Benzyloxy substituted aromatics and their use as fungicides and insecticides

Compounds with fungicidal and insecticidal properties having formula ##STR1## wherein A is N or CH; V is O or NH; m and n are independently 0 and 1 provided that m+n is not 2, and U and W are independently O or N; PA0 such that when U and W are both N and n is 0 and m is 1, the bond between the 1 and 5 atoms is a double bond and the bond between the C.sub.3 -C.sub.4 atoms is a single or double bond, and when n is 1 and m is 0, the bond between the 2 and 3 atoms is a double bond and the bond between the C.sub.4 -C.sub.5 atoms is a single or double bond; PA0 and that when U is O and W is N and n=m=0, the bond between the 1 and 5 atoms is a double bond and the bond between the C.sub.3 -C.sub.4 atoms is a single or double bond; PA0 and that when U is N and W is O and n=m=0, the bond between the 2 and 3 atoms is a double bond and the bond between the C.sub.4 -C.sub.5 atoms is a single or double bond; PA0 X is independently selected from hydrogen, halo, (C.sub.1 -C.sub.4)alkyl, and C.sub.1 -C.sub.4)alkoxy; PA0 R is independently selected from hydrogen, (C.sub.1 -C.sub.12)alkyl, halo(C.sub.1 -C.sub.12)alkyl, (C.sub.2 -C.sub.8)alkenyl, (C.sub.2 -C.sub.8)alkynyl(C.sub.1 -C.sub.12)alkoxy(C.sub.1 -C.sub.12)alkyl, (C.sub.3 -C.sub.7)cycloalkyl, (C.sub.3 -C.sub.7)cycloalkyl(C.sub.1 -C.sub.4)alkyl, aryl, aralkyl, heterocyclic and PA0 R.sub.1 is independently selected from hydrogen, (C.sub.1 -C.sub.6)alkyl, and aryl; and PA0 Z is selected from (C.sub.1 -C.sub.6)alkyl, halo(C.sub.1 -C.sub.6)alkyl, (C.sub.3 -C.sub.7) cycloalkyl, (C.sub.3 -C.sub.7)cycloalkyl(C.sub.1 -C.sub.4)alkyl, aryl and aralkyl.

The present invention relates to benzyloxy substitutedphenyl compounds, 
compositions containing these compounds and methods for controlling fungi 
and insects by the use of a fungitoxic and insecticidal amount of these 
compounds. 
It is known that propenoic acids and oxime ethers of certain benzyloxy 
substituted phenyl compounds are useful as fungicides. The substitution of 
the phenyl ring big certain heterocycles is known in the art (see for 
example U.S. Pat. No. 5,185,342) 
We have discovered phenyl derivatives which possess a five membered ring 
heterocycle. These novel compositions also possess fungicidal and 
insecticidal properties. 
The novel benzyloxy substitutedphenyl compounds of the present invention 
have the Formula (I) 
##STR2## 
wherein A is N or CH; V is O or NH; m and n are independently 0 and 1 
provided that m+n is not 2, and U and W are independently O or N; 
such that when U and W are both N and n is 0 and m is 1, the bond between 
the 1 and 5 atoms is a double bond and the bond between the C3-C4 atoms is 
a single or double bond, and when n is 1 and m is 0, the bond between the 
2 and 3 atoms is a double bond and the bond between the C4-C5 atoms is a 
single or double bond; 
and that when U is O and W is N and n=m=0, the bond between the 1 and 5 
atoms is a double bond and the bond between the C3-C4 atoms is a single or 
double bond; 
and that when U is N and W is O and n=m=0, the bond between the 2 and 3 
atoms is a double bond and the bond between the C4-C5 atoms is a single or 
double bond; 
X is independently selected from hydrogen, halo, (C.sub.1 -C.sub.4)alkyl, 
and C.sub.1 -C.sub.4)alkoxy; 
R is independently selected from hydrogen, (C.sub.1 -C.sub.12)alkyl, 
halo(C.sub.1 -C.sub.12)alkyl, (C.sub.2 -C.sub.8)alkenyl, (C.sub.2 
-C.sub.8)alkynyl, (C.sub.1 -C.sub.12)alkoxy(C.sub.1 -C.sub.12)alkyl, 
(C.sub.3 -C.sub.7)cycloalkyl, (C.sub.3 -C.sub.7)cyctoalkyl(C.sub.1 
-C.sub.4)alkyl, aryl, aralkyl, heterocyclic; and 
R.sub.1 is independently selected hydrogen, (C.sub.1 -C.sub.6)alkyl, and 
aryl; 
Z is selected from (C.sub.1 -C.sub.6)alkyl, halo(C.sub.1 -C.sub.6)alkyl, 
(C.sub.3 -C.sub.7)cycloalkyl, (C.sub.3 
-C.sub.7)cycloalkyl(C.sub.1-C.sub.4)alkyl, aryl, aralkyl. 
The aforementioned (C.sub.1 -C.sub.12)alkyl, (C.sub.1 -C.sub.2)alkoxy, 
(C.sub.2 -C.sub.8)alkenyl, (C.sub.2 -C.sub.8) alkynyl and (C.sub.3 
-C.sub.7)cycloalkyl groups may be optionally substituted with up to three 
substituents selected from the group consisting of halogen, nitro, 
trihalomethyl and cyano. 
The term alkyl includes both branched and straight chained alkyl groups 
from 1 to 12 carbon atoms. Typical alkyl groups are methyl, ethyl, 
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, 
isopentyl, n-hexyl, n-heptyl, isooctyl, nonyl, decyl, undecyl, dodecyl and 
the like. The term haloalkyl refers to an alkyl group substituted with 1 
to 3 halogens. 
The term alkenyl refers to an ethylenically unsaturated hydrocarbon group, 
straight or branched, having a chain length of 2 to 12 carbon atoms and 1 
or 2 ethylenic bonds. The term haloalkenyl refers to an alkenyl group 
substitued with 1 to 3 halogen atoms. The term alkynyl refers to an 
unsaturated hydrocarbon group, straight or branched, having a chain length 
of 2 to 12 carbon atoms and 1 or 2 acetylenic bonds. 
The term cycloalkyl refers to a saturated ring system having 3 to 7 carbon 
atoms. 
The term aryl is understood to be plhenyl or napthyl, which is optionally 
substituted with up to three substituents selected from the group 
consisting of halogen, cyano, nitro, trihalomethyl, phenyl, phenoxy, 
(C.sub.1 -C.sub.4)alkyl, (C.sub.1 -C.sub.4)alkylthio, (C.sub.1 
-C.sub.4)alkylsulfoxide (C.sub.1 -C.sub.6)alkoxy and halo(C.sub.1 
-C.sub.4)alkyl. 
Typical aryl substituents include but are not limited to 4-chlorophenyl, 
4-fluorophenyl, 4-bromnophenyl, 2-nmethoxyphenyt, 2-methylpllenyl, 
3-methyphenyl, 4-methylphenyl, 2,4-dibromophenyl, 3,5-difluolroplhenyl, 
2,4,6-trichlorophenyl, 4-methoxyphenyl, 2-chloronapthyl, 
2,4-dimethoxyphenyl, 4-(trifluoromethyl)phenyl and 2-iodo-4-methylphenyl. 
The term heterocyclic refers to a substituted or unsubstituted 5 or 6 
membered unsaturated ring containing one, two or three heteroatoms, 
preferably one or two heteroatoms selected from oxygen, nitrogen and 
sulfur; or is a bicyclic unsaturated ring system containing up to 10 atoms 
including one heteratom selected from oxygen, nitrogen and sulfur. 
Examples of heterocycles includes, but is not limited to, 2-, 3- or 
4-pyridinyl, pyrazinyl, 2-, 4-, or 5-pyrimidinyl, pyridazinyl, triazolyl, 
imidazolyl, 2- or 3-thienyl, 2- or 3-furyl, pyrrolyl, oxazolyl, 
isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, quinolyl 
and isoquinolyl. The heterocyclic ring may be optionally substituted with 
up to two substituents independently selected from (C.sub.1 
-C.sub.4)alkyl, halogen, cyano, nitro and trihalomethyl. 
The term aralkyl is used to describe a group wherein the the alkyl chain is 
from 1 to 10 carbon atoms and can be branched or straight chain, 
preferably a straight chain, with a terminal aryl portion, as defined 
above. Typical aralkyl moieties include, but are not limited to, 
optionally substituted benzyl, phenethyl, phenpropyl and phenbutyl 
moieties. Typical benzyl moieties are 2-chlorobenzyl, 3-chlorobenzyl, 
4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 
4-trifluoromethylbenzyl, 2,4-dichloro-benzyl, 2,4-dibromobenzyl, 
2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl. Typical phenethyl 
moieties are 2-(2-chlorophenyl)ethyl, 2-(3-chloroplhenyl)ethyl, 
2-(4-chloroplhenyl)ethyl, 2-(2-fluorophenyl)ethyl, 
2-(3-fluorophenyl)ethyl, 2-(4-fluoro-phenyl)ethyl, 
2-(2-methylphenyl)ethyl, 2-(3-methylphenyl)ethyl, 
2-(4-methyl-phenyl)ethyl, 2-(4-trifluoromnethylphenyl)ethyl, 
2-(2-methoxyphenyl)ethyl, 2-(3-methoxyphenyl)ethyl, 
2-(4-methoxyphenyl)ethyl, 2-(2,4-dichlorophenyl)ethyl, 
2-(3,5-dinmethoxyphenyl)ethyl. Typical phenpropyl moieties are 
3-phenylpropyl, 3-(2-chloro-phenyl)propyl, 3-(3-chlorophenyl)propyl, 
3-(4-chlorophenyl)propyl, 3-(2,4-dichloro-phenyl)propyl, 
3-(2-fluorophenyl)propyl, 3-(3-fluorophenyl)propyl, 
3-(4-fluorophenyl)-propyl, 3-(2-methylphenyl)propyl, 
3-(3-methylphenyl)propyl, 3-(4-methylphenyl)-ethyl, 
3-(2-methoxyphenyl)propyl, 3-(3-mnethoxyphenyl)propyl, 3-(4-methoxyphenyl) 
propyl, 3-(4-trifluoromethylphenyl)propyl, 3-(2,4-dichlorophenyl)propyl 
and 3-(3,5-dimethoxyphenyl)propyl. Typical phenbutyl moities include are 
4-phenylbutyl, 4-(2-chloroplienyl)butyl, 4-(3-chlorophenyl)butyl, 
4-(4-chlorophenyl)butyl, 4-(2-fluorophenyl)butyl, 4-(3-fluorophenyl)butyl, 
4-(4-fluorophenyl)butyl, 4-(2-methylphenyl)butyl, 4-(3-methylphenyl)butyl, 
4-(4-methylphenyl)butyl, 4-(2,4-dichlorophenyl)butyl, 
4-(2-methoxyphenyl)butyl, 4-(3-methoxyphenyl)butyl and 
4-(4-niethoxy-phenyl)butyl. 
Halogen or halo is meant to include iodo, fluoro, bromo and chloro 
moieties. 
Because of the C.dbd.C or C.dbd.N double bonds the novel compounds of the 
general Formula I mnay be obtained in preparation as E/Z isomeric 
mixtures. These isomers can be separated into individual components by 
conventional means. The pyrazolines and isoxazolines of Formula I may be 
obtained in preparation as cis and trans isomeric mixtures. These isomers 
can be separated into individual components by conventional means. Both 
the individual isomeric compounds and mixtures thereof form subjects of 
the invention and can be used as fungicides. 
A preferred embodiment of this invention are the compounds, enantiomorphs, 
salts and complexes of Formula (I) when R is (C.sub.1 -C.sub.12)alkyl; 
phenyl substituted with preferably one or two substituents independently 
selected from halo, trihalomethyl, cyano, (C.sub.1 -C.sub.4)alkyl, 
(C.sub.1 -C.sub.4)alkylthio, (C.sub.1 -C.sub.4)alkoxy; or phenyl, R.sub.1 
is H, where the OCH.sub.2 (2-substitutedphenyl) moiety is bonded at the 
meta position to the 5-menmbered ring substituent of the phenyl ring as 
shown in Formula I'. 
A more preferred embodiment of this invention are the compounds, 
enantiomorphs, salts and complexes of Formula (I) is when X is hydrogen 
and R is halophenyl and A is CH and V is O. The preferred geometry when A 
is CH or N is the E isomer. 
##STR3## 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 1 of Formula II, III and IV where 
X.dbd.H, R.sub.1 .dbd.H, U and W are N and n=0 and m=1. 
TABLE 1 
______________________________________ 
##STR4## 
##STR5## 
##STR6## 
Cmpd# R Formula Z A V 
______________________________________ 
1.01 Ar II CH.sub.3 
CH O 
1.02 Ar III CH.sub.3 
CH O 
1.03 Ar IV CH.sub.3 
CH O 
1.04 4-Cl(Ar) II CH.sub.3 
CH O 
1.05 4-Cl(Ar) III CH.sub.3 
CH O 
1.06 4-Cl(Ar) IV CH.sub.3 
CH O 
1.07 4-F(Ar) II CH.sub.3 
CH O 
1.08 4-F(Ar) III CH.sub.3 
CH O 
1.09 4-F(Ar) IV CH.sub.3 
CH O 
1.10 2-CH.sub.3 (Ar) 
II CH.sub.3 
CH O 
1.11 2-CH.sub.3 (Ar) 
III CH.sub.3 
CH O 
1.12 2-CH.sub.3 (Ar) 
IV CH.sub.3 
CH O 
1.13 4-CH.sub.3 (Ar) 
II CH.sub.3 
CH O 
1.14 4-CH.sub.3 (Ar) 
III CH.sub.3 
CH O 
1.15 4-CH.sub.3 (Ar) 
IV CH.sub.3 
CH O 
1.16 4-CF.sub.3 (Ar) 
II CH.sub.3 
CH O 
1.17 2,4-Cl(Ar) II CH.sub.3 
CH O 
1.18 CH.sub.3 II CH.sub.3 
CH O 
1.19 CH.sub.2 CH.sub.3 
II CH.sub.3 
CH O 
1.20 CH.sub.2 CH.sub.2 CH.sub.3 
II CH.sub.3 
CH O 
1.21 CH(CH.sub.3).sub.2 
II CH.sub.3 
CH O 
1.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
II CH.sub.3 
CH O 
1.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
II CH.sub.3 
CH O 
1.24 CH.sub.2 CH(CH.sub.3).sub.2 
II CH.sub.3 
CH O 
1.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
II CH.sub.3 
CH O 
1.26 C(CH.sub.3).sub.3 
II CH.sub.3 
CH O 
1.27 CH.sub.2 C(CH.sub.3).sub.3 
II CH.sub.3 
CH O 
1.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
II CH.sub.3 
CH O 
1.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
II CH.sub.3 
CH O 
1.30 CF.sub.3 II CH.sub.3 
CH O 
1.31 CF.sub.2 CF.sub.3 
II CH.sub.3 
CH O 
1.32 CH.sub.2 CF.sub.3 
II CH.sub.3 
CH O 
1.33 CHCH.sub.2 II CH.sub.3 
CH O 
1.34 cyclopropyl II CH.sub.3 
CH O 
1.35 cyclopentyl II CH.sub.3 
CH O 
1.36 cyclohexyl II CH.sub.3 
CH O 
1.37 CH.sub.2 OCH.sub.3 
II CH.sub.3 
CH O 
1.38 CH.sub.2 OCH.sub.2 CH.sub.3 
II CH.sub.3 
CH O 
1.39 CH.sub.2 CH.sub.2 OCOAr 
II CH.sub.3 
CH O 
1.40 CH.sub.2 OCH.sub.2 Ar 
II CH.sub.3 
CH O 
1.41 2-pyridyl II CH.sub.3 
CH O 
1.42 3-pyridyl II CH.sub.3 
CH O 
1.43 2-pyrimidyl II CH.sub.3 
CH O 
1.44 4-pyrimidyl II CH.sub.3 
CH O 
1.45 2-thienyl II CH.sub.3 
CH O 
1.46 3-thienyl II CH.sub.3 
CH O 
1.47 2-napthyl II CH.sub.3 
CH O 
1.48 Ar II C.sub.2 H.sub.5 
CH O 
1.49 4-Cl(Ar) II C.sub.2 H.sub.5 
CH O 
1.50 CH.sub.3 II C.sub.2 H.sub.5 
CH O 
1.51 CH.sub.2 CH.sub.3 
II C.sub.2 H.sub.5 
CH O 
1.52 CH.sub.2 CH.sub.2 CH.sub.3 
II C.sub.2 H.sub.5 
CH O 
1.53 CH(CH.sub.3).sub.2 
II C.sub.2 H.sub.5 
CH O 
1.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
II C.sub.2 H.sub.5 
CH O 
1.55 CH.sub.2 CH(CH.sub.3).sub.2 
II C.sub.2 H.sub.5 
CH O 
1.56 C(CH.sub.3).sub.3 
II C.sub.2 H.sub.5 
CH O 
1.57 Ar III 4-Cl(Ar) 
CH O 
1.58 Ar II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.59 CH.sub.3 II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.60 CH.sub.2 CH.sub.2 CH.sub.3 
II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.61 CH(CH.sub.3).sub.2 
II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.63 CH.sub.2 CH(CH.sub.3).sub.2 
II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.64 C(CH.sub.3).sub.3 
II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.65 2-pyridyl II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.66 3-pyridyl II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.67 4-pyrimidyl II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.68 2-thienyl II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.69 3-thienyl II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
1.70 2-napthyl II CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
______________________________________ 
Further typical compounds described by the present invention are described 
in the following tables. 
Table 2: 
Compounds 2.1 to 2.47 are Conpounds of Table 1 of Formula II, III, IV where 
Z is Ar. 
Table 3: 
Compounds 3.1 to 3.47 are Compounds of Table 1 of Formula II, III, IV where 
Z is CH.sub.2 Ar. 
Table 4: 
Compounds 4.1 to 4.47 are Compounds of Table 1 of Formula II, III, IV where 
Z is CH.sub.2 CF.sub.3. 
Table 5: 
Compounds 5.1 to 5.47 are Compounds of Table 2 of Formula II, III, IV where 
V.dbd.O and A is N. 
Table 6: 
Compounds 6.1 to 6.47 are Compounds of Table 2 of Formula II, III, IV where 
V.dbd.NH and A is N. 
Table 7: 
Compounds 7.1 to 7.47 are Compounds of Table 3 of Formula II, III, IV where 
V.dbd.O and A is N. 
Table 8: 
Compounds 8.1 to 7.47 are Compounds of Table 3 of Formula II, III, IV where 
V.dbd.NH and A is N. 
Table 9: 
Compounds 9.1 to 9.47 are Compounds of Table 4 of Formula II, III, IV where 
V.dbd.O and A is N. 
Table 10: 
Compounds 10.1 to 10.47 are Compounds of Table 4 of Formula II, III, IV 
where V.dbd.NH and A is N. 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 11 of Formula V, VI and VII where 
X.dbd.H, R.sub.1 .dbd.H, U and W are N and n=1 and m=0. 
TABLE 11 
______________________________________ 
##STR7## 
##STR8## 
##STR9## 
Cmpd# R Formula Z A V 
______________________________________ 
11.01 Ar V CH.sub.3 
CH O 
11.02 Ar VI CH.sub.3 
CH O 
11.03 Ar VII CH.sub.3 
CH O 
11.04 4-Cl(Ar) V CH.sub.3 
CH O 
11.05 4-Cl(Ar) VI CH.sub.3 
CH O 
11.06 4-Cl(Ar) VII CH.sub.3 
CH O 
11.07 4-F(Ar) V CH.sub.3 
CH O 
11.08 4-F(Ar) VI CH.sub.3 
CH O 
11.09 4-F(Ar) VII CH.sub.3 
CH O 
11.10 2-CH.sub.3 (Ar) 
V CH.sub.3 
CH O 
11.11 2-CH.sub.3 (Ar) 
VI CH.sub.3 
CH O 
11.12 2-CH.sub.3 (Ar) 
VII CH.sub.3 
CH O 
11.13 4-CH.sub.3 (Ar) 
V CH.sub.3 
CH O 
11.14 4-CH.sub.3 (Ar) 
VI CH.sub.3 
CH O 
11.15 4-CH.sub.3 (Ar) 
VII CH.sub.3 
CH O 
11.16 4-CF.sub.3 (Ar) 
V CH.sub.3 
CH O 
11.17 2,4-Cl(Ar) V CH.sub.3 
CH O 
11.18 CH.sub.3 V CH.sub.3 
CH O 
11.19 CH.sub.2 CH.sub.3 
V CH.sub.3 
CH O 
11.20 CH.sub.2 CH.sub.2 CH.sub.3 
V CH.sub.3 
CH O 
11.21 CH(CH.sub.3).sub.2 
V CH.sub.3 
CH O 
11.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
V CH.sub.3 
CH O 
11.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
V CH.sub.3 
CH O 
11.24 CH.sub.2 CH(CH.sub.3).sub.2 
V CH.sub.3 
CH O 
11.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
V CH.sub.3 
CH O 
11.26 C(CH.sub.3).sub.3 
V CH.sub.3 
CH O 
11.27 CH.sub.2 C(CH.sub.3).sub.3 
V CH.sub.3 
CH O 
11.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
V CH.sub.3 
CH O 
11.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
V CH.sub.3 
CH O 
11.30 CF.sub.3 V CH.sub.3 
CH O 
11.31 CF.sub.2 CF.sub.3 
V CH.sub.3 
CH O 
11.32 CH.sub.2 CF.sub.3 
V CH.sub.3 
CH O 
11.33 CHCH.sub.2 V CH.sub.3 
CH O 
11.34 cyclopropyl V CH.sub.3 
CH O 
11.35 cyclopentyl V CH.sub.3 
CH O 
11.36 cyclohexyl V CH.sub.3 
CH O 
11.37 CH.sub.2 OCH.sub.3 
V CH.sub.3 
CH O 
11.38 CH.sub.2 OCH.sub.2 CH.sub.3 
V CH.sub.3 
CH O 
11.39 CH.sub.2 CH.sub.2 OCOAr 
V CH.sub.3 
CH O 
11.40 CH.sub.2 OCH.sub.2 Ar 
V CH.sub.3 
CH O 
11.41 2-pyridyl V CH.sub.3 
CH O 
11.42 3-pyridyl V CH.sub.3 
CH O 
11.43 2-pyrimidyl V CH.sub.3 
CH O 
11.44 4-pyrimidyl V CH.sub.3 
CH O 
11.45 2-thienyl V CH.sub.3 
CH O 
11.46 3-thienyl V CH.sub.3 
CH O 
11.47 2-napthyl V CH.sub.3 
CH O 
11.48 Ar V C.sub.2 H.sub.5 
CH O 
11.49 4-Cl(Ar) V C.sub.2 H.sub.5 
CH O 
11.50 CH.sub.3 V C.sub.2 H.sub.5 
CH O 
11.51 CH.sub.2 CH.sub.3 
V C.sub.2 H.sub.5 
CH O 
11.52 CH.sub.2 CH.sub.2 CH.sub.3 
V C.sub.2 H.sub.5 
CH O 
11.53 CH(CH.sub.3).sub.2 
V C.sub.2 H.sub.5 
CH O 
11.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
V C.sub.2 H.sub.5 
CH O 
11.55 CH.sub.2 CH(CH.sub.3).sub.2 
V C.sub.2 H.sub.5 
CH O 
11.56 C(CH.sub.3).sub.3 
V C.sub.2 H.sub.5 
CH O 
11.57 Ar VI 4-Cl(Ar) 
CH O 
11.58 Ar V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.59 CH.sub.3 V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.60 CH.sub.2 CH.sub.2 CH.sub.3 
V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.61 CH(CH.sub.3).sub.2 
V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.63 CH.sub.2 CH(CH.sub.3).sub.2 
V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.64 C(CH.sub.3).sub.3 
V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.65 2-pyridyl V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.66 3-pyridyl V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.67 4-pyrimidyl V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.68 2-thienyl V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.69 3-thienyl V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
11.70 2-napthyl V CH.sub.2 CH.sub.2 CH.sub.3 
CH O 
______________________________________ 
Further typical compounds described by the present invention are described 
in the following tables. 
Table 12: 
Compounds 12.1 to 12.47 are Compounds of Table 11 of Formula V, VI, VII 
where Z is Ar. 
Table 13: 
Compounds 13.1 to 13.47 are Compounds of Table 11 of Formula V, VI, VII 
where Z is CH.sub.2 Ar. 
Table 14: 
Compounds 14.1 to 14.47 are Compounds of Table 11 of Formula V, VI, VII 
where Z is CH.sub.2 CF.sub.3. 
Table 15: 
Compounds 15.1 to 15.47 are Compounds of Table 12 of Formula V, VI, VII 
where V.dbd.O and A is N. 
Table 16: 
Compounds 16.1 to 16.47 are Compounds of Table 12 of Formula V, VI, VII 
where V.dbd.NH and A is N. 
Table 17: 
Compounds 17.1 to 17.47 are Compounds of Table 13 of Formula V, VI, VII 
where V.dbd.O and A is N 
Table 18: 
Compounds 18.1 to 18.47 are Compounds of Table 13 of Formula V, VI, VII 
where V.dbd.NH and A is N. 
Table 19: 
Compounds 19.1 to 19.47 are Compounds of Table 14 of Formula V, VI, VII 
where V.dbd.O and A is N. 
Table 20: 
Compounds 20.1 to 20.47 are Compounds of Table 14 of Formula V, VI, VII 
where V.dbd.NH and A is N. 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 21 of Formula VIII, IX and X where 
X.dbd.H, R.sub.1 .dbd.H, U and W are N and n=0 and m=1. 
TABLE 21 
______________________________________ 
##STR10## 
##STR11## 
##STR12## 
Cmpd# R Formula Z A V 
______________________________________ 
21.01 Ar VIII CH.sub.3 
CH O 
21.02 Ar IX CH.sub.3 
CH O 
21.03 Ar X CH.sub.3 
CH O 
21.04 4-Cl(Ar) VIII CH.sub.3 
CH O 
21.05 4-Cl(Ar) IX CH.sub.3 
CH O 
21.06 4-Cl(Ar) X CH.sub.3 
CH O 
21.07 4-F(Ar) VIII CH.sub.3 
CH O 
21.08 4-F(Ar) IX CH.sub.3 
CH O 
21.09 4-F(Ar) X CH.sub.3 
CH O 
21.10 2-CH.sub.3 (Ar) 
VIII CH.sub.3 
CH O 
21.11 2-CH.sub.3 (Ar) 
IX CH.sub.3 
CH O 
21.12 2-CH.sub.3 (Ar) 
X CH.sub.3 
CH O 
21.13 4-CH.sub.3 (Ar) 
VIII CH.sub.3 
CH O 
21.14 4-CH.sub.3 (Ar) 
IX CH.sub.3 
CH O 
21.15 4-CH.sub.3 (Ar) 
X CH.sub.3 
CH O 
21.16 4-CF.sub.3 (Ar) 
VIII CH.sub.3 
CH O 
21.17 2,4-Cl(Ar) VIII CH.sub.3 
CH O 
21.18 CH.sub.3 VIII CH.sub.3 
CH O 
21.19 CH.sub.2 CH.sub.3 
VIII CH.sub.3 
CH O 
21.20 CH.sub.2 CH.sub.2 CH.sub.3 
VIII CH.sub.3 
CH O 
21.21 CH(CH.sub.3).sub.2 
VIII CH.sub.3 
CH O 
21.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
VIII CH.sub.3 
CH O 
21.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
VIII CH.sub.3 
CH O 
21.24 CH.sub.2 CH(CH.sub.3).sub.2 
VIII CH.sub.3 
CH O 
21.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
VIII CH.sub.3 
CH O 
21.26 C(CH.sub.3).sub.3 
VIII CH.sub.3 
CH O 
21.27 CH.sub.2 C(CH.sub.3).sub.3 
VIII CH.sub.3 
CH O 
21.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
VIII CH.sub.3 
CH O 
21.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
VIII CH.sub.3 
CH O 
21.30 CF.sub.3 VIII CH.sub.3 
CH O 
21.31 CF.sub.2 CF.sub.3 
VIII CH.sub.3 
CH O 
21.32 CH.sub.2 CF.sub.3 
VIII CH.sub.3 
CH O 
21.33 CHCH.sub.2 VIII CH.sub.3 
CH O 
21.34 cyclopropyl VIII CH.sub.3 
CH O 
21.35 cyclopentyl VIII CH.sub.3 
CH O 
21.36 cyclohexyl VIII CH.sub.3 
CH O 
21.37 CH.sub.2 OCH.sub.3 
VIII CH.sub.3 
CH O 
21.38 CH.sub.2 OCH.sub.2 CH.sub.3 
VIII CH.sub.3 
CH O 
21.39 CH.sub.2 CH.sub.2 OCOAr 
VIII CH.sub.3 
CH O 
21.40 CH.sub.2 OCH.sub.2 Ar 
VIII CH.sub.3 
CH O 
21.41 2-pyridyl VIII CH.sub.3 
CH O 
21.42 3-pyridyl VIII CH.sub.3 
CH O 
21.43 2-pyrimidyl VIII CH.sub.3 
CH O 
21.44 4-pyrimidyl VIII CH.sub.3 
CH O 
21.45 2-thienyl VIII CH.sub.3 
CH O 
21.46 3-thienyl VIII CH.sub.3 
CH O 
21.47 2-napthyl VIII CH.sub.3 
CH O 
21.48 Ar VIII Ar CH O 
21.49 4-Cl(Ar) VIII Ar CH O 
21.50 CH.sub.3 VIII Ar CH O 
21.51 CH.sub.2 CH.sub.3 
VIII Ar CH O 
21.52 CH.sub.2 CH.sub.2 CH.sub.3 
VIII Ar CH O 
21.53 CH(CH.sub.3).sub.2 
VIII Ar CH O 
21.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
VIII Ar CH O 
21.55 CH.sub.2 CH(CH.sub.3).sub.2 
VIII Ar CH O 
21.56 C(CH.sub.3).sub.3 
VIII Ar CH O 
21.57 Ar VIII CH.sub.2 Ar 
CH O 
21.58 4-Cl(Ar) VIII CH.sub.2 Ar 
CH O 
21.59 CH.sub.3 VIII CH.sub.2 Ar 
CH O 
21.60 CH.sub.2 CH.sub.2 CH.sub.3 
VIII CH.sub.2 Ar 
CH O 
21.61 CH(CH.sub.3).sub.2 
VIII CH.sub.2 Ar 
CH O 
21.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
VIII CH.sub.2 Ar 
CH O 
21.63 CH.sub.2 CH(CH.sub.3).sub.2 
VIII CH.sub.2 Ar 
CH O 
21.64 C(CH.sub.3).sub.3 
VIII CH.sub.2 Ar 
CH O 
21.65 Ar VIII CF.sub.2 CF.sub.3 
CH O 
21.66 4-Cl(Ar) VIII CF.sub.2 CF.sub.3 
CH O 
21.67 CH.sub.3 VIII CF.sub.2 CF.sub.3 
CH O 
21.68 CH.sub.2 CH.sub.2 CH.sub.3 
VIII CF.sub.2 CF.sub.3 
CH O 
21.69 C(CH.sub.3).sub.3 
VIII CF.sub.2 CF.sub.3 
CH O 
21.70 2-thienyl VIII CF.sub.2 CF.sub.3 
CH O 
______________________________________ 
Further typical compounds described by the present invention are described 
in the following tables. 
Table 22 
Compounds 22.1 to 22.70 are Compounds of Table 19 of Formula VIII, IX, X 
where V.dbd.O and A is N. 
Table 23: 
Compounds 23.1 to 23.70 are Compounds of Table 19 of Formula VIII, IX, X 
where V.dbd.NH and A is N. 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 24. of Formula XI, XII, XIII where 
X.dbd.H, R.sub.1 .dbd.H, U and W are N and n=1 and m=0. 
TABLE 24 
______________________________________ 
##STR13## 
##STR14## 
##STR15## 
Cmpd# R Formula Z A V 
______________________________________ 
24.01 Ar XI CH.sub.3 
CH O 
24.02 Ar XII CH.sub.3 
CH O 
24.03 Ar XIII CH.sub.3 
CH O 
24.04 4-Cl(Ar) XI CH.sub.3 
CH O 
24.05 4-Cl(Ar) XII CH.sub.3 
CH O 
24.06 4-Cl(Ar) XIII CH.sub.3 
CH O 
24.07 4-F(Ar) XI CH.sub.3 
CH O 
24.08 4-F(Ar) XII CH.sub.3 
CH O 
24.09 4-F(Ar) XIII CH.sub.3 
CH O 
24.10 2-CH.sub.3 (Ar) 
XI CH.sub.3 
CH O 
24.11 2-CH.sub.3 (Ar) 
XII CH.sub.3 
CH O 
24.12 2-CH.sub.3 (Ar) 
XIII CH.sub.3 
CH O 
24.13 4-CH.sub.3 (Ar) 
XI CH.sub.3 
CH O 
24.14 4-CH.sub.3 (Ar) 
XII CH.sub.3 
CH O 
24.15 4-CH.sub.3 (Ar) 
XIII CH.sub.3 
CH O 
24.16 4-CF.sub.3 (Ar) 
XIII CH.sub.3 
CH O 
24.17 2,4-Cl(Ar) XIII CH.sub.3 
CH O 
24.18 CH.sub.3 XIII CH.sub.3 
CH O 
24.19 CH.sub.2 CH.sub.3 
XIII CH.sub.3 
CH O 
24.20 CH.sub.2 CH.sub.2 CH.sub.3 
XIII CH.sub.3 
CH O 
24.21 CH(CH.sub.3).sub.2 
XIII CH.sub.3 
CH O 
24.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIII CH.sub.3 
CH O 
24.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
XIII CH.sub.3 
CH O 
24.24 CH.sub.2 CH(CH.sub.3).sub.2 
XIII CH.sub.3 
CH O 
24.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
XIII CH.sub.3 
CH O 
24.26 C(CH.sub.3).sub.3 
XIII CH.sub.3 
CH O 
24.27 CH.sub.2 C(CH.sub.3).sub.3 
XIII CH.sub.3 
CH O 
24.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
XIII CH.sub.3 
CH O 
24.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
XIII CH.sub.3 
CH O 
24.30 CF.sub.3 XIII CH.sub.3 
CH O 
24.31 CF.sub.2 CF.sub.3 
XIII CH.sub.3 
CH O 
24.32 CH.sub.2 CF.sub.3 
XIII CH.sub.3 
CH O 
24.33 CHCH.sub.2 XIII CH.sub.3 
CH O 
24.34 cyclopropyl XIII CH.sub.3 
CH O 
24.35 cyclopentyl XIII CH.sub.3 
CH O 
24.36 cyclohexyl XIII CH.sub.3 
CH O 
24.37 CH.sub.2 OCH.sub.3 
XIII CH.sub.3 
CH O 
24.38 CH.sub.2 OCH.sub.2 CH.sub.3 
XIII CH.sub.3 
CH O 
24.39 CH.sub.2 CH.sub.2 OCOAr 
XIII CH.sub.3 
CH O 
24.40 CH.sub.2 OCH.sub.2 Ar 
XIII CH.sub.3 
CH O 
24.41 2-pyridyl XIII CH.sub.3 
CH O 
24.42 3-pyridyl XIII CH.sub.3 
CH O 
24.43 2-pyrimidyl XIII CH.sub.3 
CH O 
24.44 4-pyrimidyl XIII CH.sub.3 
CH O 
24.45 2-thienyl XIII CH.sub.3 
CH O 
24.46 3-thienyl XIII CH.sub.3 
CH O 
24.47 2-napthyl XIII CH.sub.3 
CH O 
24.48 Ar XIII Ar CH O 
24.49 4-Cl(Ar) XIII Ar CH O 
24.50 CH.sub.3 XIII Ar CH O 
24.51 CH.sub.2 CH.sub.3 
XIII Ar CH O 
24.52 CH.sub.2 CH.sub.2 CH.sub.3 
XIII Ar CH O 
24.53 CH(CH.sub.3).sub.2 
XIII Ar CH O 
24.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIII Ar CH O 
24.55 CH.sub.2 CH(CH.sub.3).sub.2 
XIII Ar CH O 
24.56 C(CH.sub.3).sub.3 
XIII Ar CH O 
24.57 Ar XIII CH.sub.2 Ar 
CH O 
24.58 4-Cl(Ar) XIII CH.sub.2 Ar 
CH O 
24.59 CH.sub.3 XIII CH.sub.2 Ar 
CH O 
24.60 CH.sub.2 CH.sub.2 CH.sub.3 
XIII CH.sub.2 Ar 
CH O 
24.61 CH(CH.sub.3).sub.2 
XIII CH.sub.2 Ar 
CH O 
24.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIII CH.sub.2 Ar 
CH O 
24.63 CH.sub.2 CH(CH.sub.3).sub.2 
XIII CH.sub.2 Ar 
CH O 
24.64 C(CH.sub.3).sub.3 
XIII CH.sub.2 Ar 
CH O 
24.65 Ar XIII CF.sub.2 CF.sub.3 
CH O 
24.66 4-Cl(Ar) XIII CF.sub.2 CF.sub.3 
CH O 
24.67 CH.sub.3 XIII CF.sub.2 CF.sub.3 
CH O 
24.68 CH.sub.2 CH.sub.2 CH.sub.3 
XIII CF.sub.2 CF.sub.3 
CH O 
24.69 C(CH.sub.3).sub.3 
XIII CF.sub.2 CF.sub.3 
CH O 
24.70 2-thienyl XIII CF.sub.2 CF.sub.3 
CH O 
______________________________________ 
Further typical compounds described by the present invention are described 
in the following tables. 
Table 25: 
Compounds 25.01 to 25.70 are Compounds of Table 24 of Formula XI, XII, XIII 
where V.dbd.O and A is N. 
Table 26: 
Compounds 26.01 to 26.70 are Compounds of Table 24 of Formula XI, XII, XIII 
where V.dbd.NH and A is N. 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 27. of Formula XIV, XV, XVI where 
X.dbd.H, R.sub.1 .dbd.H, U is O, W is N and n and m are 0. 
TABLE 27 
______________________________________ 
##STR16## 
##STR17## 
##STR18## 
Cmpd# R Formula A V 
______________________________________ 
27.01 Ar XIV CH O 
27.02 Ar XV CH O 
27.03 Ar XVI CH O 
27.04 4-Cl(Ar) XIV CH O 
27.05 4-Cl(Ar) XV CH O 
27.06 4-Cl(Ar) XVI CH O 
27.07 4-F(Ar) XIV CH O 
27.08 4-F(Ar) XV CH O 
27.09 4-F(Ar) XVI CH O 
27.10 2-CH.sub.3 (Ar) XIV CH O 
27.11 2-CH.sub.3 (Ar) XV CH O 
27.12 2-CH.sub.3 (Ar) XVI CH O 
27.13 4-CH.sub.3 (Ar) XIV CH O 
27.14 4-CH.sub.3 (Ar) XV CH O 
27.15 4-CH.sub.3 (Ar) XVI CH O 
27.16 4-CF.sub.3 (Ar) XIV CH O 
27.17 2,4-Cl(Ar) XIV CH O 
27.18 CH.sub.3 XIV CH O 
27.19 CH.sub.2 CH.sub.3 
XIV CH O 
27.20 CH.sub.2 CH.sub.2 CH.sub.3 
XIV CH O 
27.21 CH(CH.sub.3).sub.2 
XIV CH O 
27.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIV CH O 
27.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
XIV CH O 
27.24 CH.sub.2 CH(CH.sub.3).sub.2 
XIV CH O 
27.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
XIV CH O 
27.26 C(CH.sub.3).sub.3 
XIV CH O 
27.27 CH.sub.2 C(CH.sub.3).sub.3 
XIV CH O 
27.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
XIV CH O 
27.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
XIV CH O 
27.30 CF.sub.3 XIV CH O 
27.31 CF.sub.2 CF.sub.3 
XIV CH O 
27.32 CH.sub.2 CF.sub.3 
XIV CH O 
27.33 CHCH.sub.2 XIV CH O 
27.34 cyclopropyl XIV CH O 
27.35 cyclopentyl XIV CH O 
27.36 cyclohexyl XIV CH O 
27.37 CH.sub.2 OCH.sub.3 
XIV CH O 
27.38 CH.sub.2 OCH.sub.2 CH.sub.3 
XIV CH O 
27.39 CH.sub.2 CH.sub.2 OCOAr 
XIV CH O 
27.40 CH.sub.2 OCH.sub.2 Ar 
XIV CH O 
27.41 2-pyridyl XIV CH O 
27.42 3-pyridyl XIV CH O 
27.43 2-pyrimidyl XIV CH O 
27.44 4-pyrimidyl XIV CH O 
27.45 2-thienyl XIV CH O 
27.46 3-thienyl XIV CH O 
27.47 2-napthyl XIV CH O 
27.48 Ar XIV N O 
27.49 4-Cl(Ar) XIV N O 
27.50 CH.sub.3 XIV N O 
27.51 CH.sub.2 CH.sub.3 
XIV N O 
27.52 CH.sub.2 CH.sub.2 CH.sub.3 
XIV N O 
27.53 CH(CH.sub.3).sub.2 
XIV N O 
27.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIV N O 
27.55 CH.sub.2 CH(CH.sub.3).sub.2 
XIV N O 
27.56 C(CH.sub.3).sub.3 
XIV N O 
27.57 Ar XIV N NH 
27.58 4-Cl(Ar) XIV N NH 
27.59 CH.sub.3 XIV N NH 
27.60 CH.sub.2 CH.sub.2 CH.sub.3 
XIV N NH 
27.61 CH(CH.sub.3).sub.2 
XIV N NH 
27.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIV N NH 
27.63 CH.sub.2 CH(CH.sub.3).sub.2 
XIV N NH 
27.64 C(CH.sub.3).sub.3 
XIV N NH 
27.65 2-thienyl XIV N NH 
27.66 3-thienyl XIV N NH 
27.67 2-pyridyl XIV N NH 
27.68 3-pyridyl XIV N NH 
27.69 5-pyrimidinyl XIV N NH 
27.70 2-napthyl XIV N NH 
______________________________________ 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 28. of Formula XVII, XVIII, XIX where 
X.dbd.H, R.sub.1 .dbd.H, U is N, W is O and n and m are 0. 
TABLE 28 
______________________________________ 
##STR19## 
##STR20## 
##STR21## 
Cmpd# R Formula A V 
______________________________________ 
28.01 Ar XVII CH O 
28.02 Ar XVIII CH O 
28.03 Ar XIX CH O 
28.04 4-Cl(Ar) XVII CH O 
28.05 4-Cl(Ar) XVIII CH O 
28.06 4-Cl(Ar) XIX CH O 
28.07 4-FAr) XVII CH O 
28.08 4-F(Ar) XVIII CH O 
28.09 4-F(Ar) XIX CH O 
28.10 2-CH.sub.3 (Ar) XVII CH O 
28.11 2-CH.sub.3 (Ar) XVIII CH O 
28.12 2-CH.sub.3 (Ar) XIX CH O 
28.13 4-CH.sub.3 (Ar) XVII CH O 
28.14 4-CH.sub.3 (Ar) XVIII CH O 
28.15 4-CH.sub.3 (Ar) XIX CH O 
28.16 4-CF.sub.3 (Ar) XIX CH O 
28.17 2,4-Cl(Ar) XIX CH O 
28.18 CH.sub.3 XIX CH O 
28.19 CH.sub.2 CH.sub.3 
XIX CH O 
28.20 CH.sub.2 CH.sub.2 CH.sub.3 
XIX CH O 
28.21 CH(CH.sub.3).sub.2 
XIX CH O 
28.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIX CH O 
28.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
XIX CH O 
28.24 CH.sub.2 CH(CH.sub.3).sub.2 
XIX CH O 
28.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
XIX CH O 
28.26 C(CH.sub.3).sub.3 
XIX CH O 
28.27 CH.sub.2 C(CH.sub.3).sub.3 
XIX CH O 
28.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
XIX CH O 
28.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
XIX CH O 
28.30 CF.sub.3 XIX CH O 
28.31 CF.sub.2 CF.sub.3 
XIX CH O 
28.32 CH.sub.2 CF.sub.3 
XIX CH O 
28.33 CHCH.sub.2 XIX CH O 
28.34 cyclopropyl XIX CH O 
28.35 cyclopentyl XIX CH O 
28.36 cyclohexyl XIX CH O 
28.37 CH.sub.2 OCH.sub.3 
XIX CH O 
28.38 CH.sub.2 OCH.sub.2 CH.sub.3 
XIX CH O 
28.39 CH.sub.2 CH.sub.2 OCOAr 
XIX CH O 
28.40 CH.sub.2 OCH.sub.2 Ar 
XIX CH O 
28.41 2-pyridyl XIX CH O 
28.42 3-pyridyl XIX CH O 
28.43 2-pyrimidyl XIX CH O 
28.44 4-pyrimidyl XIX CH O 
28.45 2-thienyl XIX CH O 
28.46 3-thienyl XIX CH O 
28.47 2-napthyl XIX CH O 
28.48 Ar XIX N O 
28.49 4-Cl(Ar) XIX N O 
28.50 CH.sub.3 XIX N O 
28.51 CH.sub.2 CH.sub.3 
XIX N O 
28.52 CH.sub.2 CH.sub.2 CH.sub.3 
XIX N O 
28.53 CH(CH.sub.3).sub.2 
XIX N O 
28.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIX N O 
28.55 CH.sub.2 CH(CH.sub.3).sub.2 
XIX N O 
28.56 C(CH.sub.3).sub.3 
XIX N O 
28.57 Ar XIX N NH 
28.58 4-Cl(Ar) XIX N NH 
28.59 CH.sub.3 XIX N NH 
28.60 CH.sub.2 CH.sub.2 CH.sub.3 
XIX N NH 
28.61 CH(CH.sub.3).sub.2 
XIX N NH 
28.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XIX N NH 
28.63 CH.sub.2 CH(CH.sub.3).sub.2 
XIX N NH 
28.64 C(CH.sub.3).sub.3 
XIX N NH 
28.65 2-thienyl XIX N NH 
28.66 3-thienyl XIX N NH 
28.67 2-pyridyl XIX N NH 
28.68 3-pyridyl XIX N NH 
28.69 5-pyrimidinyl XIX N NH 
28.70 2-napthyl XIX N NH 
______________________________________ 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 29. of Formula XX, XXI, XXII where 
X.dbd.H, R.sub.1 .dbd.H, U is O, W is N and n and m are 0. 
TABLE 29 
______________________________________ 
##STR22## 
##STR23## 
##STR24## 
Cmpd# R Formula A V 
______________________________________ 
29.01 Ar XX CH O 
29.02 Ar XXI CH O 
29.03 Ar XXII CH O 
29.04 4-Cl(Ar) XX CH O 
29.05 4-Cl(Ar) XXI CH O 
29.06 4-Cl(Ar) XXII CH O 
29.07 4-F(Ar) XX CH O 
29.08 4-F(Ar) XXI CH O 
29.09 4-F(Ar) XXII CH O 
29.10 2-CH.sub.3 (Ar) XX CH O 
29.11 2-CH.sub.3 (Ar) XXI CH O 
29.12 2-CH.sub.3 (Ar) XXII CH O 
29.13 4-CH.sub.3 (Ar) XX CH O 
29.14 4-CH.sub.3 (Ar) XXI CH O 
29.15 4-CH.sub.3 (Ar) XXII CH O 
29.16 4-CF.sub.3 (Ar) XX CH O 
29.17 2,4-Cl(Ar) XX CH O 
29.18 CH.sub.3 XX CH O 
29.19 CH.sub.2 CH.sub.3 
XX CH O 
29.20 CH.sub.2 CH.sub.2 CH.sub.3 
XX CH O 
29.21 CH(CH.sub.3).sub.2 
XX CH O 
29.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XX CH O 
29.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
XX CH O 
29.24 CH.sub.2 CH(CH.sub.3).sub.2 
XX CH O 
29.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
XX CH O 
29.26 C(CH.sub.3).sub.3 
XX CH O 
29.27 CH.sub.2 C(CH.sub.3).sub.3 
XX CH O 
29.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
XX CH O 
29.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
XX CH O 
29.30 CF.sub.3 XX CH O 
29.31 CF.sub.2 CF.sub.3 
XX CH O 
29.32 CH.sub.2 CF.sub.3 
XX CH O 
29.33 CHCH.sub.2 XX CH O 
29.34 cyclopropyl XX CH O 
29.35 cyclopentyl XX CH O 
29.36 cyclohexyl XX CH O 
29.37 CH.sub.2 OCH.sub.3 
XX CH O 
29.38 CH.sub.2 OCH.sub.2 CH.sub.3 
XX CH O 
29.39 CH.sub.2 CH.sub.2 OCOAr 
XX CH O 
29.40 CH.sub.2 OCH.sub.2 Ar 
XX CH O 
29.41 2-pyridyl XX CH O 
29.42 3-pyridyl XX CH O 
29.43 2-pyrimidyl XX CH O 
29.44 4-pyrimidyl XX CH O 
29.45 2-thienyl XX CH O 
29.46 3-thienyl XX CH O 
29.47 2-napthyl XX CH O 
29.48 Ar XX N O 
29.49 4-Cl(Ar) XX N O 
29.50 CH.sub.3 XX N O 
29.51 CH.sub.2 CH.sub.3 
XX N O 
29.52 CH.sub.2 CH.sub.2 CH.sub.3 
XX N O 
29.53 CH(CH.sub.3).sub.2 
XX N O 
29.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XX N O 
29.55 CH.sub.2 CH(CH.sub.3).sub.2 
XX N O 
29.56 C(CH.sub.3).sub.3 
XX N O 
29.57 Ar XX N NH 
29.58 4-Cl(Ar) XX N NH 
29.59 CH.sub.3 XX N NH 
29.60 CH.sub.2 CH.sub.2 CH.sub.3 
XX N NH 
29.61 CH(CH.sub.3).sub.2 
XX N NH 
29.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XX N NH 
29.63 CH.sub.2 CH(CH.sub.3).sub.2 
XX N NH 
29.64 C(CH.sub.3).sub.3 
XX N NH 
29.65 2-thienyl XX N NH 
29.66 3-thienyl XX N NH 
29.67 2-pyridyl XX N NH 
29.68 3-pyridyl XX N NH 
29.69 5-pyrimidinyl XX N NH 
29.70 2-napthyl XX N NH 
______________________________________ 
Typical compounds encompassed by the present invention of Formula I include 
those compounds presented in Table 30. of Formula XXIII, XXIV, XXV where 
X.dbd.H, R.sub.1 .dbd.H, U is N, W is O and n and m are 0. 
TABLE 30 
______________________________________ 
##STR25## 
##STR26## 
##STR27## 
Cmpd# R Formula A V 
______________________________________ 
30.01 Ar XXIII CH O 
30.02 Ar XXIV CH O 
30.03 Ar XXV CH O 
30.04 4-Cl(Ar) XXIII CH O 
30.05 4-Cl(Ar) XXIV CH O 
30.06 4-Cl(Ar) XXV CH O 
30.07 4-F(Ar) XXIII CH O 
30.08 4-F(Ar) XXIV CH O 
30.09 4-F(Ar) XXV CH O 
30.10 2-CH.sub.3 (Ar) XXIII CH O 
30.11 2-CH.sub.3 (Ar) XXIV CH O 
30.12 2-CH.sub.3 (Ar) XXV CH O 
30.13 4-CH.sub.3 (Ar) XXIII CH O 
30.14 4-CH.sub.3 (Ar) XXIV CH O 
30.15 4-CH.sub.3 (Ar) XXV CH O 
30.16 4-CF.sub.3 (Ar) XXIII CH O 
30.17 2,4-Cl(Ar) XXIII CH O 
30.18 CH.sub.3 XXIII CH O 
30.19 CH.sub.2 CH.sub.3 
XXIII CH O 
30.20 CH.sub.2 CH.sub.2 CH.sub.3 
XXIII CH O 
30.21 CH(CH.sub.3).sub.2 
XXIII CH O 
30.22 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XXIII CH O 
30.23 CH.sub.2 (CH.sub.2).sub.4 CH.sub.3 
XXIII CH O 
30.24 CH.sub.2 CH(CH.sub.3).sub.2 
XXIII CH O 
30.25 CH(CH.sub.3)CH.sub.2 CH.sub.3 
XXIII CH O 
30.26 C(CH.sub.3).sub.3 
XXIII CH O 
30.27 CH.sub.2 C(CH.sub.3).sub.3 
XXIII CH O 
30.28 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
XXIII CH O 
30.29 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3 
XXIII CH O 
30.30 CF.sub.3 XXIII CH O 
30.31 CF.sub.2 CF.sub.3 
XXIII CH O 
30.32 CH.sub.2 CF.sub.3 
XXIII CH O 
30.33 CHCH.sub.2 XXIII CH O 
30.34 cyclopropyl XXIII CH O 
30.35 cyclopentyl XXIII CH O 
30.36 cyclohexyl XXIII CH O 
30.37 CH.sub.2 OCH.sub.3 
XXIII CH O 
30.38 CH.sub.2 OCH.sub.2 CH.sub.3 
XXIII CH O 
30.39 CH.sub.2 CH.sub.2 OCOAr 
XXIII CH O 
30.40 CH.sub.2 OCH.sub.2 Ar 
XXIII CH O 
30.41 2-pyridyl XXIII CH O 
30.42 3-pyridyl XXIII CH O 
30.43 2-pyrimidyl XXIII CH O 
30.44 4-pyrimidyl XXIII CH O 
30.45 2-thienyl XXIII CH O 
30.46 3-thienyl XXIII CH O 
30.47 2-napthyl XXIII CH O 
30.48 Ar XXIII N O 
30.49 4-Cl(Ar) XXIII N O 
30.50 CH.sub.3 XXIII N O 
30.51 CH.sub.2 CH.sub.3 
XXIII N O 
30.52 CH.sub.2 CH.sub.2 CH.sub.3 
XXIII N O 
30.53 CH(CH.sub.3).sub.2 
XXIII N O 
30.54 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XXIII N O 
30.55 CH.sub.2 CH(CH.sub.3).sub.2 
XXIII N O 
30.56 C(CH.sub.3).sub.3 
XXIII N O 
30.57 (Ar) XXIII N NH 
30.58 4-Cl(Ar) XXIII N NH 
30.59 CH.sub.3 XXIII N NH 
30.60 CH.sub.2 CH.sub.2 CH.sub.3 
XXIII N NH 
30.61 CH(CH.sub.3).sub.2 
XXIII N NH 
30.62 CH.sub.2 (CH.sub.2).sub.3 CH.sub.3 
XXIII N NH 
30.63 CH.sub.2 CH(CH.sub.3).sub.2 
XXIII N NH 
30.64 C(CH.sub.3).sub.3 
XXIII N NH 
30.65 2-thienyl XXIII N NH 
30.66 3-thienyl XXIII N NH 
30.67 2-pyridyl XXIII N NH 
30.68 3-pyridyl XXIII N NH 
30.69 5-pyrimidinyl XXIII N NH 
30.70 2-napthyl XXIII N NH 
______________________________________ 
As used in Tables 1 to 30 Ar is understood to be phenyl. 
The compounds of Formula I are prepared in a three step sequence. Schemes A 
and B describes the preparation of compounds of the formula (I) where n=1 
and m=0. The .alpha.,.beta. unsaturated compounds (XXV I) can be prepared 
by conventional condensation techniques. For example Organic Reactions, 
Volume 16, describes the general aldol condensation and specifically the 
condensation of benzaldehdydes with ketones. A hydroxybenzaldehdyde is 
condensed with a ketone, RCOCH.sub.2 R.sub.1, which when R.sub.1 .dbd.H is 
a methyl ketone, provides the unsaturated intermediate XXVI'. Substituted 
hydroxybenzaldehyde such as ortho, meta or parahydroxybenzaldehyde 
provides three regioisomeric intermediates XXVI and XXVI'. A varietal of 
reaction conditions can be employed to prepare the enones (XXVI and XXVI') 
which are described in Organic Reactions, Volume 16, pp. 69-85. For 
example, a ketone is dissolved in a hydroxylic solvent, such as ethanol, 
to which is added dropwise a solution of the hydroxybenzaldehyde in an 
aqueous basic solution. The bases used can be alkali metal hydroxides, 
such as potassium or sodium hydroxide and the dropwise addition is 
conducted from 0.degree. C. to 35.degree. C. preferably at ambient 
temperature. 
The intermediate enone XXVI' is reacted with hydrazine or a substituted 
hydrazine to provide the intermediate XXVII' pyrazolines. Typical 
preparation of pyrazolines from unsaturated enones by treatment with 
hydrazine (for Z=H) are described in Synthetic Commun, 25(12), 1877-1883 
(1995); JACS 73, 3840 (1951); Indian J. Chem Soc Sect B 98-104 (1992) and 
J. Indian Chem Soc 643-644 (1993). For example, in JACS 73, 3840 (1951), 
styryl cyclopropyl ketone is reacted with aqueous hydrazine in 95% ethanol 
and stirred on a steam bath for 1 hour which after distillation gave the 
pyrazoline in 86% yield. Similarly in Synthetic Commun, 25(12), 1877-1883 
(1995) chalcones are treated with hydrazine monohydrate and stirred at 
reflux in ethanol and gave the pyrazolines in &gt;90% yield. 
Typical preparation of N-phenylpyrazolines (when Z is phenyl) from 
unsaturated enones are described in Indian J. Chem Soc Sect B 98-104 
(1992), J. Chem Res. Synop. 5, 168-169(1994) and Bull Soc. Chim Belg 
707(1958). For example in J. Chem Res. Synop. 5, 168-169, a chalcone is 
treated with excess phenylhydrazine at reflux in ethanol to give the 
N-phenyl pyrazolines in 60-70% yield. Similarly, in Indian J. Chem Soc 
Sect B 98-104, an N-phenylpyazoline was formed in 88% yield by treatment 
of an unsaturated carbonyl compound with phenylhydrazine at reflux in the 
presence of glacial acetic acid. 
The intermediate isoxazolines XXVIII' can prepared from enone XXVI' by 
reaction with hydroxylamine as described in Bull Soc. Chim Belg 96(4), 293 
(1987) and in Collect Czech Chem. Conimun. 59, 247-252 (1994). Typically 
the enone is treated with an equimolar amount of hydroxylamine 
hydrochloride in 0.3M ethanolic sodium hydroxide and stirred at reflux for 
upto 10 hours and after neutralization with HCl the product isolated by 
filtration. 
Preparation of the pyrazole XXIX' from intermediate pyrazoline XXVII' is 
described in J. Indian Chenm Soc. 64(7), 408 (1987) by oxidation with 
MnO.sub.2 at room temperature. Typically the pyrazolines are shaken with 
MnO.sub.2, 3.0 equivalents., in chloroform at room temperature for 2 hours 
and the pyrazoles are isolated by chromatography. 
Preparation of the isoxazoles XXX' from intermediate isoxazoline XXVIII' is 
described in Synthesis 837 (1977) and Synth. Commun. 219 (1978). Typically 
a 3,5-disubstituted-isoxazoline in 10:1 benzene: dioxane is treated with 
.gamma. MnO.sub.2 (5.0 equivalents by weight) and stirred at reflux with 
azeoptropic removal of the water with a Dean Stark trap. The reaction is 
filtered through Celite and the remaining residue contains the isoxazole. 
##STR28## 
Compounds of formula (V, VI, VII; XVII, XVIII, XIX; XI, XII, XIII and 
XXIII, XXIV, XXV) are prepared by the alkylation of intermediate 
pyrazoline XXVII' (when Z is not H), isoxazolines XXVIII', pyrazole XXIX' 
(when Z is not H) and isoxazole XXX, respectively, with the appropriately 
substituted benzyl bromides as shown in Scheme B. 
When Z is H, the intermediates XXVII' and XXIX' are alkylated with Z--L, 
where L is halogen, and the resulting O,N dialkylated products are 
selectively O-dealkylated with HBr to provide intermediates XXVII' and 
XXIX' where Z is not H. 
Alkylation of pyrazoline intermediate XXVII' derived from 
meta-hydroxybenzaldehdyde provides compounds of Tables 11 to 20 of Formula 
V (wherein R.sub.1 .dbd.H). Alkylation of intermediate XXVII' derived from 
ortho-hydroxybenzaldehdyde provides compounds of Tables 11-20 of Formula 
VI (wherein R.sub.1 .dbd.H). Alkylation of intermediate XXVII' derived 
from para-hydroxybenzaldehdyde provides compounds of Tables 11-20 of 
Formula VII (wherein R.sub.1 .dbd.H). Alkylation of isoxazoline 
intermediate XXVIII' derived from meta-hydroxyberzaldehdyde provides 
compounds of Table 28 of Formula XVII (wherein R.sub.1 .dbd.H). Alkylation 
of intermediate XXVIII' derived from ortho-hydroxybenzaldehdyde provides 
compounds of Table 28 of Formula XVIII (wherein R.sub.1 .dbd.H). 
Alkylation of intermediate XXVIII' derived from para-hydroxybenzaldehdyde 
provides compounds of Table 28 of Formula XVIII (wherein R.sub.1 .dbd.H). 
Alkylation of pyrazole intermediate XXIX' derived from pyrazoline XXVII' 
provides compounds of Tables 24 to 26 of Formula XI, XII and XII (wherein 
R.sub.1 .dbd.H). Alkylation of intermediate isoxazole XXX' derived from 
isoxazoline XXVIII' provides compounds of Table 30 of Formula XXIII, XXIV 
and XXV (wherein R.sub.1 .dbd.H). 
Compounds of formula I where A is CH and V is O are prepared by alkylation 
methyl E-.alpha.-(2-bromoomethylphenyl)-.beta.-methoxyacrylate in the 
presence of a base such as a metal hydride, preferably NaH, in an aprotic 
solvent such as N,N-dimethyl-formamide. Methyl 
E-.alpha.-(2-bromomethylphenyl)-.beta.-methoxyacrylate, as a single E 
isomer, can be prepared in two steps from 2-methylphenylacetate as 
described previously in U.S. Pat. No. 4,914,128, columns 3-4. 
Compounds of formula I where A is N and V is oxygen are prepared by the 
reaction with methyl E-2-(bromomethyl)phenylglyoxylate O-methyloxime in 
the presence of a base such as a metal hydride, preferably NaH, in an 
aprotic solvent such as N,N dimethylformamide. Methyl 
2-(bromnomethyl)phenylglyoxylate O-methyloxime can be prepared as 
described in U.S. Pat. Nos. 4,999,042, columns 17-18 and 5,157,144, 
columns 17-18. Methyl 2-(bromonmethyl)phenylglyoxylate O-methyloxime is 
prepared from methyl 2-methylphenylacetate by treatment with an alkyl 
nitrite under basic conditions to provide after methylation, methyl 
2-methylphenylglyoxalate O-methyl oxime which can also be prepared from 
methyl 2-methylphenylglyoxalate by treatment with 2-hydroxylamine 
hydrochloride and methylation or by treatment with methoxylamine 
hydrochloride. 
An alternative synthetic route to examples when A is N and V is oxygen, is 
provided by the alkylation with methyl 2-(bromomethyl)phenylglyoxylate 
followed by reaction with methoxylamine HCl or hydroxylamine HCl followed 
by methylation. 
The amminolysis of oximinoacetates to oximinoacetamides has been described 
in U.S. Pat. Nos. 5,185,342, cols. 22, 48 and 57; 5,221,691, cols 26-27; 
and 5,407,902, col 8. Compounds of Formula (VI) where A is N and V is O 
are treated with 40% aqueous methylamine in methanol to provide compounds 
of Formula (V) where V is NH(CH.sub.3). V and V' is reacted with N-methyl 
E-2-methoxyimino-2-2-(bromomethyl)phenyl!acetamide in the presence of a 
base such as a metal hydride, preferably NaH, in an aprotic solvent such 
as dimethyl formide (DMF). N-methyl 
E-2-methoxyimino-2-2-(bromomethyl)phenyl!acetamide is described in U.S. 
Pat. No. 5,387,714, col. 13. 
##STR29## 
Scheme C describes the preparation of compounds of the formula (I) where 
n=0 and m=1. The .alpha.,.beta. unsaturated compounds (XXXI) can be 
prepared by conventional condensation techniques. For example Organic 
Reactions, Volume 16 describes the general aldol condensation and 
specifically the condensation of aldehdydes with ketones. An aldehyde, for 
example a substituted benzaldehyde, is condensed with 
hydroxyphenylketones, (OH)ArCOCH2R.sub.1, which when R.sub.1 .dbd.H is a 
methyl ketone to provide the unsaturated intermediate XXXI'. 
##STR30## 
Substituted hydroxyphenylketones such as ortho, meta or 
para-hydroxyacetophenone provides three regioisomeric intermediates XXXI' 
where R.sub.1 .dbd.X.dbd.H. The intermediate enone XXXI' is reacted with 
hydrazine, substituted hydazines and hydroxylamine in the same manner as 
intermediate XXVI' (Scheme A). The pyrazoles XXIV' and the isoxazoles 
XXXV' are prepared by oxidation of the pyazoline XXXII" and isoxazoline 
XXXIII', respectively, in the same manner as described in Scheme A. 
Compounds of formula (II, III, IV; VIII, IX, X; XIV, XV, XVI, and XX, XXI, 
XXII) are prepared by the alkylation of intermediate pyrazoline XXXII', 
isoxazolines XXXIII', pyrazole XXIV and XXXV, respectively, with the 
appropriately substituted benzyl bromides as shown in Scheme D. 
Alkylation of pyrazoline intermediate XXXII' derived from 
meta-hydroxyacetophenone provides compounds of Tables 1 to 10 of Formula 
II (wherein R.sub.1 .dbd.H). Alkylation of isoxazoline intermediate XXXII' 
derived from ortho-acetophenone provides compounds of Tables 1 to 10 of 
Formula III (wherein R.sub.1 .dbd.H). Alkylation of intermediate XXXII' 
derived from para-hydroxyacetophenone provides compounds of Tables 1-10 of 
Formula IV (wherein R.sub.1 .dbd.H). Alkylation of intermediate XXXIII' 
derived from meta-hydroxyacetophenone provides compounds of Table 27 of 
Formula XIV (wherein R.sub.1 .dbd.H). Alkylation of intermediate XXXIII' 
derived from ortho-hydroxy-acetophenone provides compounds of Table 27 of 
Formula XV (wherein R.sub.1 .dbd.H). Alkylation of intermediate XXXIII' 
derived from para-hydroxyacetophenone provides compounds of Table 27 of 
Formula XVI (wherein R.sub.1 .dbd.H). 
Alkylation of pyrazole intermediate XXXIV' derived from pyrazoline XXXII' 
provides compounds of Tables 21 to 23 of Formula VIII, IX and X (wherein 
R.sub.1 .dbd.H). Alkylation of intermediate isoxazole XXXV' derived from 
isoxazoline XXXIII' provides compounds of Table 29 of Fornmula XX, XXI and 
XXII (wherein R.sub.1 .dbd.H). 
##STR31##

The compounds of this invention can be made according to the the following 
procedures: 
EXAMPLE 1 
Methyl 
3-methoxy-2-2-(3-(1-methyl-5-phenyl-2-pyrazolin-3-yl)phenoxymethyl)phenyl 
! propenoate (Compound 1.01, Table 1) 
To a 25 ml vial, equipped with magnetic stirrer was charged 1.1 g (0.0045 
moles) of 3-(3-hydroxylphenyl)-1n-methyl-5-phenyl-2-pyrazoline and 
0..sup.3 g (0.0045 moles) of powdered potassium hydroxide (85%), and 15 ml 
of dry N,N-dimethylformamide. To this solution was then added 1.3 g 
(0.0045 moles) of .alpha.-(2-(bromomethyl)phenyl)-.beta.-methoxyacrylate. 
The vial was capped, and stirred overnight at ambient temperature. The 
contents were then poured into 100 ml of water and extracted with 
2.times.100 ml of ethyl acetate. The organic extract was then washed with 
2.times.100 ml of water and 100 ml of saturated aqueous sodium chloride 
solution. The organic extract was then dried over anhydrous magnesium 
sulfate, then filtered. The filtrated was concentrated under reduced 
pressure and the residue was chromatographed on a mixed bed of neutral 
alumina and silica gel with a 50% ethyl acetate, 50% hexane mobile phase. 
The pure fractions were combined and concentrated under reduced pressure, 
to afford 1.9 g of Methyl 
3-methoxy-2-2-(3-(1-methyl-5-phenyl-2-pyrazolin-3-yl)phenoxymethyl)phenyl 
! propenoate as an amber oil in 92% isolate yield. 
H-NMR 200 MHz (CDCL.sub.3): 2.9(s, 3H); 3.5(m, 2H); 3.7(s, 3H); 3.9(s, 3H); 
4.1(m, 1H); 5.0(s, 2H); 6.9(m, 1H); 7.1-7.5(m, 12H); 7.6(s, 1H). 
Preparation of 3-(3-hydroxyphenyl)-1-methyl-5-phenyl-2-pyrazoline from 
3'-hydroxychalcone 
To a 100 ml round bottom flask equipped with a magnetic stirrer and reflux 
condenser was charged 1.0 g (0.0045 moles) of 3'-hydroxychalcone, and 25 
mls of absolute ethanol. To this solution was then added 0.21 g (0.0045 
moles) of methyl hydrazine in one portion. The reaction was then heated to 
reflux for two hours, then cooled. The solvent was removed under reduced 
pressure to afford 1.1 g of 
3-(3-hydroxylphenyl)-1-methyl-5-phenyl-2-pyrazoline as a thick brown oil 
in 97% yield 
H-NMR 200 MHz (CDCL.sub.3): 2.9(s, 3H); 3.0(t, 1H); 3.4(dd, 1H); 4.2(dd, 
1H); 6.8-7.6(m, 9H); 11.0(br s, 1H). 
EXAMPLE 2 
Methyl 
3-methoxy-2-2-(3-(1-methyl-3-phenyl-2-pyrazolin-5-yl)phenoxymethyl)phenyl 
! propenoate (Compound 11.01, Table 11). 
To a 25 ml vial, equipped with magnetic stirrer was charged 1.1 g (0.0045 
moles) of the of 5-(3-hydroxyphenyl)-1-methyl-3-phenyl-2-pyrazoline, 0.3 
g(0.0045 moles) of powdered potassium hydroxide (85%), and 15 ml of dry 
N,N-dimethylformamide. To this solution was then added 1.3 g (0.0045 
moles) of .alpha.-(2-(bromomethyl)phenyl)-.beta.-methoxyacrylate. The vial 
was capped, and stirred overnight at ambient temperature. The contents 
were then poured into 100 ml of water and extracted with 2.times.100 ml of 
ethyl acetate. The organic extract was then washed with 2.times.100 ml of 
water and 100 ml of saturated aqueous sodium chloride solution. The 
organic extract was then dried over anhydrous magnesium sulfate, then 
filtered. The filtrated was concentrated under reduced pressure and the 
residue was chromatographed on a mixed bed of neutral alumina and silica 
gel with a 50% ethyl acetate, 50% hexane mobile phase. The pure fractions 
were combined and concentrated under reduced pressure, to afford 1.8 g of 
Methyl 
3-methoxy-2-2-(3-(1-methyl-3-phenyl-2-pyrazolin-5-yl)phenoxymethyl)phenyl 
! propenoate as an amber oil in 88% isolated yield. 
H-NMR 200 MHz (CDCL.sub.3): 2.8(s, 3H); 3.0(t, 1H); 3.5 (m, 1H); 3.7(s, 
3H); 3.9(s, 4.1(m, 1H); 5.0(s, 2H); 6.8(d,1H); 6.9(d, 1H); 7.1-7.8(m, 12H) 
Preparation of 5-(3-hydroxyphenyl)-1-methyl-3-phenyl-2-pyrazoline from 
3-hydroxychalcone 
To a 100 ml round bottom flask equipped with a magnetic stirrer and reflux 
condensor was charged 1.0 g (0.0045 moles) of 3-hydroxychalcone, and 25 
mls of absolute ethanol. To this solution was then added 0.21 g (0.0045 
moles) of methyl hydrazine in one portion. The reaction was then heated to 
reflux for two hours, then cooled. The solvent was removed under reduced 
pressure to afford 1.1 g of 
5-(3-hydroxyphenyl)-1-methyl-3-phenyl-2-pyrazoline as a thick brown oil. 
97% yield. 
H-NMR 200 MHz (CDCL.sub.3): 2.9(s, 3H); 3.0(t, 1H); 3.4(dd, 1H); 4.2(dd, 
1H); 6.8-7.6(m, 9H); 11.0(bs, 1H) 
EXAMPLE 3 
Proton NMR data (200 MHz) are provided in Table 31 for typical examples of 
Tables 1 to 12 and are illustrative of the present invention. 
TABLE 31 
______________________________________ 
Compound # 
______________________________________ 
1.01 2.9(s, 3H); 3.5(m, 2H); 3.7(s, 3H); 3.9(s, 3H); 4.1(m, 1H); 
5.0(s, 2H); 6.9(m, 1H); 7.1-7.5(m, 12H); 7.6(s, 1H) 
1.02 2.85(s, 3H); 3.3(m, 1H); 3.5(m, 1H); 3.7(s, 3H); 3.9(s, 3H); 
4.1(m, 1H); 5.0(s, 2H); 6.8(d, 1H); 6.9(t, 1H); 7.1-7.5(m, 
10H); 7.6(s, 1H); 7.8(d, 1H) 
1.03 2.8(s, 3H); 3.0(t, 1H); 3.5(m, 1H); 3.7(s, 3H); 3.9(s, 3H); 
4.1(m, 1H); 5.0(s, 2H); 6.8(d, lH); 7.1(m, 1H); 7.2-7.7(m, 
12H) 
1.57 3.2(m, 1H); 3.7(s, 3H); 3.9(s, 3H); 4.1(m, 1H); 5.0(s, 2H); 
5.2(m, 1H); 6.8(d, 1H); 7.2-7.6(m, 15H); 7.7(s, 1H); 
8.0(m, 1H) 
11.01 2.8(s, 3H); 3.0(t, 1H); 3.5(m, 1H); 3.7(s, 3H); 3.9(s, 3H); 
4.1(m, 1H); 5.0(s, 2H); 6.8(d, 1H); 6.9(d, 1H); 7.1-7.8(m, 
12H) 
11.02 2.8(m, 1H); 2.9(s, 3H); 3.6(m, 1H); 3.7(s, 3H); 3.9(s, 3H); 
4.5(m, 1H); 5.0(s, 2H); 6.8(d, 1H); 6.9(t, 1H); 7.1-7.5(m, 
7H); 7.6(m, 1H); 7.7(m, 4H) 
12.01 3.2(m, 1H); 3.7(s, 3H); 3.8(s, 3H); 3.9(m, 1H); 5.0(s, 2H); 
5.2(m, 1H); 6.7(d, 1H); 6.9(m, 1H); 7.1-7.7(m, 14H); 
7.8(s, 2H); 8.0(m, 1H) 
14.01 3.0(m, 1H); 3.4-3.6(m, 3H); 3.7(s, 3H); 3.9(s, 3H); 
4.6(m, 1H); 5.0(s, 2H); 6.9(d, 1H); 7.0(m, 1H); 7.1-7.7(m, 
12H) 
______________________________________ 
EXAMPLE 4 
Numerous compounds of this invention were tested for fungicidal activity in 
vivo against the diseases described below. The compounds were dissolved in 
a 2:1:1 mixture of water, acetone and methanol (by volume), sprayed onto 
the plants, allowed to dry (one to two hours) and then the plants were 
inoculated with the fungus. Each test utilized control plants which were 
sprayed with the water, acetone and methanol mixture and inoculated with 
the fungus. The remainder of the technique of each of the tests is given 
below and the results for various compounds described herein by the 
Example number in Table 4 against the various fungi at a dose of 300 grams 
per hectare. The results are reported as percent disease control, compared 
to the control wherein) one hundred was rated as total disease control and 
zero was no disease control. The application of the fungi to the test 
plants was as follows: 
Wheat Leaf Rust (WLR) 
Puccinia recondita (f. sp. tritici) was cultured on 7 day old wheat 
(cultivar Fielder) over a 14 day period in the greenhouse. Spores were 
collected from the leaves by settling on aluminum foil. The spores were 
cleaned by sieving through a 250 micron opening screen and stored or used 
fresh. Storage employed sealed bags in an Ultralow freezer. A spore 
suspension was prepared from dry uredia by adding 20 mg (9.5 million 
spores) per mL of Soltrol oil. The suspension was dispensed into gelatin 
capsules (0.7 mL capacity) which attach to the oil atomizers. One capsule 
is used per flat of twenty of the 2 inch square pots of 7 day old Fielder 
wheat. After waiting for at least 15 minutes for the oil to evaporate from 
the wheat leaves, the plants were placed in a dark mist chamber 
(18.degree.-2020 C. and 100% relative humidity) for 24 hours. The plants 
were then put in the greenhouse for the latent period and scored after 10 
days for disease levels. For protective tests the plants are inoculated 
one day after spraying the plants with the fungicide compounds. 
Wheat Leaf Blotch (SNW) 
Septoria nodorum was maintained on Czapek-Dox V-8 juice agar plates in an 
incubator in the dark at 20.degree. C. for 48 to 72 hours, then incubated 
at 20.degree. C. with alternating perios do 12 hours of light and 12 hours 
of darkness. A water suspension of the spores was obtained by shaking the 
portion of the plate with fungal material in deionized water and filtering 
through cheesecloth. The spore containing water suspension was diluted to 
a spore concentration of 3.0.times.10.sup.6 spores per ml. The inoculum 
was dispersed by a DeVilbiss atomizer over one week old Fielder wheat 
plants which had been previously sprayed with the fungicide compound. The 
inoculated plants were placed in a humidity cabinet at 20.degree. C. with 
alternating 12 hours of light and 12 hours of darkness for 96 hours. The 
inoculated seedlings were then moved to a controlled environment room at 
20.degree. C. for 8 days of incubation. Disease control values were 
recorded as percent control. 
Wheat Powdery Mildew (WPM) 
Erysiphe graminis (f. sp. tritici) was cultured on wheat seedlings in a 
controlled temperature room at 6520 to 7020 F. Mildew spores were shaken 
from the culture plants onto wheat seedlings which had been previously 
sprayed with the fungicide compound. The inoculated seedlings were kept in 
a controlled temperature room at 6520 to 7520 F. and subirrigated. The 
percent disease control was rated 8 to 10 days after the inoculation. 
Cucumber Powdery Mildew (CPM) 
Sphaerotheca fulginea was maintained on cucumber plants, cv. Bush Champion, 
in the greenhouse. Inoculum was prepared by washing the spores from the 
leaves with water which had 1 drop of Tween 80 per 100 ml. After shaking 
the plants, the inoculum was filtered through cheese cloth and misted onto 
the plants with a squirt bottle mister. The plants were then placed in the 
greenhouse for infection and incubation. The plants were scored seven days 
after inoculation. Disease control values were recorded as percent 
control. 
Tomato Late Blight (TLB) 
Phytophthora infestans was cultured on V8 juice plus CaCO.sub.3 agar for 
three to four weeks. The spores were washed from the arag with water and 
sipsersed by DeVilbiss atomizer over the leaves of three week old Pixie 
tomato plants which had been sprayed previously with experimental 
fungicides. The inoculated plants were placed in a humidity cabinet at 
20.degree. C. for 24 hours for infection. The plants were then removed to 
a controlled environment room at 20.degree. C. The plants were scored for 
disease control after five days. 
Grape Downy Mildew (GDM) 
Plasmopara vticola was maintained on leaves of live grape plants, cv. 
Delaware, in the controlled temperature chamber at 20.degree. C. in humid 
air with moderate light intensity for 7 to 8 days. A water suspension of 
the spores from infested leaves was obtained and the spore concentration 
was adjusted to about 3.times.10.sup.5 per ml of water. Delaware grape 
plants were inoculated by spraying the underside of leaves with a De 
Vilbiss atomizer until small drops were observed on the leaves. The 
inoculated plants were incubated in a mist chamber for 24 hours at 
20.degree. C. Disease control values were recorded as percent control 
seven days after inoculation. 
When tested against cucumber powdery mildew at a dose of 300 grams per 
hectare, Examples 1.02, 11.02, 12.01, 14.01 exhibited 90% or better 
control. 
When tested against septoria nodorum at 300 grams per hectare Examples 
1.02, 11.01, 12.01, 14.01 exhibited 90% or better control. 
At 300 grams per hectare Examples 1.01, 1.02, 11.01, 11.02, 12.01, 14.01 
exhibited 90% or better control against wheat leaf rust. 
At 300 grams per hectare Examples 1.01, 1.02, 12.01 exhibited 75% or better 
control against wheat powdery mildew 
At 300 grams/hectare, Examples 1.01, 1.02, 11.01, 11.02, 12.01, 14.01 
exhibited 95% or better control against grape downy mildew. 
The compounds of this invention are useful as agricultural fungicides and, 
as such, can be applied to various loci such as the seed, the soil or the 
foliage. 
The compounds of this invention can be applied as fungicidal sprays by 
methods commonly employed, such as conventional high-gallonage hydraulic 
sprays, low-gallonage sprays, air-blast spray, aerial sprays and dusts. 
The dilution and rate of application will depend upon the type of 
equipment employed, the method of application, plants to be treated and 
diseases to be controlled. Generally, the compounds of this invention will 
be applied in amount of from about 0.005 kilogram to about 50 kilograms 
per hectare and preferably from about 0.025 to about 25 kilograms per 
hectare of the active ingredient. 
As a seed protectant, the amount of toxicant coated on the seed is usually 
at a dosage rate of from about 0.05 to about 20, preferably from about 
0.05 to about 4, and more preferably from about 0.1 to about 1 grams per 
hundred kilograms of seed. As a soil fungicide the chemical can be 
incorporated in the soil or applied to the surface usually at a rate of 
from about 0.02 to about 20, preferably from about 0.05 to about 10, and 
more preferably from about 0.1 to about 5 kilograms per hectare. As a 
foliar fungicide, the toxicant is usually applied to growing plants at a 
rate of from about 0.01 to about 10, preferably from about 0.02 to 5, and 
more preferably from about 0.25 to about 1 kilograms per hectare. 
In as much as the compounds of this invention display fungicidal activity, 
these compounds can be combined with other known fungicides to provide 
broad spectrum activity. Suitable fungicides include, but are not limited 
to, those compounds listed in U.S. Pat. No. 5,252,594 (see in particular 
columns 14 and 15). 
The compounds of this invention can be advantageously employed in various 
ways. Since these compounds possess broad spectrum fungicidal activity, 
they can be employed in the storage of cereal grain. These complexes can 
also be employed as fungicides in cereals including wheat, barley and rye, 
in rice, peanuts, beans and grapes, on turf, in fruit, nut and vegetable 
orchards, and for golf course applications. 
Examples of diseases against which the compounds of the invention are 
useful include helminthosporium of corn and barley, wheat and barley 
powdery mildew, wheat leaf and stem rusts, tomato early blight, tonmato 
late blight, peanut early leaf spot, grape powdery mildew, serape black 
rot, apple scab, apple powdery mildew, cucumber powdery mildew, brown rot 
of fruits, botrytis, bean powdery mildew, cucumber anthracnose, wheat 
septoria nodorum, rice sheath blight and rice blast. 
EXAMPLE 5 
Numerous compounds of this invention were tested for insecticidal activity 
in vivo against the insects described below. The following test method was 
used to evaluate compounds of the present invention for insectidal 
activity. The compound to be evaluated was dissolved in an appropriate 
solvent, usually a mix of acetone, methanol and water, and sprayed over 
three excised leaf disks using a flat fan nozzle. After spraying, the leaf 
disks were allowed to dry. Two disks were infested with the leaf chewing 
insects (southern armyworm and Mexican bean beetle) and the third leaf 
disk was already infested with the two-spotted spider mite prior to 
spraying. The tested insect species were: 
______________________________________ 
AW southern armyworm 
Spodoptera eridamia 
BB Mexican bean beetle 
Epilachna varivestis 
MTA two-spotted spider mite 
Teranychus uricate 
______________________________________ 
Observations as percent control were made by visual inspection 24-48 hours 
after spraying. 
When tested against Mexican bean beetle at 300 grams/hectare Examples 1.02, 
11.01, 11.02, 12.01, 14.01 provided 50% or better control. 
When tested against and two-spotted spider mite at 300 grams/hectare 
Examples 1.02, 1101, 14.01 provided 90% or better control. 
The compositions and compounds of this invention can be applied directly to 
the locus to be protected, as for example, the area around or upon 
economic plants infected with insects or to plants on which infestation is 
to be prevented. Examples of injurious insects belong to the orders 
Lepidoptera, Coleoptera, Diptera, Thysanoptera, Hymenoptera, Heteroptera, 
Homoptera, Orthoptera, and Acarina. The compounds and compositions may be 
used either as contact or systemic pesticides. The compounds of the 
invention are applied to the insect's habitat at a rate of 0.0005 to 10 
kilograms per hectare, preferably 0.05 to 5 and most preferably from 0.1 
to 1 kilogram per hectare. 
In the practice of the method of the invention, the active compound may be 
applied to the soil or foliage where it is absorbed by the plant, 
translocated to other plant parts and ultimately ingested by the pest or 
insects by means of ingestion of the plant part(s). This means of 
application is referred to as "systemic" application. Alternatively, the 
active compound may be applied to the soil and contacted therein with the 
insects and other pests to be controlled. This means of application is 
referred to as "soil" application. In another alternative, the active 
compound may be foliarly applied to the plants to be freed from insects 
and other pests which feed on the foliage. 
Compositions and formulations according to the present invention may also 
include known pesticidal compounds. This expands the spectrum of activity 
of the preparation and may give rise to synergism. Suitable insecticides 
known in the art inlcude those listed in U.S. Pat. No. 5,075,471, see in 
particular columns 14 and 15. 
The compounds of the present invention can be used in the form of 
compositions or formulations. Examples of the preparation of compositions 
and formulations can be found in the American Chemical Society publication 
"Pesticidal Formulation Research," (1969), Advances in Chemistry Series 
No. 86, written by Wade Van Valkenburg; and the Marcel Dekker, Inc. 
publication "Pesticide Formulations", (1973) edited by Wade Van 
Valkenburg. In these compositions and formulations, the active substance 
is mixed with conventional inert agronomically acceptable (i.e., plant 
compatible and/or pesticidally inert) pesticide diluents or extenders such 
as solid carrier material or liquid carrier material, of the type usable 
in conventional pesticide compositions or formulations. By "agronomically 
acceptable carrier is meant any substance which can be used to dissolve, 
disperse of diffuse the active ingredient in the composition without 
impairing the active ingredients effectiveness and which by itself has no 
significant detrimental effect on the soil, equipment, desirable plants, 
or agronomic enviornment. If desired, adjuvants such as surfactants, 
stabilizers, antifoam agents and antidrift agents may also be combined. 
Examples of compositions and lormulations according to the invention are 
aqueous solutions and dispersions, oily solutions and oil dispersions, 
pastes, dusting powders, wettable powders, emulsifiable concentrates, 
flowables, granules, baits, invert emulsions, aerosol compositions and 
fumigating candles. Wettable powders, pastes, flowables and enulsifiable 
concentrates are concentrated preparations which are diluted with water 
before or during use. In such formulations, the compounds are extended 
with a liquid or solid carrier and, when desired, suitable surfactants are 
incorporated. Baits are preparations generally comprising a food or other 
substance attractive to insects, that includes at least one compound of 
the instantinvention. 
It is usually desirable, particularly in the case of foliar spray 
formulations, to include adjuvants, such as wetting agents, spreading 
agents, dispersing agents, stickers, adhesive and the like in accordance 
with agricultural practices. Such adjuvants commonly used in the art, and 
a discussion of adjuvants can be found in many references, such as in the 
John W. McCutcheon, Inc. publication "Detergents and Emulsifiers, Annual." 
The active compounds of the present invention may be employed alone or in 
the form of mixtures with one another and/or with such solid and/or liquid 
dispersible carrier vehicles and/or witlh other known compatible active 
agents, especially plant protection agents, such as other insecticides, 
arthropodicides, nematicides, fungicides, bactericides, rodenticides, 
herbicides, fertilizers, growth regulating agents, synergists. 
In the compositions of the invention, the active compound is present in an 
amount substantially between about 0.0001-99% by weight. For compositions 
suitable for storage or transportation, the amount of active ingredient is 
preferably between about 0.5-90% by weight, and more preferably between 
about 1-75% by weight of the mixture. Compositions suitable for direct 
application or field application generally contain the active compound in 
an amount substantially between about 0.0001-95%, preferably between about 
0.0005-90% by weight, and more preferably between about 0.001-75% by 
weight of the mixture. The composition can also be stated as a ratio of 
the compound to the carrier. In the present invention the weight ratio of 
these materials (active compound/carrier) can vary from 99:1 to 1:4 and 
more preferably from 10:1 to 1:3. 
In general, the compounds of this invention can be dissolved in certain 
solvents such as acetone, methanol, ethanol, dimethylformamide, pyridine 
or dimethyl sulfoxide and such solutions can be diluted with water. The 
concentrations of the solution can vary from about 1% to about 90% with a 
preferred range being from about 5% to about 50%. 
For the preparation of emulsifiable concentrates, the compound can be 
dissolved in suitable organic solvents, or a mixture of solvents, together 
with an emulsifying agent to enhance dispersion of the compound in water. 
The concentration of the active ingredient in emulsifiable concentrates is 
usually from about 10% to about 90%, and in flowable emulsion 
concentrates, can be as high as about 75%. 
Wettable powders suitable for spraying, can be prepared by admixing the 
compound with a finely divided solid, such as clays, inorganic silicates 
and carbonates, and silicas and incorporating wetting agents, sticking 
agents, and/or dispersing agents in such mixtures. The concentration of 
active ingredients in such formulations is usually in the range of from 
about 20% to about 99%, preferably from about 40% to about 75%. A typical 
wettable powder is made by blending 50 parts of a pyridazinone, 45 parts 
of a synthetic precipitated hydrated silicon dioxide, such as that sold 
under the trademark Hi-SilR, and 5 parts of sodium lignosulfonate. In 
another preparation a kaolin type (Barden) clay is used in place of the 
Hi-Sil in the above wettable powder, and in another such preparation 25% 
of the Hi-Sil is replaced with a synthetic sodium silicoaluminate sold 
under the trademark Zeolex.RTM.7. 
Dusts are prepared by mixing the compound of Formula I, or the 
enantiomorphs, salts and complexes thereof with finely divided inert 
solids which can be organic or inorganic in nature. Materials useful for 
this purpose include botanical flours, silicas, silicates, carbonates and 
clays. One convenient method of preparing a dust is to dilute a wettable 
powder with a finely divided carrier. Dust concentrates containing from 
about 20% to about 80% of the active ingredient are commonly made and are 
subsequently diluted to from about 1% to about 10% use concentration. 
The active compounds can be applied as insecticide sprays by methods 
commonly employed, such as conventional high-gallonage hydraulic sprays, 
low gallonage sprays, ultra-low-volume sprays, airblast spray, aerial 
sprays, and dusts. 
The present invention also contemplates methods of killing, combatting or 
controlling pests which compromises contacting pests with a combative or 
toxic amount (i.e. a pesticidally effective amount) of at least one active 
compound of the invention alone or together with a carrier vehicle 
(composition or formulation) as noted above. The term "contacting" as 
employed in the specification and claims means applying to at least one of 
(a) such pests and (b) the corresponding habit at thereof (i.e., the locus 
to be protected, for example, to a growing crop or to an area where a crop 
is to be grown) the active compound of this invention alone or as a 
constituent of a composition or formulation. 
In addition to the aforementioned ingredients the preparations according to 
the invention may also contain other substances commonly used in 
preparations of this kind. For example, a lubricant, such as calcium 
stearate or magnesium stearate, may be added to a wettable powder or to a 
mixture to be granulated. Furthermore there may, for example, be added 
"adhesives" such as polyvinylalcohol-cellulose derivatives or other 
colloidal materials, such as casein, to improve the adherence of the 
pesticide to the surface to be protected.