siliceous sand, ammonium sulfate and urea; and liquid carriers such as isopropyl alcohol, xylene, and cyclohexanone. Illustrative examples of the surfactant and dispersant may include salts of alcohol-sulfuric acid esters, alkylarylsulfonic acid salts, diarylmethanedisulfonic acid salts, ligninsulfonic acid salts, polyoxyethyleneglycol ethers, polyoxyethylenealkyl aryl ethers, polyoxyethylenesorbitan monoalkylates, and so on. Suitable examples of the adjuvants include carboxymethylcellulose, polyethylene glycol, gum arabi, etc. These preparations can be applied after diluting same to a suitable concentration of the active ingredient, or they can be applied directly.

The proportion of the active ingredient in the composition may be increased or decreased as needed. When formulated into a dust or granules, 0.1-20 wt. % of the active ingredient is preferred. For an emulsifiable concentrate or wettable powder, 5-80 wt. % of the active ingredient is preferred.

The rate of application of the fungicidally active compound of this invention may vary depending on the type of the active compound employed, the kind of the disease to be controlled, the nature of occurrence of the disease, the degree of damage, environmental conditions, the preparation form to be used, etc. When the composition of this invention is applied directly in the form of dust or granules, it is recommendable that the rate of application of the active ingredient is suitably chosen in a range of 10 to 500 g per 10 ares. When the composition of this invention in the form of an emulsifiable concentrate or a wettable powder is diluted with water before its application and then the liquid preparation obtained is applied, it is preferred that the concentration of the active ingredient in the diluted liquid preparation is suitably chosen in a range of 10 to 1000 ppm. Generally, however, the compound of this invention can be applied in an amount of from about 0.1 g to about 100 kg per hectare, preferably 1 g to 10 kg per hectare. When it is sprayed to leaves and stem of plants, it is usuallly diluted to a concentration of about 0.1 to 10,000 ppm, preferably 10 to 3,000 ppm.

The fungicidal composition of this invention are now illustrated with reference to the following Examples 34-37, wherein all designations of "%" are given in percent by weight.

EXAMPLE 34

(Dust)

Two percent of Compound 1, 5% of diatomaceous earth and 93% of clay were uniformly mixed and ground into a dust.

EXAMPLE 35 cl (Wettable Powder)

Fifty percent of Compound 7, 45% of diatomaceous earth, 2% of sodium dinaphthylmethanedisulfonate and 3% of dosium ligninsulfonate were uniformly mixed and ground into a wettable powder.

EXAMPLE 36 cl (Emulsifiable Concentrate)

Thirty percent of Compound 126, 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene were evenly dissolved together to prepare an emulsifiable concentrate.

EXAMPLE 37

(Granules)

Five percent of Compound 264, 2% of the sodium salt of the ester of lauryl alcohol and sulfuric acid, 5% of sodium ligninsulfonate, 2% of carboxymethylcellulose and 86% of clay were mixed together and ground uniformly. The mixture was added and kneaded with 20% of water. The resulting mixture was formed into granules of 14-32 mesh by means of an extrusion granulator and was then dried into granules.

The fungicidal compounds of this invention have excellent properties. They show broad antibacterial and antifungal spectra against pathogenic microorganisms of various, agricultural and horticultural diseases of plants, such as rice sheath blight (Rhizoctonia solani), rice blast (Pyricularia oryzae), cucumber downy mildew (Pseudoperonospora cubensis), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber gray mold (Botrytis cinerea) and Alternaria sooty spot of Chinese mustard (Alternaria brassicicola). In particular, the compounds of this invention exhibit outstanding activity to control rice sheath blight (Rhizoctonia solani). Their fungicidal activities can appear in both the preventive treatment and curative treatment of the plant diseases and moreover are long-lasting. In addition, the new compounds of this invention are of high safety, due to their low toxicity to crops, warm-blooded animals, and a variety of fish and shellfish.

Effects of the fungicidal compounds of this invention are now illustrated by the following Tests.

TEST 1

(Test on the preventative effects for rice sheath blight, Rhizoctonia solani)

Rice seeds (variety: Kinmaze) were sown at a rate of 15 grains each in unglazed pots having a diameter of 7 cm. The seeds were allowed to grow for 4-5 weeks in a greenhouse. A wettable powder containing a test compound and formulated in accordance with the procedure of Example 35 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then sprayed at a rate of 10 ml per pot to the rice seedling at their 5 leaf stage. After dried in the air, the seedlings were inoculated at the basal parts with fungi, Rhizoctonia solani which had been cultured for 7 days in a rice hulls-wheat bran culture medium, and the inoculated rice plants were then kept in a moist room (28.degree. C.). Five days later, the heights of lesions formed on rice leaf sheaths were measured individually. Control value (%) was then evaluated in accordance with the following equation. ##EQU1##

Comparative Chemicals 1 and 2, the known compounds as identified hereinafter, were also tested in the same manner as above, for the comparision purpose.

Test results obtained are shown in Table 3a, Table 3b, Table 3c and Table 3d below.

TABLE 3a______________________________________Com-pound Control Compound Control Compound ControlNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________1 100 29 94 64 982 100 31 80 65 993 100 32 100 66 994 86 33 100 68 805 100 34 100 69 906 100 35 100 70 957 100 36 100 71 808 100 37 100 72 859 100 38 99 73 10010 100 40 98 76 10011 100 42 78 77 10012 100 43 92 78 10013 100 44 100 79 10014 100 52 100 81 10015 100 53 90 82 10016 92 55 100 83 9817 99 56 100 84 10018 83 57 99 85 9919 100 58 100 86 8220 100 59 87 87 9322 98 60 95 88 10026 96 61 95 89 8627 96 63 99 90 10091 100 120 89 153 9992 97 121 92 155 10093 100 123 93 156 8095 100 124 84 159 10096 100 128 99 160 9797 100 129 100 161 100101 99 130 100 162 98102 100 131 97 164 100104 100 132 100 165 100105 96 133 99 166 100106 98 134 100 167 100107 97 135 100 168 96108 95 136 97 169 97109 100 137 100 170 100110 99 138 97 171 98111 97 139 97 172 96112 96 140 100 173 99113 94 142 99 174 97114 99 143 100 176 100116 99 145 100 178 100117 98 146 97 179 100118 98 149 96 180 100119 99 152 100 181 100182 100 213 100 255 100183 100 214 100 256 99184 98 217 96 257 100185 100 219 98 258 99186 100 220 99 259 100187 100 224 100 260 100188 100 226 100 261 95189 100 227 100 262 92192 100 229 100 266 100193 100 230 100 267 100194 96 235 98 268 100195 100 237 97 269 99196 100 238 100 270 99197 100 239 100 272 96198 97 241 93 273 91201 73 242 100 274 94202 96 244 100 275 88203 99 245 100 276 87206 72 246 99 277 87208 88 247 100 278 94209 96 249 92 279 78210 100 250 100 281 100211 92 252 100 282 99283 97 317 99 346 99284 98 318 99 347 99285 100 321 97 348 92286 88 322 95 349 97288 100 324 94 350 100289 82 325 100 351 100291 99 327 100 352 98292 97 328 98 353 100293 97 329 95 354 99296 100 331 78 355 99298 98 333 81 356 99299 98 334 97 357 99300 93 335 100 358 97301 100 336 100 359 100302 80 337 100 360 100303 100 338 100 361 100305 99 339 100 362 98309 100 340 100 363 100310 100 341 100 364 100311 96 342 99 365 100313 93 343 99 366 95314 87 344 99 367 100316 93 345 100 368 100369 100 392 100 415 100370 97 393 99 416 100371 100 394 98 417 99372 96 395 100 418 100373 100 396 100 419 95374 100 397 100 420 100375 96 398 100 471 100376 100 399 99 472 100377 98 400 100 473 99378 100 401 100 474 97379 100 402 98 475 100380 100 403 97 476 100381 100 404 98 477 100382 100 405 100 478 100383 100 406 100 479 100384 100 407 99 480 100385 100 408 100 481 100386 100 409 100 482 99387 99 410 97 483 100388 100 411 97 484 100389 100 412 100 485 96390 99 413 97 486 98391 92 414 87 487 99______________________________________Compound Control Compound ControlNo. value No. valuetested (%) tested (%)______________________________________488 90 542 96489 100 543 90490 100 Comparative Chemical 1 0491 100492 100 Comparative Chemical 2 13493 100494 100495 97511 100514 100515 100516 100522 98525 96527 77529 91530 90531 80532 88534 70535 97538 98541 70______________________________________ TABLE 3b______________________________________Compound Control Compound ControlNo. value No. valuetested (%) tested (%)______________________________________544 100 568 100545 100 569 100546 100 570 100547 100 571 100548 100549 100 572 100550 100 573 100551 100 574 100552 100 575 100553 100554 100555 100 Comparative Chemical 1 0556 100557 100 Comparative Chemical 2 13558 100559 100560 100561 100562 100563 100565 100566 100______________________________________ TABLE 3c______________________________________Com-pound Control Compound Control Compound ControlNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________581 100 602 100 626 100582 100 604 100 627 100583 100 605 100 628 100584 100 606 100 629 100585 100 607 100 630 100586 100 608 100 631 100587 100 609 100 632 100588 100 610 100 633 100589 98.5 611 100 634 100590 100 612 100 635 100591 100 613 100 636 100592 100 614 100 637 100593 100 615 100 638 100594 100 616 100 639 100595 100 617 100 640 100596 100 618 100 641 100597 100 621 100 642 100598 97.8 622 100 643 100599 100 623 100 644 100600 100 624 100 645 100601 100 625 100 646 100 647 100______________________________________ TABLE 3d______________________________________ Con- Con- Con-Compound trol Compound trol Compound trolNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________648 100 672 81.0 695 100649 91.1 673 100 696 100650 100 674 99.3 697 100651 100 675 100 698 100652 100 676 98.5 699 89.0653 97.6 677 100 700 100654 100 678 100 701 100655 100 679 100 702 100656 88.3 680 100 707 100658 100 681 100 708 100659 100 682 98.5 712 100660 79.3 683 100 713 94.3662 91.2 684 100 714 100 715 97.7663 100 685 100 716 100664 100 686 100 717 100665 100 687 100 718 100666 100 688 100 719 100667 97.8 689 100 720 100668 100 690 100 721 87.4669 100 691 100 723 82.7670 100 692 100 725 100671 83.9 693 100 726 100______________________________________Compound Control Compound ControlNo. value No. valuetested (%) tested (%)______________________________________727 100 757 100728 100 758 100729 100 Comparative730 100 Chemical 1 0731 100 Comparative732 100 Chemical 2 15733 100734 100735 100736 100737 88.2738 100739 100740 100741 100742 100743 100744 100745 100746 100747 100755 100756 94.9______________________________________ Note: In Tables 3a-3d, Comparative Chemical 1: ##STR82## (Disclosed in Japanese Patent Application first publication "Kokai" No. 65871/81) Comparative Chemical 2: ##STR83## - (Disclosed in Japanese Patent Application first publication "Kokai" No. 102504/80)

TEST 2

(Test on the preventive effects for rice blast, Pyricularia oryzae)

Unhulled rice seeds (variety: Aichi Asahi) were sown at a rate of 20 grains each in white porcelain pots having a diameter of 9 cm. The seeds were allowed to germinate and grow for 3-4 weeks in a greenhouse. A wettable powder containing a test compounds and formulated in accordance with the procedure of Example 35 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then sprayed at a rate of 10 ml per pot to the rice seedlings at their 4 leaf stage. After dried in the air, the seedlings were inoculated with a spore suspension of rice blast fungi, Pyricularia oryzae and then placed in a moist room at 25.degree. C. On the fifth day after the inoculation, the number of lesions was counted to evaluate the control value. ##EQU2##

Test results obtained are shown in Table 4a-4d. The same comparative chemicals as in Test 1 were also tested in the same manner as above, for the comparison purpose.

TABLE 4a______________________________________Com- Com-pound Control pound Control Compound ControlNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________1 100 82 93 125 832 94 83 91 129 1006 80 84 83 130 938 93 89 85 133 849 78 93 100 135 10013 86 95 92 136 8216 100 97 93 137 9438 90 102 100 145 10052 85 104 85 150 8960 92 106 79 151 9361 89 107 91 153 8565 100 108 83 160 9466 74 109 93 164 9367 83 110 100 165 8168 100 111 90 168 8471 84 112 90 170 10074 90 113 92 173 10076 93 114 88 174 10077 100 117 89 176 10078 100 123 90 177 10079 100 124 89 179 100182 82 260 100 348 92183 82 261 94 349 100186 100 266 73 351 100187 84 272 100 353 90188 80 277 73 354 82194 100 279 81 355 100198 92 288 100 356 100211 100 295 81 357 100213 91 305 90 358 93219 83 310 80 359 100226 100 318 90 360 100227 100 328 90 361 100229 91 335 80 362 100235 94 337 100 364 91244 100 338 88 365 100245 100 339 85 367 93246 100 340 100 370 100247 100 341 84 371 89252 82 342 100 373 84254 81 344 100 374 100255 100 345 100 376 92257 89 346 100 377 88259 89 347 85 379 94380 100 417 100 Comparative Chemical 1 0381 100 418 100382 100 419 92 Comparative 471 89 Chemical 2 0383 100 472 100385 94 473 84386 93 474 82387 87 475 92388 100 476 90390 100 479 81392 100 481 90393 100 489 88394 100 490 98395 100 491 94396 100 493 100397 100 494 100398 100 495 100400 100 511 97401 86 514 92408 100 525 100409 100 526 81415 90 542 91416 100______________________________________ TABLE 4b______________________________________ Compound No. Control Compound No. Control tested value (%) tested value (%)______________________________________ 544 100 565 97.5 545 100 566 99.5 546 100 569 86.9 547 98.9 572 94.5 548 100 573 100 549 100 574 100 550 96.6 575 98.5 551 97.1 576 100 552 97.1 577 98.5 553 98.3 578 100 554 97.1 579 100 555 100 556 100 Comparative 557 100 Chemical 1 0 558 99.4 Comparative 559 100 Chemical 2 0 560 95.7 561 100 562 97.5 563 97.5 564 98.5______________________________________ TABLE 4c______________________________________Com- Com- Com-pound Control pound Control pound ControlNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________581 100 604 98.4 630 100582 100 605 100 631 100583 99.3 606 100 632 85.3584 98.7 607 100 633 100585 99.5 608 100 634 98.0587 100 609 98.0 635 99.3588 100 611 100 636 100589 91.9 612 99.3 637 100590 91.9 613 100 638 100591 98.3 614 91.1 639 100592 100 615 97.4 640 100593 96.8 616 99.0 641 100 617 100594 99.3 618 100 642 100595 100 621 100 643 98.0596 100 623 98.8 644 99.5597 100 624 100 645 100598 90.5 625 100 646 100599 100 626 98.0 647 100600 100 627 99.3601 99.3 628 99.3602 99.0 629 99.3______________________________________ TABLE 4d______________________________________Com- Com- Com-pound Control pound Control pound ControlNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________648 88.1 677 100 702 100650 100 678 99.4 712 95.8651 97.1 679 98.3 713 100652 91.3 680 92.5 714 90.9653 95.7 681 87.6 716 75.8654 96.3 682 75.8 717 100655 95.7 683 90.0 718 97.4657 71.6 684 75.3 725 92.4658 91.1 685 91.8 726 81.8659 98.6 686 95.9 727 95.0660 99.4 687 88.8 728 81.0661 77.9 688 72.9 730 88.0663 100 689 74.7 731 95.0664 77.5 693 98.5 732 97.6665 100 694 76.8 733 100666 98.3 695 78.1 734 100667 89.6 696 96.9 735 100668 94.8 697 95.9 736 78.3669 96.5 698 96.6 737 68.0670 97.1 700 94.3 738 100673 93.1 701 96.6 739 100740 79.5741 95.8742 95.2743 100744 96.4745 88.5747 100755 92.5Com- 0parativeChemicalCom- 0parativeChemical2______________________________________

TESTS 3

(Test on the preventive effects for cucumber downy mildew, Pseudoperonospora cubensis)

Cucumber seeds (variety: Sagami Hanjiro) were sown at a rate of 12 seeds each in PVC-made pots of 9 cm .times.9 cm. The seeds were allowed to grow in a greenhouse for 7 days. A wettable powder containing a test compound and formulated in accordance with the procedure of Example 35 was diluted with water to concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then applied at a rate of 10 ml per pot to the cucumber seedlings at their cotyledonous stage. After dried in the air, the seedlings were sprayed and inoculated with a spore suspension of cucumber downy mildew fungi, Pseudoperonospora cubensis and then placed in a moist room at 20.degree.-22.degree. C. On the seventh day after the inoculation, the extent of lesion was rated in accordance with the following standards and equation to estimate the degree of development of disease and the control value.

______________________________________Extent of disease:Healthy: No lesion was observed.Slight: Leaf area infected < 1/3 of the whole - leaf areaMedium: Leaf area infected: 2/3 to 1/3 of the - whole leaf areaSevere: Leaf area infected > 2/3 of the whole leaf areaDegree of development of disease (%) =[{(number of healthy leaves .times. 0) + (number ofslightly-infected leaves .times. 1) + (number ofmedium-infected leaves .times. 2) + (number ofseverely-infected leaves .times. 3)} .div. 3N] .times. 100where N denotes the total number of the leave under test. ##STR84##______________________________________

Test Results ar shown in Table 5a-5d below. The same comparative chemicals as in Test 1 were also tested in the same procedure as above, for the comparison purpose.

TABLE 5a______________________________________Com- Com- Com-pound Control pound Control pound ControlNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________1 83 130 100 195 912 83 142 92 196 835 100 143 90 198 866 92 161 94 210 1007 92 166 100 212 838 100 168 100 219 8216 100 169 83 226 10017 100 173 100 235 9220 90 174 100 244 10042 92 176 100 245 9052 80 177 90 247 10065 100 178 83 250 10069 100 179 100 254 8973 100 181 100 255 10076 91 182 100 256 9288 100 183 100 258 9191 83 185 92 266 8392 100 186 100 270 8393 100 187 92 328 8596 95 188 88 329 83104 83 194 100 343 85 401 92 Com- 0345 85 402 100 parative346 100 403 90 Chemical 1361 100 404 80 Com- 0362 100 407 92 parative365 92 408 100 Chemical 2374 100 409 100375 100 416 92376 100 418 100377 100 471 100380 90 478 92381 100 480 92382 100 481 92383 100 482 92388 100 490 100390 100 493 100392 100 495 100393 90 522 100394 85 526 100395 89 527 100397 100 542 91398 100400 100______________________________________ TABLE 5b______________________________________Compound No. tested Control value (%)______________________________________547 100548 83.3549 100550 100551 100553 100555 90557 100558 100566 90573 100575 100576 100577 100578 100Comparative Chemical 1 0Comparative Chemical 2 0______________________________________ TABLE 5c______________________________________Com- Com- Com-pound Control pound Control pound ControlNo. value No. value No valuetested (%) tested (%) tested (%)______________________________________581 100 611 100 640 91.7582 91.7 613 100 641 100583 100 615 75.0 642 100584 100 616 100 645 100585 83.8 618 100 646 100587 100 621 100 647 100588 100 623 100590 91.7 624 100591 100 625 100592 100 627 100595 100 628 100596 100 630 100597 100 631 100600 100 632 100601 100 633 100602 100 634 100604 100 635 100605 100 636 100606 100 637 100607 100 638 91.7609 91.7 639 100______________________________________ TABLE 5d______________________________________Com- Com- Com-pound Control pound Control pound ControlNo. value No. value No. valuetested (%) tested (%) tested (%)______________________________________648 86.0 685 100 727 100650 100 686 100 728 100651 100 687 100 729 83.3655 80.0 690 100 730 100660 100 693 100 731 100663 100 697 83.3 732 100664 91.7 698 100 733 100665 100 700 100 734 100666 100 701 91.7 735 100667 91.7 702 91.7 736 83.3668 100 707 100 737 83.3669 100 708 100 738 100673 100 710 100 739 100675 100 713 100 742 100676 100 714 100 743 100677 100 716 100 744 83.3678 100 717 100 747 100679 100 718 100 755 100680 100 720 83.3 757 100681 91.7 725 100 758 100684 100 726 100 Com- 0 parative Chemical 1 Com- 0 parative Chemical 2______________________________________

TEST 4

(Test on the preventive effects for cucumber gray mold, Botrytis cinerea)

Cucumber seeds (variety: Sagami Hanjiro) were sown at a rate of 12 seeds each in PVC-made pots of 9 cm .times.9 cm. The seeds were allowed to grow for 7 days in a greenhouse. A wettable powder containing a test compound and formulated in accordance with the procedure of Example 35 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then sprayed at a rate of 10 ml per pot to the cucumber seedlings at their cotyledonous stage. After dried in the air, the seedlings were sprayed and inoculated with a suspension of homogenized hypha of cucumber gray fungi, Botrytis cinerea and then placed in a moist chamber at 20.degree.-23.degree. C. On the fourth day after the inoculation, the overall extent of development of disease in each pot was rated in accordance with the following standard.

Infection index

0: No lesion was observed. . 1: Infected area of less than 25% of the total leaf area 2: Infected area of 26-50% of the total leaf area 3: Infected area of 51-75% of the total leaf area 4: Infected area of 76% or more of the total leaf area

Results are shown in Table 6a-Table 6c below. The same comparative chemicals as in Test 1 were also tested in the same way as above, for the comparison purpose.

TABLE 6a______________________________________Com- Com- Com-pound Infec- pound Infec- pound Infec-No. tion No. tion No tiontested Index tested Index tested Index______________________________________ 8 0 284 1 387 1 15 1 288 1 388 0 76 0 305 1 392 0 88 0 335 1 393 0135 0 336 0 394 0159 1 337 1 396 0160 1 338 1 397 0174 1 340 1 410 1176 0 351 0 412 1177 1 353 1 471 1178 1 356 0 472 1179 0 357 1 481 1188 1 361 0 490 1193 1 362 0 493 0194 0 365 0 495 1226 1 367 0 525 1244 0 374 0245 0 381 0 Com- 4246 1 382 1 parative Chemical 1247 0 383 0 Com- 4255 1 385 0 parative260 1 386 0 Chemical 2______________________________________ TABLE 6b______________________________________Compound No. tested Infection Index______________________________________545 0547 0548 0549 0551 0552 0557 0558 0559 1561 1565 0573 0574 0575 0576 0577 0578 0579 0Comparative Chemical 1 0Comparative Chemical 2 1______________________________________ TABLE 6c______________________________________Compound Infec- Compound Infec- Compound Infec-No. tion No. tion No. tiontested Index tested Index tested Index______________________________________581 0.0 611 0.0 640 0.0582 0.0 612 0.0 641 1.0583 0.0 613 0.0 642 0.0585 0.0 621 1.0 644 0.0587 0.0 622 0.0 645 0.0588 0.0 623 0.0 646 0.0589 1.0 624 0.5 647 0.0590 0.0 625 0.0591 1.0 626 1.0592 0.0 627 0.0593 0.0 628 0.0595 0.0 629 0.0596 0.0 630 0.0597 0.0 631 0.0599 0.0 632 0.0600 0.0 633 0.0601 0.0 634 0.0 635 0.0605 0.0 636 0.0606 0.0 637 0.0607 0.0 638 1.0608 1.0 639 0.5______________________________________

TEST 5

(Test on the preventive effects for cucumber powdery mildew, Sphaerotheca fuliginea)

Cucumber seeds (variety: Sagami Hanjiro) were sown at a rate of 12 seeds each in PVC-made pots of 9 cm .times.9 cm. The seeds were allowed to germinate and grow for 7 days in a greenhouse. A wettable powder containing a test compound and formulated in accordance with the procedure of Example 35 was diluted with water to a concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then sprayed at a rate of 10 ml per pot to the cucumber seedlings at their cotyledonous stage. After dried in the air, the seedlings were inoculated with spores of cucumber powdery mildew fungi, Sphaerotheca fuliginea and then placed in a greenhouse at 25.degree.-30.degree. C. On the tenth day after the inoculation, the overall extent of development of disease in each pot was rated in accordance with the following standard.

Infection index

0: No lesion was observed. 1: Infected area of less than 25% of the total leaf area. 2: Infected area of 26-50% of the total leaf area 3: Infected area of 51-75% of the total leaf area 4: Infected area of 76% or more of the total leaf area.

Results are shown in Table 7a-Table 7c below. The same comparative chemicals as in Test 1 were also tested in the same way as above, for the comparison purpose.

TABLE 7a______________________________________Compound Infec- Compound Infec- Compound Infec-No. tion No. tion No. tiontested Index tested Index tested Index______________________________________ 1 1 245 0 383 1 2 1 247 0 385 0 5 1 255 0 388 0 8 0 288 1 392 0 16 1 305 1 393 0 93 1 316 1 394 0 96 1 335 1 397 0104 1 336 0 400 0130 1 337 0 471 1135 1 338 1 472 0160 1 340 0 490 0173 1 351 0 493 1174 0 356 1 495 1176 1 359 1 511 0179 0 361 0 542 1181 1 362 1182 1 365 0 Comparative Chemical 1 3183 1 374 1186 1 376 1 Comparative Chemical 2 4226 0 380 0241 1 381 0244 1 382 1______________________________________ TABLE 7b______________________________________Compound No. tested Infection Index______________________________________545 0546 0547 0548 0549 0551 0553 0557 0558 0559 0561 0566 0573 0574 0575 0576 0577 0578 0579 0Comparative Chemical 1 3Comparative Chemical 2 4______________________________________ TABLE 7c______________________________________Compound Infec- Compound Infec- Compound Infec-No. tion No. tion No. tiontested Index tested Index tested Index______________________________________581 0.0 611 0.0 640 0.0582 0.0 612 0.0 641 0.0583 0.0 613 0.0 642 0.0584 1.0 616 0.0 645 0.0585 0.0 618 0.0 646 0.0587 0.0 622 1.0 647 0.0588 0.0 623 0.0590 0.0 624 1.0591 0.0 625 0.0592 0.0 627 0.0593 0.0 628 0.0595 0.0 629 0.0596 0.0 630 0.0597 0.0 631 0.0599 0.0 632 0.0600 0.0 633 0.0601 0.0 634 0.0602 0.0 635 0.0604 0.0 636 0.0605 0.0 637 0.0606 0.0 638 0.0607 0.0 639 0.0______________________________________

TEST 6

(Test on the preventive effects for Alternaria sooty spot of Chinese mustard, Alternaria brassicicola)

Seeds of Chinese mustard were sown at a rate of 12 seeds each in PVC-made pots of 9 cm .times.9 xm. The seeds were allowed to row for 7 days in a greenhouse. A wettable powder containing a test compound and formulated in accordance with the procedure of Example 35 was diluted with water to concentration of 500 ppm of the active ingredient, and the aqueous preparation obtained was then sprayed at a rate of 10 ml per pot to the seedlings of the Chinese mustard at their cotyledon stage. After dried in the air, the seedlings were sprayed and inoculated with a spore suspension of Alternaria sooty spot fungi, Alternaria brassicicola and then placed in a moist chamber at 30.degree. C. On the third day after the inoculation, the average number of lesions per leaf was determined to estimate the control value in accordance with the following equation. Test Results of rating evaluated in accordance with the following evaluation standard are given in Table 8a-8c below. ##EQU3##

Again, the same comparative chemicals as those employed in Test 1 were also tested for the comparison purpose.

TABLE 8a______________________________________Compound Compound CompoundNo. Evalu- No. Evalu- No. Evalu-tested ation tested ation tested ation______________________________________ 1 A 173 B 288 B 2 A 174 A 292 B 5 B 176 A 298 B 8 A 179 B 299 B 9 B 181 B 324 B 10 B 182 B 337 A 16 A 183 B 341 B 18 B 187 A 342 B 26 B 194 A 345 B 31 B 196 B 351 B 35 B 198 A 356 A 65 B 219 B 357 A 76 A 226 A 358 A 91 A 227 A 360 A 93 A 244 A 361 A109 B 245 A 362 A110 B 247 A 365 A123 B 249 B 366 B135 B 250 A 373 B159 B 255 A 374 A164 B 259 B 376 A380 B 490 A381 A 493 B382 B 525 B383 A385 B Comparative Chemical 1 D387 A Comparative388 A Chemical 2 D390 A392 A393 A394 A395 B396 A397 A398 B400 A408 B409 A417 B472 A474 B484 B______________________________________ TABLE 8b______________________________________Compound No.tested Evaluation______________________________________545 B547 B548 A549 A550 B551 A553 B555 B556 B557 B558 A559 B560 B561 A665 B566 B573 B574 B575 A576 A577 B578 B579 BComparativeChemical 1 DComparativeChemical 2 D______________________________________ TABLE 8c______________________________________Compound Compound CompoundNo. Evalu- No. Evalu- No. Evalu-tested ation tested ation tested ation______________________________________581 A 609 A 635 A582 A 610 A 636 A583 A 611 A 637 A585 A 612 A 638 A586 C 613 A 639 A587 A 614 B 640 A588 A 615 A 641 A590 A 616 A 642 A591 A 618 A 643 A592 A 621 A 644 A593 C 622 A 645 A595 A 623 A 646 A596 A 624 A 647 A597 A 625 A599 A 626 A600 A 627 A601 A 628 A602 A 629 A604 A 630 A605 A 631 A606 A 632 A607 A 633 A608 A 634 A______________________________________

TEST 7

(Test on the preventive effects for rice sheath blight at low rate application of test compounds)

Each 9 seedlings of rice plants (variety: Kinmaze) were transplanted in a white porcelain pot of 9 cm diameter containing paddy soils. The plants were allowed to grow to the 7-8 leaf stage in a greenhouse. A wettable powder containing a test compound formulated in accordance with the procedure of Example 35 was diluted in water to concentrations of the active ingredient as specified in the following Table 9. The aqueous preparation obtained was sprayed onto the rice plants at a rate of 10 ml per pot. After dried in the air, the each plant so treated was inoculated with an agar disk of the pathogenic fungus of rice sheath blight (Rhizoctonia solani) which has been cultured on a potato dextrose agar medium for 2 days, on the basal part of the sheath. The plants inoculated were kept in a moist chamber to allow the disease development at 28.degree. C. Seven days later, the height of lesion formed on the sheath was measured.

Then, the control value (%) of the disease provided by the test compound was calculated according to the following equation. ##EQU4## The test was made in three replicates using 3 pots in each plot. The results obtained are summarized in Table 9 below.

TABLE 9______________________________________ Control value (%) Concentration of the active ingre- dient in the sprayed liquidCompound No. preparationtested 1 ppm 3 ppm 10 ppm______________________________________ 93 64.5 79.3 84.3388 89.1 93.9 98.0392 80.0 97.5 99.2135 87.9 91.5 98.6503 86.7 94.7 98.3557 88.9 92.4 96.6558 85.5 94.9 97.5642 96.8 99.4 99.8583 94.2 96.7 97.5693 72.0 81.1 97.2665 60.9 71.7 93.5244 90.0 92.9 98.6472 71.6 85.4 98.1336 66.1 87.6 88.3154 81.2 88.9 97.3632 76.4 97.7 97.7625 81.3 94.6 97.6592 92.5 97.5 98.4659 73.3 97.2 99.1Untreated 0 0 0______________________________________

In the untreated plot, the average height of the sheath blight lesions amounted to 10.86 cm.

TEST 8

the procedures of Tests 1 to 6 were respectively repeated using some compounds of this invention as indicated in Table 10 shown below, as well as another, comparative compounds A to comparative compound E as indicated in Table 10. The control value (%) for the respective plant disease was evaluated in the same manner as in Tests 1, 2, 3 and 6, or the infection index was evaluated in the same manner as in Tests 4 and 5 above.

The test results obtained are rated in accordance with the following evaluation standards:

Class A: Control value of greater than 90%, or Infection index of 0. Class B: Control value of from 70% and up to 90%, or Infection index of 1. Class C: Control value of greater than 50% and up to 70%, or Infection index of 2. Class D: Control value of less than 50%, or Infection index of 3-4.

The results ar summarised in Table 10 below.

TABLE 10__________________________________________________________________________ ##STR85## Evaluation of Control value Cucum- Cucum- Cucum- Alter- Rice ber ber ber naria Substituents in tested compound sheath Rice downy gray powdery spoty X.sub.l Y.sub.m Z.sub.n A R blight blast mildew mold mildew spot__________________________________________________________________________Compound No.tested93 3,5-(OCH.sub.3).sub.2 H H O CH.sub.3 A A A D B A388 3,5-(OCH.sub.3).sub.2 2-Cl H O CH.sub.3 A A A A A A392 3,5-(OCH.sub.3).sub.2 4-OCH.sub.3 H O CH.sub.3 A A A A A A135 2-Cl 5-OCH.sub.3 H H O CH.sub.3 A A C A B B503 2-Cl 5-OCH.sub.3 H 2-F O CH.sub.3 A A A A A A557 2-Cl 3,5-(OCH.sub.3).sub.2 H 2-F O CH.sub.3 A A A A A A558 3,5-(OCH.sub.3).sub.2 2-F 2-F O CH.sub.3 A A A A A A642 3,5-(OCH.sub.3).sub.2 2,4-F.sub.2 2-F O CH.sub.3 A A A A A A583 H 2-Cl 2-F O CH.sub.3 A A A A A A693 3,5-(OCH.sub.3).sub.2 2-F 2-F O Cl A A A A A A665 3,5-(OCH.sub.3).sub.2 2-F 2-F S CH.sub.3 A A A A A A244 H 2,4-F.sub.2 H O CH.sub.3 A A A A B A472 2-Cl H 2-F O CH.sub.3 A A C B A A336 2-Cl 2-Cl H O CH.sub.3 A B C A A B154 2-Cl 3,5-(OCH.sub.3).sub.2 H H O CH.sub.3 A A A A A A633 3,5-(OCH.sub.3).sub.2 2-Cl 2-F O CH.sub.3 A A A A A A625 2-Cl 3,5-(OCH.sub.3).sub.2 4-OCH.sub.3 2-F O CH.sub.3 A A A A A A592 2-Br 3,5-(OCH.sub.3).sub.2 H 2-F O CH.sub.3 A A A A A AComparativecompound A H H H O H B D B D C DComparative 2-Cl H H O H A D D D D Bcompound BComparative 3-OCH.sub.3 H H O H A D B D D Ccompound CComparative H H H O CH.sub.3 A D D D D Dcompound DComparative 3-CH.sub.3 H H O CH.sub.3 A D D D D Ccompound E__________________________________________________________________________ In Table 10 above, when "H" is shown in the columns of "X.sub.l ", "Y.sub.m " and/or "Z.sub.n ", this again means that the substituent X, Y and Z are absent, that is say, that the value of l, m and/or n is zero.

Claims

1. A 4(1H)-pyridinone derivative represented by the formula ##STR86## wherein X, Y and Z are the same or different and are independently a halogen atom, a nitro group, a cyano group, a hydroxy group, aldehyde group (--CHO), a lower alkyl group, a halogen-substituted lower alkyl group, a lower cyanoalkyl group, a lower hydroxyalkyl group, a lower alkoxyalkyl group, a lower alkoxy group, a halogen-substituted lower alkoxy group, a lower alkoxyalkoxy group, a lower alkenyl group, a lower alkenyloxy group, a lower alkynyl group, a lower alkynyloxy group, a lower alkanoyl group, a lower alkanoyloxy group, a phenyl group, a phenoxy group, a carbamoyl group, a lower alkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or a lower alkyl group, or a substituted or unsubstituted amino group of the formula ##STR87## where R.sup.2 and R.sup.3 are the same or different and are each a hydrogen atom, a lower alkyl group or a lower alkanoyl group; or X, Y and Z are independently a group of the formula --(O).sub.p --S--R.sup.4 is a lower alkyl group and p is an integer of 0 to 3; or X, Y and Z are independently a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the same benzene ring to which X, Y and Z is linking so that X, Y and Z taken together with said two adjacent two carbon atoms of the same benzene ring forms a 5-membered ring,

l, m and n are independently an integer of 0 to 5,

R is a halogen atom, a cyano group, a lower alkyl group, a halogen-substituted lower alkyl group, a lower alkoxy group, a lower alkenyl group, a lower alkynyl group, a phenyl group, a benzyl group, a trimethylsilylethynyl group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is as defined above, or a substituted methyl group of the formula --CH.sub.2 OR.sup.5 where R.sup.5 is a hydrogen atom, a lower alkyl group or a benzoyl group,

A is an oxygen atom or a sulfur atom, provided that when R is methyl and A is an oxygen atom, l, m and n do not denote zero simultaneously; and provided that when R and X are each a methyl group, A is an oxygen atom and l is l, m and n do not denote zero simultaneously, and a salt of the compound of the formula (I) above.

2. A compound as claimed in claim 1 in which R is a (C.sub.1 -C.sub.6) alkyl group, a halogen atom, a cyano group or a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or a lower alkyl group.

3. A compound as claimed in claim 1, in which R is a (C.sub.1 -C.sub.4) alkyl group, a chlorine atom or a bromine atom.

4. A compound as claimed in claim 1 in which X, Y and Z are the same or different and are independently a lower alkyl group, a lower alkoxy group, a halogen-substituted lower alkyl group, a lower alkoxy group, a halogen-substituted lower alkoxy group, a halogen group, nitro group, cyano group, a lower alkenyl group, a lower alkenyloxy group, a lower alkynyl group or a lower alkynyloxy group, or X, Y and Z are independently a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the same benzene ring to which X, Y or Z is linking so that X, Y or Z taken together with said two carbon atoms of the same benzene ring forms a 5-membered ring,

l, m and n are independently an integer of 0 to 5,

A is an oxygen atom or a sulfur atom.

5. A compound as claimed in claim 1 in which two or more groups are present for each of the groups X, Y and Z and they are the same or different from each other in their nature.

6. A compound as claimed in claim 1 in which the sum of l, m and n is equal to 2 or greater than 2.

7. A compound as claimed in claim 1 in which X is a halogen atom or a lower alkoxy group or a combination of halogen atom(s) and lower alkoxy group(s); Y is a halogen atom or a lower alkoxy group or a combination of halogen atom(s) and lower alkoxy group(s); and Z is a halogen atom or a lower alkoxy group or a combination of halogen atom(s) and lower alkoxy group(s).

8. A compound as claimed in claim 1 in which one, two or three groups for X is or are present therein and positioned at the 2-position, the 3-position, the 2- and 4-positions, the 3- and 5-positions or the 2-, 3- and 5-positions of the benzene ring to which the group(s) X is or are linking.

9. A compound as claimed in claim 1, which is represented by the formula ##STR88## wherein X.sup.a is a halogen atom, a nitro group, a cyano group, a hydroxy group, a lower alkyl group, a halogen-substituted lower alkyl group, a lower cyanoalkyl group, a lower hydroxyalkyl group, a lower alkoxyalkyl group, a lower alkoxy group, a halogen-substituted lower alkoxy group, a lower alkoxyalkoxy group, a lower alkenyl group, a lower alkenyloxy group, a lower alkynyl group, a lower alkynyloxy group, a lower alkanoyl group, a lower alkanoyloxy group, a phenyl group, a phenoxy group, a carbamoyl group, a lower alkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or a lower alkyl group, or a substituted or unsubstituted amino group of the formula ##STR89## where R.sup.2 and R.sup.3 are the same or different and are each a hydrogen atom, a lower alkyl group or a lower alkanoyl group; or X.sup.a is a group of the formula --(O).sub.p --S--R.sup.4 where R.sup.4 is a lower alkyl group and p is an integer of 0 to 3; or X.sup.a is a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the same benzene ring to which X.sup.a is linking so that X.sup.a taken together with said two adjacent two carbon atoms of the benzene ring forms a 5-membered ring,

Y.sup.a is a halogen atom, a nitro group, a cyano group, a hydroxy group, a lower alkyl group, a halogen-substituted lower alkyl group, a lower hydroxyalkyl group, an lower alkoxyalkyl group, a lower alkoxy group, a halogen-substituted lower alkoxy group, a lower alkoxyalkoxy group, a lower alkenyl group, a lower alkneyloxy group, a lower alkynyl group, a lower alkynyloxy group, a lower alkanoyl group, a lower alkanoyloxy group, a carbamoyl group, a lower alkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or a lower alkyl group, or Y.sup.a is a group of the formula --(O).sub.p --S--R.sup.4 where R.sup.4 is a lower alkyl group and p is an integer of 0 to 3; or Y.sup.a is a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the same benzene ring to which Y.sup.a is linking so that Y.sup.a taken together with said two adjacent carbon atoms of the same benzene ring forms a 5-membered ring,

Z.sup.a is a halogen atom, a nitro group, a cyano group, a hydroxyl group, aldehyde group (--CHO), a lower alkyl group, a halogen-substituted lower alkyl group, a lower hydroxyalkyl group, a lower alkoxyalkyl group, a lower alkoxy group, a halogen-substituted lower alkoxy group, a lower alkoxyalkoxy group, a lower alkenyl group, a lower alkenyloxy group, a lower alkynyl group, a lower alkynyloxy group, a lower alkanoyl group, a lower alkanoyloxy group, a carbamoyl group, a lower alkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is a hydrogen atom or a lower alkyl group, or Z.sup.a is a group of the formula --(O).sub.p --S--R.sup.4 where R.sup.4 is a lower alkyl group and p is an integer of 0 to 3; or Z.sup.a is a trimethylene group or a methylene-dioxo group bonded to and bridging between the adjacent two carbon atoms of the same benzene ring to which Z.sup.a is linking so that Z.sup.a taken together with said two adjacent two carbon atoms of the same benzene ring forms a 5-membered ring, s is an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; and r is an integer of zero, 1 or 2,

R.sup.a is a halogen atom, a cyano group, a lower alkyl group, a halogen-substituted lower alkyl group, a lower alkoxy group, a lower alkenyl group, a lower alkynyl group, a phenyl group, a benzyl group, a trimethylsilyethynyl group, a carboxyl or carboxylate group of the formula --COOR.sup.1 where R.sup.1 is as defined above, or a substituted methyl group of the formula --CH.sub.2 OR.sup.5 where R.sup.5 is a hydrogen atom, a lower alkyl group or a benzoyl group, provided that when R.sup.a is methyl, s, t, and r do not denote zero simultaneously.

10. A compound as claimed in claim 1, which is represented by the formula ##STR90## wherein X.sup.b is a halogen atom or a lower alkoxy group or a combination of halogen atom(s) and lower alkoxy group(s); Y.sup.b is a halogen atom, or a lower alkoxy group; and Z.sup.b is a halogen atom,

s is an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; and r is an integer of zero, 1 or 2.

R.sup.b is a lower alkyl group or a halogen atom, provided that when R.sup.b is methyl, s, t and r do not denote zero simultaneously.

11. A compound as claimed in claim 1, which is represented by the formula ##STR91## wherein X, Y and Z are the same or different and are independently a halogen atom, a lower alkoxy group, a lower alkenyl group, a lower alkenyloxy group, a lower alkynyl group or a lower alkynyloxy group,

l, m and n are independently an integer of 0 to 5,

R is a lower alkyl group or a halogen-substituted lower alkyl group.

12. A compound as claimed in claim 1, which is represented by the formula ##STR92## wherein X.sup.c is a lower alkyl group; Y.sup.c is a halogen atom, a lower alkyl group, or a lower alkoxy group; and Z.sup.c is a halogen atom,

s is an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; and r is an integer of zero, 1 or 2,

R.sup.c is a lower alkyl group or a halogen atom, provided that when R.sup.c is methyl, s, t and r do not denote zero simultaneously, and provided that t and r do not denote zero simultaneously.

13. A compound as claimed in claim 1 or claim 9, which is selected from a compound of the formula: ##STR93##

14. A compound as claimed in claim 1, selected from the group consisting of ##STR94##

15. A fungicidal composition for agricultural and horticultural utilities, which comprises a compound of the formula (I) as defined in claim 1 or a salt thereof as the active ingredient, in combination with a carrier for the active ingredient.