Fungicidal methods, compounds and compositions containing benzophenones

There is provided a method for the control of phytopathogenic fungi and disease caused thereby which comprises contacting said fungi with a fungicidally effective amount of a benzophenone compound of formula I ##STR1## There are further provided benzophenone compounds of formula Ia which are useful as fungicidal agents and compositions useful for the protection of plants from the damaging effects of phytopathogenic fungi and fungal disease.

BACKGROUND OF THE INVENTION 
Food production relies upon a variety of agricultural technologies to 
ensure the growing population's dietary needs remain affordable, 
nutritious and readily available on grocery store shelves. Fungicides are 
one of these agricultural technologies which are available to the world 
community. Fungicides are agrochemical compounds which shield crops and 
foods from fungus and fungal diseases. Crops and food are constantly 
threatened by a variety of fungal organisms, which, if left uncontrolled, 
can cause ruined crops and devastated harvests. 
In particular, ascomycetes, the causative agent for powdery mildew diseases 
are an ever-present threat especially to cereal and fruit crops. However, 
applications of fungicidal agents at disease control rates can cause 
phytotoxic damage to the target plants. 
Therefore it is an object of this invention to provide a method to control 
phytopathogenic fungus without causing concurrent phytotoxic damage to the 
host plant. 
It is another object of this invention to provide an effective and safe 
method for the protection of important agronomic crops from the damage and 
loss caused by a phytopathogenic fungal infection and the disease caused 
thereby. 
It is a further object of this invention to provide benzophenone fungicidal 
agents and fungicidal compositions comprising a benzophenone compound. 
These and other objects and features of the invention will become apparent 
from the detailed description provided hereinbelow. 
SUMMARY OF THE INVENTION 
The present invention provides a method for the control of a 
phytopathogenic fungus or a disease caused thereby which comprises 
contacting said fungus with a fungicidally effective amount of a 
benzophenone compound of formula I 
##STR2## 
wherein R.sup.1 represents a halogen atom, an optionally substituted alkyl 
or alkoxy group, a cyano or a nitro group; m is 0 or an integer of 1, 2, 3 
or 4; R.sup.2 independently represents a halogen atom, an optionally 
substituted alkyl or alkoxy group, a nitro group or when R.sup.1 and 
R.sup.2 are attached to adjacent carbon atoms, R.sup.1 and one R.sup.2 may 
be taken together to represent --CH.dbd.CH--CH.dbd.CH-- or optionally 
substituted alkylene or oxyalkyleneoxy, such as O--CF.sub.2 --O; R.sup.3 
represents hydrogen, halogen, an optionally substituted alkyl, alkoxy, 
alkenyl, alkylthio, alkylsulphinyl, alkylsulphonyl, cyano, carboxy, 
hydroxy, nitro, or an optionally substituted amino group; R.sup.4 
represents a hydrogen atom or an optionally substituted alkyl or acyl 
group; R.sup.5 represents a hydrogen, halogen, an optionally substituted 
alkyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, cycloalkyl, 
cycloalkyloxy, a nitro, hydroxy, phenoxy, trialkylsilyloxy group, --ONa, 
--OK, --OC(O)R.sup.7, --OCHR.sup.8 C(O)R.sup.7, --OC(O)NR.sup.8 R.sup.9, 
--OS(O).sub.2 R.sup.8, --OS(O).sub.2 NR.sup.8 R.sup.9, --OP(X.sup.1) 
(OR.sup.8)OR.sup.9, --OP(X.sup.1) (R.sup.8)R.sup.9, --S(O)R.sup.8, 
--S(O).sub.2 R.sup.8, or R.sup.4 and R.sup.5 may be taken together to 
represent an optionally substituted alkylene or alkyleneoxy chain; n is 0, 
or an integer of 1 or 2; R.sup.6 independently represents a halogen atom, 
an optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, 
alkynyloxy, cycloalkyl, cycloalkoxy, hydroxy, --OC(O)R.sup.10 group, or 
when R5 and R6 are attached to adjacent carbon atoms, R.sup.5 and one 
R.sup.6 may be taken together to represent --CH.dbd.CH--CH.dbd.CH-- or an 
optionally substituted oxyalkyleneoxy chain; R.sup.7 represents a hydrogen 
atom or an optionally substituted alkyl, alkoxy or aryl group; R.sup.8, 
R.sup.9 and R.sup.10 independently represent a hydrogen atom, an alkyl, 
aryl or aralkyl group, or R.sup.8 and R.sup.9 may be taken together to 
represent an alkylene chain optionally interrupted by an oxygen or 
nitrogen atom; X represents an oxygen atom, a sulphur atom or a group NOR; 
X.sup.1 represents an oxygen or sulphur atom; Y represents an oxygen or 
sulphur atom or a sulphonyl or sulphinyl group; and R represents a 
hydrogen atom or an optionally substituted alkyl, aralkyl, aryl or acyl 
group. 
As used in the specification and claims, the term "benzophenone" 
encompasses oxime derivatives of benzophenone (X=NOR), benzothiophenones 
(X=S) and the underivatized benzophenone ketone (X=O). 
The present invention also provides crop protection methods, fungicidal 
benzophenone compounds of formula Ia, methods of preparation of said 
benzophenone compounds and fungicidal compositions comprising at least one 
formula I or Ia compound and an agriculturally acceptable carrier.

DETAILED DESCRIPTION OF THE INVENTION 
Huge economic losses have resulted from the devastation and damage of 
important agronomic and horticultural crops caused by fungal infection and 
infestation. Pest management strategies, field resistance, and virulent 
strains have all contributed to agriculturalists'concerns for combatting 
phytopathogenic fungal disease. In particular, ascomycetes, the causative 
agents for powdery mildew diseases continues to be a serious concern in 
cereal crop and fruit production. Further, in a variety of fungicidal 
agent applications concomitant phytotoxic injury to the host plant may be 
observed. 
It has now been found that benzophenone compounds of formula I are highly 
effective fungicidal agents and are particularly effective for controlling 
mildew diseases such as powdery mildew. Compounds of formula I useful in 
fungus control methods are those benzophenones having the structure 
##STR3## 
wherein X, Y, R.sup.1, R.sup.2 , R.sup.3, R.sup.4, R.sup.5, R.sup.6, m and 
n are described hereinabove. 
Alkyl as a substituent or as a part of other substituents, such as alkoxy 
or alkylthio may be straight-chain or branched and may contain up to 
eighteen, preferably up to 14, and especially up to 10, carbon atoms, 
individual examples including: methyl, ethyl, propyl, butyl, pentyl, 
hexyl, etc. as well as their isomers such as isopropyl, isobutyl, 
tertiary-butyl, isopentyl, and the like. Lower alkyl or alkoxy groups have 
from 1 to 10 carbon atoms. A cycloalkyl moiety as a substituent or as a 
part of other substituents suitably contains from 3 to 10, preferably from 
3 to 6, carbon atoms. An alkenyl or alkynyl group suitably has from 2 to 
6, preferably from 2 to 4 chain members, for example, ethenyl, propenyl, 
allyl, butenyl and the like as well as for chains with more than one 
double bond such as pentadienyl and the like. An alkylene chain usefully 
has 1 to 5, preferably 1 to 4, members. 
An acyl group is formally formed by the removal of hydroxyl from a carboxyl 
group, and is used herein to include formyl and optionally substituted 
alkylcarbonyl and arylcarbonyl groups. 
A halogen atom represents fluorine, chlorine, bromine and iodine, 
preferably chlorine. Preferred haloalkyl moieties are difluoromethyl and 
trifluoromethyl. 
Optionally substituted moieties may be unsubstituted or have from one up to 
the maximal chemically possible number of substituents. Optional 
substituents may be any of those customarily employed in the development 
of biocidal compounds, and/or the modification of such compounds to 
influence their activity, persistence, penetration and any other property. 
Specific examples of such substituents include halogen, especially 
fluorine, chlorine or bromine, nitro, cyano, hydroxy, carboxy, amino, 
alkyl- or aralkylamino, dialkylamino, cycloalkylamino, piperidyl, 
piperidinyl, morpholinyl, carbamoyl, aryl- or benzylcarbamoyl, mono- or 
dialkylcarbamoyl, morpholinocarbonyl, trialkylsilyl, alkyl, alkenyl, 
alkynyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, cycloalkoxy, acyl, 
optionally substituted benzoyl, benzoxazolyl, alkoxycarbonyl, optionally 
substituted pyridyl, phenoxy or naphthyl, phenyl or phenyl substituted by 
one or more substituents selected from the group comprising halogen, 
alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, phenylthio, 
benzylthio, aralkoxy, hydroxy, carboxy, carbalkoxy, cyano, optionally 
substituted amino, nitro, trifluoromethyl, trifluoromethoxy and the like. 
Alkyl moieties of such optional substituents may have from 1 to 6 carbon 
atoms, preferably 1 or 2 carbon atoms. If a substituted group mentioned 
herein does contain two or more substituents, such substituents may be 
identical or different. 
The benzophenone compounds according to formula I are oils, gums, or, 
predominantly, crystalline solid materials and possess valuable fungicidal 
properties. For example, they can be used in agriculture, or related 
fields such as horticulture and viticulture, for the control of 
phytopathogenic fungi, especially ascomycetes, and powdery mildew disease 
such as Erysiphe graminis, Podosphaera leucotricha, Uncinula necator and 
the like. Said benzophenone compounds possess a high fungicidal activity 
within a wide concentration range and may be used in agriculture without 
harmful phytotoxic effects. 
Preferred formula I compounds useful in the method of invention are those 
in which R.sup.1 represents a halogen atom or an optionally substituted 
alkyl or alkoxy group; m is 0 or an integer of 1, 2 or 3; and R.sup.2 
independently represents a halogen atom or an optionally substituted alkyl 
or alkoxy group; or R.sup.1 and R.sup.2 together represent 
--CH.dbd.CH--CH.dbd.CH--, oxyalkyleneoxy, difluorooxymethyleneoxy or 
alkylene; R.sup.3 represents a halogen atom, an optionally substituted 
alkyl, alkenyl, alkylthio or alkylsulphonyl group, a nitro group, or an 
optionally substituted amino group; R.sup.5 represents a hydrogen atom, an 
optionally substituted alkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy 
or alkylthio group, a hydroxy group, a trialkylsilyloxy group, or a 
--OC(O)R.sup.7, --OCHR.sup.8 C(O)R.sup.7, --OC(O)NR.sup.8 R.sup.9, 
NH--CO--R.sup.7, --OS(O).sub.2 R.sup.8 or --OS(O).sub.2 NR.sup.8 R.sup.9 
group; or R.sup.4 and R.sup.5 together represent an optionally substituted 
alkyleneoxy chain; n is 0 or the integer 1; R.sup.6 represents an 
optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, 
alkynyloxy, cycloalkyl or cycloalkoxy group or a --OC(O)R.sup.10 group; 
R.sup.7 represents a hydrogen atom or an alkyl or alkoxy group; X 
represents an oxygen atom or an NOR group; and R represents a hydrogen 
atom or an optionally substituted alkyl group. 
Good control of phytopathogenic fungi is obtained with a fungicidally 
effective amount of a compound of formula I wherein R.sup.1 represents a 
halogen atom or an optionally substituted lower alkyl group; m is an 
integer of 1 or 3; R.sup.2 independently represents a halogen atom or an 
optionally substituted lower alkyl group; R.sup.3 represents a halogen 
atom, an optionally substituted alkyl or alkenyl group, or an optionally 
substituted amino group; R.sup.5 represents an optionally substituted 
alkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy or alkylthio group or 
R.sup.4 and R.sup.5 may be taken together to represent an optionally 
substituted alkyleneoxy chain; n is 0 or the integer 1; R.sup.6 represents 
an optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, 
alkynyloxy, cycloalkyl or cycloalkoxy group or a --OC(O)R.sup.10 group; 
R.sup.7 represents an alkyl or alkoxy group; X represents an oxygen atom 
or NOR group; Y represents an oxygen atom; and R represents hydrogen or 
C.sub.1 -C.sub.4 alkyl. 
Especially preferred are those formula I compounds in which R.sup.1 
represents a halogen atom or C.sub.1 -C.sub.4 alkyl group; R.sup.2 
independently represents a halogen atom or C.sub.1 -C.sub.4 alkyl group; 
R.sup.3 represents a halogen atom or an optionally substituted C.sub.1 
-C.sub.4 alkyl group; R.sup.4 represents an optionally substituted C.sub.1 
-C.sub.4 alkyl group; R.sup.5 represents an optionally substituted lower 
alkyl, alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy group; R.sup.6 
represents an optionally substituted C.sub.1 -C.sub.6 alkoxy, alkenyloxy, 
alkynyloxy or cyloalkoxy group 
Effective control of phytopathogenic fungi may be achieved, for example, 
with a fungicidally effective amount of one or more of the following 
compounds: 
2,3,5,6-tetramethyl-4',5',6'-trimethoxy-2'-methylbenzophenone; 
2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone-O-methyloxime; 
2,6-dichloro-5'-t-butoxy-4'-methoxy-2'-methylbenzophenone; 
2,6-dichloro-5',6'-di-n-butoxy-4'-methoxy-2'-methylbenzophenone; 
2'-allyloxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone; 
2 '-benzyloxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone; 
2'-butoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone; 
2'-cyclohexylmethoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone; 
2'-benzoylmethoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone; 
2'-cyclopentyloxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone; 
2,6-dichloro-2',3',4'-trimethoxy-6'-methylbenzophenone; 
2,6-dichloro-2'-ethoxy-3',4'-dimethoxy-6'-methylbenzophenone; 
2,6-dichloro-2'-heptyloxy-3',4'-dimethoxy-6'-methylbenzophenone; 
2,6-dichloro-2'-hexyloxy-3',4'-dimethoxy-6'-methylbenzophenone; 
2,6-dichloro-3',4'-dimethoxy-2'-(2-methoxy-ethoxy)-6'-methylbenzophenone; 
2,6-dichloro-3',4'-dimethoxy-6'-methyl-2'-(3-methylbutoxy)benzophenone; 
2,6-dichloro-3',4'-dimethoxy-6'-methyl-2'-(prop-2-ynyloxy)benzophenone; 
2,6-dichloro-3',4'-dimethoxy-6'-methyl-2'-pentyloxybenzophenone; 
2,6-dichloro-3',4'-dimethoxy-6'-methyl-2'-propoxybenzophenone; 
2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone; 
2,6-dichloro-4'-methoxy-2'-methyl-5'-(3-methylbutoxy)benzophenone; 
2,6-dichloro-4'-methoxy-2'-methyl-5'-(prop-2-ynyloxy)benzophenone; 
2,6-dichloro-4'-methoxy-2'-methyl-5'-(octyloxy)benzophenone; 
2,6-dichloro-4'-methoxy-2'-methyl-5'-(pentyloxy)benzophenone; 
2,6-dichloro-4'-methoxy-2'-methyl-5'-propoxybenzophenone; 
2,6-dichloro-4'-methoxy-2'-methyl-5'-trimethylsilanylmethoxybenzophenone; 
2,6-dichloro-5'-(1-ethyl-propoxy)-4'-methoxy-2'-methylbenzophenone; 
2,6-dichloro-5-difluoromethoxy-4'-methoxy-2'-methylbenzophenone; 
2,6-dichloro-5'-ethoxy-4'-methoxy-2'-methylbenzophenone; 
2,6-dichloro-5'-heptyloxy-4'-methoxy-2'-methylbenzophenone; 
2,6-dichloro-5'-hexyloxy-4'-methoxy-2'-methylbenzophenone; 
2,6-dichloro-5'-isobutoxy-4'-methoxy-2'-methylbenzophenone; 
2,6-dichloro-5'-isopropoxy-4'-methoxy-2'-methylbenzophenone; 
5'-butoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone; 
5'-cyclohexylmethoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone; 
5'-cyclohexyloxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone; 
5'-cyclopentyloxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone; 
5'-cyclopropylmethoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone; or 
5'-decyloxy-2,6-dichloro-4'-methoxy-2'-methyl-benzophenone. 
Compounds of particular fungicidal use are those compounds of Formula I B. 
##STR4## 
wherein Q represents a hydrogen or a chlorine atom; R represents a 
hydrogen atom, a C.sub.3 -C.sub.8 cycloalkoxy group or a C.sub.1 -C.sub.8 
-alkoxy group optionally substituted with one or more fluorine atoms, or 
one phenyl, phenoxy, phenylthio or benzyloxy group, wherein the phenyl 
moiety may be substituted by halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 
-C.sub.4 -alkoxy, trifluoromethyl or trifluoromethoxy; and R' represents 
hydrogen or C.sub.1 -C.sub.10 -alkyl optionally substituted with one or 
more halogen, C.sub.1 -C.sub.4 -alkoxy, phenyl, phenoxy or phenylthio 
groups, wherein the phenyl moiety may be substituted by halogen, C.sub.1 
-C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, trifluoromethyl or 
trifluoromethoxy, with the proviso, that when Q and R represent hydrogen 
then R' must be other than methyl. 
Preferred compounds of formula I B are those wherein Q represents a 
hydrogen or a chlorine atom; R represents a hydrogen atom, a C.sub.5 
-C.sub.7 -cycloalkoxy group, a C.sub.1 -C.sub.6 -alkoxy group optionally 
substituted by one or more fluorine atoms, or one phenyl, phenoxy, 
phenylthio or benzyloxy group, wherein the phenyl moiety may be 
substituted by halogen, methyl, methoxy, trifluoromethyl or 
trifluoromethoxy; and R' represents hydrogen or C.sub.1 -C.sub.8 -alkyl 
optionally substituted by fluorine, chlorine, C.sub.1 -C.sub.4 -alkoxy, 
phenyl, phenoxy or phenylthio, wherein the phenyl moiety may be 
substituted by fluorine, chlorine, bromine, methyl, methoxy, 
trifluoromethyl or trifluoromethoxy. 
Further compounds of particular value are those compounds of Formula I C. 
##STR5## 
wherein Q and Q' independently represent a hydrogen atom or methyl group; 
R represents a hydrogen atom, a C.sub.3 -C.sub.8 -cycloalkoxy group or a 
C.sub.1 -C.sub.8 -alkoxy group optionally substituted with one or more 
fluorine atoms, a phenyl, phenoxy, phenylthio or benzyloxy group, wherein 
the phenyl moiety may be substituted with one or more halogen, C.sub.1 
-C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, trifluoromethyl or 
trifluoromethoxy groups; and R' represents hydrogen or C.sub.1 -C.sub.10 
-alkyl optionally substituted with one or more halogen, C.sub.1 -C.sub.4 
-alkoxy, phenyl, phenoxy or phenylthio groups, wherein the phenyl moiety 
may be substituted by one or more halogen, C.sub.1 -C.sub.4 -alkyl, 
C.sub.1 -C.sub.4 -alkoxy, trifluoromethyl or trifluoromethoxy groups. 
Preferred compounds of formula I C are those compounds, wherein Q and Q' 
independently represent a hydrogen atom or a methyl group; R represents a 
hydrogen atom, a C.sub.5 -C.sub.7 -cycloalkoxy group, a C.sub.1 -C.sub.6 
-alkoxy group optionally substituted with one or more fluorine atoms, one 
phenyl, phenoxy, phenylthio or benzyloxy group, wherein the phenyl moiety 
may be substituted by fluorine, chlorine, bromine, methyl, methoxy, 
trifluoromethyl or trifluoromethoxy; and R' represents hydrogen or C.sub.1 
-C.sub.8 -alkyl optionally substituted by one or more fluorine, chlorine, 
C.sub.1 -C.sub.4 -alkoxy, phenyl, phenoxy or phenylthio groups, wherein 
the phenyl moiety may be substituted with one or more bromine, methyl, 
methoxy, trifluoromethyl or trifluoromethoxy groups. 
The present invention also provides new benzophenone compounds of formula 
Ia 
##STR6## 
wherein R.sup.1 represents a halogen atom, an optionally substituted alkyl 
group or a cyano group; m is an integer of 2, 3 or 4; R.sup.2 
independently represents a halogen atom, an optionally substituted alkyl 
or alkoxy group or when R.sup.1 and R.sup.2 are on adjacent carbon atoms, 
R.sup.1 R.sup.2 together represent --CH.dbd.CH--CH.dbd.CH-- or an 
optionally substituted alkylene or oxyalkyleneoxy group; R.sup.3 
represents a hydrogen or halogen atom, an optionally substituted alkyl, 
alkoxy, alkenyl, alkylthio, alkylsulphinyl, alkylsulphonyl, cyano, 
carboxy, hydroxy, nitro, or an optionally substituted amino group; R.sup.4 
represents an optionally substituted alkyl or acyl group; R.sup.5 
represents a halogen atom, an optionally substituted alkoxy, alkenyloxy, 
alkynyloxy, alkylthio, cycloalkyl, cycloalkyloxy, trialkylsilyloxy, --ONa, 
--OK, --OC(O)R.sup.7, --OCHR.sup.8 C(O)R.sup.7, --OC(O)NR.sup.8 R.sup.9, 
--OS(O).sub.2 R.sup.8, --OS(O).sub.2 NR.sup.8 R.sup.9, -OP(X) 
(OR.sup.8)OR.sup.9, --OP(X.sup.1) (R.sup.8)R.sup.9, --S(O)R.sup.8 or 
--S(O).sub.2 R.sup.8 group or R.sup.4 and R.sup.5 may be taken together to 
represent an optionally substituted alkylene or alkyleneoxy chain; n is 0 
or an integer of 1 or 2; R.sup.6 independently represents an optionally 
substituted alkoxy group, a hydroxy group or a --OC(O)R.sup.10 group when 
attached to adjacent carbon atoms, or R.sup.5 and one R.sup.6 may be taken 
together to represent --CH.dbd.CH--CH.dbd.CH-- or an optionally 
substituted oxyalkyleneoxy chain; R.sup.7 represents a hydrogen atom or an 
optionally substituted alkyl, aryl or alkoxy group; R.sup.8, R.sup.9 and 
R.sup.10 independently represent a hydrogen atom or an alkyl group, or 
R.sup.8 and R.sup.9 may be taken together to represent an alkylene chain 
optionally interrupted by an oxygen or nitrogen atom; X represents an 
oxygen atom, a sulphur atom or an NOR group; X.sup.1 represents an oxygen 
or sulphur atom; Y represents an oxygen or sulphur atom or a sulphonyl or 
sulphinyl group; and R represents a hydrogen atom or an optionally 
substituted, alkyl, aralkyl, aryl or acyl group, with the provisos that 
when X represents an oxygen or sulphur atom and: 
(i) when R.sup.1 represents a halogen atom, then (R.sup.2).sub.m must be 
other than a halogen atom or no more than one alkyl or alkoxy group. 
(ii) when R.sup.1 represents an alkyl group, then R.sup.2 must be other 
than alkyl; 
(iii) when m is 1, then R.sup.2 must be other than an alkoxy group; 
(iv) when R.sup.3 represents an alkenyl group, then R.sup.3 cannot be 
substituted with an alkoxy or acyl group; 
(v) when R.sup.3 represents a haloalkyl group, then R.sup.1 and R.sup.2 
must be other than a haloalkyl group; and 
(vi) when Y represents an oxygen atom, then R.sup.3 and R.sup.5 must be 
other than a hydrogen atom and n must be 1 or 2. 
The compounds of formula I can be prepared by conventional methods. 
Thus the compounds having formula I (including those of formula Ia) may be 
prepared by a process which comprises reacting a compound of formula II 
##STR7## 
with a compound of formula III 
##STR8## 
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, Y, m and n 
are as hereinbefore defined and one of Z.sup.1 and Z.sup.2 represents a 
hydrogen atom and the other represents the group COCl; or one represents a 
magnesium halide group MgHal, wherein Hal is a halogen, preferably bromine 
or iodine, atom, and the other represents COCl or an aldehyde or nitrile 
group, followed in the last two cases by oxidation or hydrolysis, 
respectively, and optionally followed by further derivatization. 
The starting materials of formula II and III are known products, and may 
themselves be prepared according to established methods or routine 
adaptations thereof. Substituents R.sup.1 to R.sup.9 which are not 
compatible with the selected reaction conditions may be introduced after 
formation of the benzophenone. They may be generated by known methods such 
as subsequent derivatization or substitution of a suitable group or by 
cleaving off a suitable protecting group. 
When one of Z.sup.1 and Z.sup.2 is hydrogen and the other is COCl, the 
process is a Friedel Crafts reaction and is effected in the presence of a 
Lewis acid catalyst according to well-established procedures. Suitable 
catalysts include FeCl.sub.3, AlCl.sub.3, SnCl.sub.4, ZnCl.sub.2, 
TiCl.sub.4, SbCl.sub.5 and BF.sub.3, which may be in a molar equivalent 
amount (based on the acyl chloride). However, it is also possible to use 
lesser amounts of catalyst at elevated temperatures, suitably under reflux 
temperatures, preferred catalysts under these conditions being FeCl.sub.3, 
I.sub.2, ZnCl.sub.2, iron, copper, strong sulphonic acids such as F.sub.3 
CSO.sub.3 H, and acidic ion exchange resins such as Amberlyst.RTM. 15 and 
Nafion.RTM.. The preferred catalyst is FeCl.sub.3 in a 0.001 to 0.2 molar 
ratio at a temperature of about 50.degree. to 180.degree. C. The reaction 
can be carried out in a solvent inert under the reaction conditions, for 
example ethylene or methylene chloride, benzene, octane, decane or solvent 
mixtures, or in the absence of solvent, conveniently by employing one of 
the reactants in excess, e. g. in the range of 1:5 to 5:1. If AlCl.sub.3 
is being used, the molar ratio is preferably in the range of 0.5 to 2 and 
the suitable solvents are e.g. methylenechloride or ethylenechloride at a 
temperature usually between -10.degree. and -70.degree. C. If in the 
starting material R3 is methyl and R.sub.6 or one R.sub.6 represents a 
5-alkoxy group (formula III) ether cleavage is possible to give the 
6-hydroxy compound which then can be derivatized according to usual 
methods. 
If the compound of formula II represents 2,6-dichlorobenzoylchloride and 
the compound of formula III is 1,2,3-trialkoxy-5-alkylbenzene, the 
Friedel-Crafts reaction with AlCl.sub.3 can be used to prepare different 
products dependent on the reaction conditions. In case of a molar amount 
of 0.5 to 2 of aluminiumchloride, a temperature of about 0.degree. to 
25.degree. C. and a solvent such as methylene or ethylene, the ether 
cleavage takes place in the 6-position (ortho position) of the compound of 
formula I within about 1 to 20 hours; at a higher temperature (about 
40.degree. C.) with--if necessary--longer reaction times (between about 2 
and 24 hours) ether cleavage can be performed in the 5-(meta)-position 
too. 
The processes described below can analogously be applied to other starting 
compounds, if desired. 
Starting from compounds of formula 
##STR9## 
wherein R.sup.1, R.sup.2 represent preferably Cl, CH.sub.3, R is H or 
O-alkyl and alkyl is preferably methyl, ether cleavage between about 
50.degree. and 100.degree. C. with HBr/acetic acid leads to compounds of 
formula 
##STR10## 
wherein R' is H or OH. 
Starting from a compound of formula 
##STR11## 
wherein R.sup.1 and R.sup.2 are defined as before, the cleavage of the 
O-alkyl group can be carried out with AlCl.sub.3 (0.5-2 mol) in an inert 
solvent such as methylenechloride at about 20.degree.-50.degree. C. to 
give the corresponding OH compound. 
The alkylation of compounds of formula VIII, IX or the ether cleavage 
product received from X can be carried out according to usual methods. 
Compounds of formula IX wherein R' is H can be reacted with an 
alkylhalogenide (wherein the alkyl moiety may be substituted) in a lower 
alcohol in the presence of a basic compound such as potassium carbonate at 
elevated temperatures (e.g. 60.degree.-150.degree. C.). 
In case of hydroxy groups in other positions (as in VIII, R'=OH or in the 
reaction product received from X) a salt with a metal has to be produced 
by reacting the hydroxy compound with e.g. potassium hydroxide. The salt 
is then reacted with an optionally substituted alkyl halogenide in a polar 
solvent (e.g. dimethylformamide) in the absence of water. 
Dialkylation of compounds of formula IX wherein R' is OH with the same 
optionally substituted alkyl groups can be carried out starting from the 
corresponding di-alkali, preferably di-sodium salt, which can be obtained 
from the dihydroxy compound and sodium hydride in an inert solvent (e.g. 
tetrahydrofurane), the salt is then reacted in an inert polar solvent 
(e.g. dimethylformamide) with an excess of the optionally substituted 
alkylhalogenide at a temperature between about 80.degree. and 120.degree. 
C. 
Dialkylation with a dihalogen compound of formula Hal-(CH.sub.2).sub.n -Hal 
(Hal=Cl, Br or I; n=1 to 4) leads to cyclisation (compound XI; n as 
before): 
##STR12## 
The reaction of the dihydroxy compound IX (R'=OH) with the dihalogen 
compound is carried out in the presence of an excess of potassium 
carbonate and of a small amount of copperoxide as catalyst at temperatures 
between about 10.degree. and 50.degree. C., preferrably at room 
temperature. 
To prepare acylated compounds a corresponding hydroxy compound, for example 
of formula XII 
##STR13## 
wherein R.sub.1 and R.sub.2 are Cl or CH.sub.3, is reacted in form of its 
(e.g. potassium) salt in an inert polar solvent, such as 
dimethylformamide, with an optionally substituted acid chloride at a 
temperature between about 10.degree. to 50.degree. C. 
Acylation of compounds of formula IX (with R'=H)can be carried out by 
heating that compound with an acid anhydride in the presence or without an 
inert solvent at temperatures between about 80.degree. and 120.degree. C. 
For the preparation of compounds of formula XIII, 
##STR14## 
wherein R represents a t-butoxy group, R.sup.1 and R.sup.2 are defined as 
before but preferably represent Cl, the corresponding hydroxy compound 
(XIII; R=OH) is dissolved in an innert solvent, the solution cooled to 
about -70.degree. C. and after addition of a catalytical amount of 
trifluoromethane sulfonic acid a stream of 2-methylpropene is bubbled into 
the mixture for 2 to 6 hours. After neutralizing the acid, the resulting 
t-butoxy compound can be isolated. 
A 5-nitro compound of formula XIV 
##STR15## 
(R=NO.sub.2) can be prepared by nitration of the corresponding compound 
unsubstituted in the 5-position (R=H) with concentrated (65%) nitric acid 
at about 50.degree. to 100.degree. C. 
Nitration of compounds of formula XV 
##STR16## 
in the 2-position can be carried out with concentrated (65%) nitric acid 
at about 30.degree. to 60.degree. C. 
The resulting or otherwise prepared nitro compounds can be reduced to the 
corresponding amino compounds, e. g. of formula XVI 
##STR17## 
with excess powdered iron in a mixture of water/acetic acid 50:1 at 
elevated temperature (60.degree. to 100.degree. C.). 
Reaction of the amino compounds with excess formic acid at reflux 
temperature leads to formylation of the amino group. 
Compounds of formula XIV (R=H) can be brominated in 5-position when the 
equimolar amount of bromine (e. g. in trichloromethane) is added dropwise 
to the solution of the compound in trichloromethane at 10.degree. to 
30.degree. C. 
Benzophenothiones (I; X=S) can be prepared from the corresponding 
benzophenones by heating them with phosphorus pentasulfide in an inert 
solvent to reflux temperature for 2 to 10 hours. 
When the magnesium halide is reacted with a nitrile, i.e. the other group 
Z.sup.1 or Z.sup.2 (formulae II, III) represents CN, the immediate 
reaction product is an imine of formula IV: 
##STR18## 
This intermediate is readily converted to the desired benzophenone 
derivatives of formula I wherein X is an oxygen atom by acid hydrolysis, 
suitably using mineral acids such as hydrochloric or sulphuric. 
When magnesium halide is reacted with an aldehyde, i.e. the other group 
Z.sup.1 or Z.sup.2 represents CHO, the immediate reaction product is a 
tertiary alcohol of formula V: 
##STR19## 
This formula V intermediate is readily converted to the desired 
benzophenone derivatives of formula I wherein X is an oxygen atom by 
oxidation, suitably using Mn(IV), Mn(VII), Ce(IV) or Cr(VI) derivatives, 
nitric acid or oxygen in the presence of a catalyst. 
Certain oxime derivatives of formula I may be prepared by reacting the 
appropriately substituted nitrile oxide of formula VI with a suitable 
o-dimethoxybenzene of formula VII in the presence of aluminum chloride and 
an inert solvent to form an intermediate and hydrolyzing the intermediate 
in aqueous acid to give the desired product compounds of Ib. The reaction 
is shown in flow diagram I. 
##STR20## 
For compounds of formula Ib the substituents R.sup.1, R.sup.2, R.sup.3, 
R.sup.6 and n as defined hereinabove for formula I and Ia and m is 0 or an 
integer of 1, 2 or 3. The oximes of formula Ib may be O-alkylated or 
O-acylated using conventional alkylation and acylation techniques. 
The substituents of the benzophenones produced according to the processes 
of the invention may be derivatized further according to established 
methods or routine adaptations thereof, such as hydrogenation, acylation, 
cleavage of ether bonds, alkylation or nitration. 
The formula Ia compounds of the invention are excellent fungicides, 
especially for the control of phytopathogenic fungi in agriculture or 
related fields. They are useful for the control of powdery mildew 
diseases, particularly of Erysiphe graminis, Podosphaera leucotricha or 
Uncinula necator. Due to excellent plant tolerance, the compounds may be 
used in all cultivation of plants where infection by the controllable 
fungi is not desired, e.g. small grain cereals, apples, vine. The absence 
of target crop phytotoxicity at fungus control rates is a feature of the 
present invention. 
The present invention also provides a fungicidal composition which 
comprises a compound of formula I or Ia as defined hereinabove and an 
agriculturally acceptable carrier. Said composition may contain one or 
more compounds of the present invention. Preferably, at least one carrier 
in a composition according to the invention is a surface-active agent. For 
example, the composition may contain at least two carriers, at least one 
of which is a surface-active agent. 
The compounds according to formula I or Ia may be applied as technical 
material, however, said compounds are preferably applied as a composition 
comprising, besides the formula I or Ia compounds, adjuvants and 
auxiliaries which are known for formulation purposes and are manufactured 
into e.g. emulsion concentrates, solutions which may be sprayed directly 
or diluted, diluted emulsions, wettable powders, soluble powders, dusts, 
granulates, microencapsulates by well-established procedures. The form of 
application such as spraying, atomizing, dispersing, pouring may be chosen 
like the compositions according to the desired objectives and the given 
circumstances. 
It is contemplated, compounds of formula I or Ia may be formulated or 
applied, either alone or in combination, with one or more pesticides or 
plant growth regulants. Pesticides used in combination may be herbicides, 
insecticides or other fungicides or a combination thereof. When the 
formula I or Ia compounds are applied in combination with another 
pesticide or pesticides, they may be applied simultaneously or 
sequentially. Among the available fungicides which may be used in 
combination with formula I compounds are 4,6-dinitro-o-cresol, benalaxyl, 
benomyl, captafol, captan, carbendazim, chlorothalonil, copper, cymoxanil, 
dichlofluanid, dichlone, difenoconazole, dimethomorph, diniconzole, 
dinocap, dithianon, fenpiclonil, fenpropiomorph, hymaxazol, imazalil, 
iprodione, isoprothiolane, kasugamycin, mancozeb, mepronil, mercuric 
oxide, oxadixyl, oxolinic acid, penconazole, propineb, pyrifenox, 
thiabendazole, thiram, tolclofos-methyl, triadimefon, triflumizole, 
triforine validamycin A, vinclozolin, zineb, ziram, and the like. 
The fungicidal compositions of the invention may be prepared by 
well-established procedures, e.g. intensive mixing and/or grinding of the 
active ingredients with other substances, such as fillers, solvents, solid 
carriers, and optionally surface-active compounds (tensides). 
Solvents may be aromatic hydrocarbons, preferably the fractions C.sub.8 to 
C.sub.12, e.g. xylenes or xylene mixtures, substituted naphthalenes, 
phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic 
hydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols as well 
as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and 
dimethyl ether, ketones such as cyclohexanone, strongly polar solvents 
such as N-methyl 2-pyrrolidone, dimethyl sulphoxide, alkyl formamides, 
epoxidized vegetable oils, e.g. epoxidized coconut or soybean oil, water. 
Solid carriers, which may be used for dusts or dispersible powders, may be 
mineral fillers, such as calcite, talc, kaolin, montmorillonite, 
attapulgite. The physical properties may be improved by addition of highly 
dispersed silica gel or highly dispersed polymers. 
Carriers for granulates may be porous material, e.g. pumice, broken brick, 
sepiolite, bentonite, non-sorptive carriers may be calcite or sand. 
Additionally, a multitude of pre-granulated inorganic or organic materials 
may be used, such as dolomite or crushed plant residues. 
Suitable surface-active substances may be non-ionogenic, anionic or 
cationic tensides with good dispersing, emulgating and wetting properties 
depending on the nature of the benzophenone compound to be formulated. 
Tensides may also mean mixtures of tensides. 
Suitable tensides may be so-called water-soluble soaps as well as 
water-soluble synthetic surface-active compounds. Soaps usually are 
alkali, earth alkali or optionally substituted ammonium salts of higher 
fatty acids (C.sub.10 -C.sub.20), e.g. the sodium or potassium salts of 
oleic or stearic acid or of mixtures of natural fatty acids which are 
prepared, for example, from coconut or tallow oil. Furthermore, 
methyltaurine salts of fatty acids may be used. However, so-called 
synthetic tensides are preferably used, especially fatty sulphonates, 
fatty sulphates, sulphonated benzimidazole derivatives or alkyl aryl 
sulphonates. The fatty sulphates or fatty sulphonates are normally used as 
alkali, earth alkali or optionally substituted ammonium salts and have an 
alkyl moiety of 8 to 22 carbon atoms, whereby alkyl also means the alkyl 
moiety of acyl residues, such as the sodium or calcium salt of lignin 
sulphonic acid, of sulphuric acid dodecylate or of a mixture of fatty 
alcohols prepared from natural fatty acids. This also includes the salts 
of sulphuric acid esters, sulphonic acids and adducts of fatty alcohols 
and ethylene oxide. The sulphonated benzimidazole derivatives preferably 
contain 2 sulphonic acid residues and a fatty acid residue with 8 to 22 
carbon atoms. Alkyl aryl sulphonates are, for example, the sodium, calcium 
or triethyl ammonium salts of dodecyl benzene sulphonic acid, dibutyl 
naphthalene sulphonic acid or of a condensate of naphthalene sulphonic 
acid and formaldehyde. Furthermore, phosphates, such as the salts of the 
phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or 
phospholipids, may be used. 
Non-ionic tensides are preferably polyglycolether derivatives of aliphatic 
or cycloaliphatic alcohols, saturated or non-saturated fatty acids and 
alkylphenols, which have 3 to 10 glycol ether groups and 8 to 20 carbon 
atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in 
the alkyl residue of the alkyl phenols. Other suitable non-ionic tensides 
are the water-soluble, 20 to 250 ethylene glycol ether groups containing 
polyadducts of ethylene oxide and polypropylene glycol, ethylene diamino 
polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon 
atoms in the alkyl moiety, the substances normally contain 1 to 5 ethylene 
glycol units per propylene glycol unit. Examples of non-ionic tensides are 
nonylphenol polyethoxy ethanols, castor oil polyglycol ether, polyadducts 
of ethylene oxide and polypropylene, tributyl phenoxy polyethoxy ethanol, 
polyethylene glycol, octyl phenoxy polyethoxy ethanol. Furthermore, fatty 
acid esters of polyoxy ethylene sorbitan, such as polyoxy ethylene 
sorbitan trioleate may be used. 
Cationic tensides preferably are quaternary ammonium salts, which have at 
least one alkyl residue with 8 to 22 carbon atoms and, furthermore, low, 
optionally-halogenated alkyl, benzyl or hydroxyalkyl residues. The salts 
are preferably halides, methyl sulphates or alkyl sulphates, e.g. stearyl 
trimethyl ammonium chloride or benzyl bis(2-chloroethyl) ethyl ammonium 
bromide. 
The tensides generally used for compositions of the invention are disclosed 
in publications such as: "McCutheon's Detergents and Emulsifiers Annual", 
MC Publishing Corp., Ridgewood, N.J., USA 1981; H. Stache, 
"Tensid-Taschenbuch", 2nd ed., C. Hanser, Munich, Vienna, 1981; M. and J. 
Ash, "Encyclopedia of Surfactants", vol. I-III, Chemical Publishing Co., 
New York, N.Y., USA 1980-1981. 
The pesticidal compositions of the invention may comprise 0.1% to 95%, 
preferably 0.1% to 80% of at least one compound of formula I or Ia, 1% to 
99.9% of a solid or liquid adjuvant and 0% to 25%, preferably 0.1% to 25%, 
of a tenside. 
Exemplary of the compositions of the invention are: 
Emulsion Concentrates 
Active ingredient: 1% to 20%, preferably 5% to 10% Surface-active 
substance: 5% to 30%, preferably 10% to 20% Liquid carrier: 50% to 94%, 
preferably 70% to 85% 
Suspension-Concentrates 
Active ingredient: 5% to 75%, preferably 10% to 50% Water: 94% to 24%, 
preferably 88% to 30% Surface-active substance: 1% to 40%, preferably 2% 
to 30% 
Wettable Powder 
Active ingredient: 0.5% to 90%, preferably 1% to 80% Surface-active 
substance: 0.5% to 20%, preferably 1% to 15% Solid carrier: 5% to 95%, 
preferably 15% to 90% 
Dusts 
Active ingredient: 0.1% to 10%, preferably 0.1% to 1% Solid carrier: 99.9% 
to 90%, preferably 99.9% to 99% 
Granulates 
Active ingredient: 0.5% to 30%, preferably 3% to 15% Solid carrier: 99.5% 
to 70%, preferably 97% to 85% 
As commodity the inventive fungicidal compositions may preferably be in a 
concentrated form whereas the end-user generally employs diluted 
compositions. Said compositions may be diluted to a concentration of 
0.001% of active ingredient (a.i.). The doses usually are in the range 
from 0.01 to 10 kg a.i./ha. 
Said compositions may also comprise other auxiliaries such as stabilizers, 
defoamer, viscosity controlling agents, thickeners, adhesives, fertilisers 
or other active ingredients to obtain special effects. 
For a more clear understanding of the invention, the following specific 
examples are set forth below. These examples are merely illustrations and 
are not to be understood as limiting the scope and underlying principles 
of the invention in any way. Indeed, various modifications of the 
invention in addition to those shown and described herein will become 
apparent to those skilled in the art from the following examples and 
foregoing description. Such modifications are also intended to fall within 
the scope of the appended claims. The terms HNMR, CIMS and IR as used in 
the examples hereinbelow designate proton nuclear magnetic resonance, mass 
spectrum and infrared, respectively. 
EXAMPLE 1 
2,6-Dichloro-4',5'-dimethoxy-2'-methylbenzophenone (Compound 1) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R=CH.sub.3, R.sup.4 =CH.sub.3, R.sup.5 
=OCH.sub.3, X=O, Y=O, m=1, n=0) 
A mixture of 4-methyl-veratrol (76.1 g; 500 mmol), 2,6-dichlorobenzoyl 
chloride (120.4 g; 575 mmol) and iron(III)chloride (0.5 g) is heated with 
stirring. The reaction starts at 90.degree. C. under formation of hydrogen 
chloride, the main reaction is complete within 10 min at 95.degree. C. 
Subsequently, the reaction mixture is stirred for another 30 min at 
100.degree. C. and then cooled to 65.degree. C. Upon addition of methanol 
(350 ml) Compound 1 begins to crystallize. A water/methanol mixture (1:1 
v/v; 300 ml) is then slowly added at 40.degree. C. and the mixture is 
cooled to room temperature with stirring for 30 min. The solid material is 
collected by vacuum filtration, three times washed with methanol/water 
(3:1 v/v; 100 ml each) and dried yielding colorless crystals, 148.6 g, 
(91.4% y) mp 101.5.degree. C. 
EXAMPLE 2 
Derivatization of benzophenones 
A) 2.6-Dichloro-4',5'-dimethoxy-2'-nitro-benzophenone (Compound 2) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =NO.sub.2, R.sup.4 =CH.sub.3, R.sup.5 
=OCH.sub.3, X=O, Y=O, m=1, n=0) 
A portion of 2,6-dichloro-3',4'-dimethoxybenzophenone (6.22 g, 20 mmol), 
prepared analogously to Example 1, is added within 15 min into nitric acid 
(65%; 40 ml) which is heated to 40.degree. C. The clear solution is 
stirred for 10 min at 40.degree. C., then 1 h at room temperature. The 
reaction mixture is then poured into water whereupon a slowly solidifying 
oil forms. This material is dissolved in a small amount of N,N-dimethyl 
formamide under warming, then methanol is added and the mixture is chilled 
and filtered giving Compound 2 as yellow crystals, 5.57 g, (78% y) with mp 
143.degree. C. 
B) 2'-Amino-2,6-dichloro-4',5'-dimethoxybenzophenone (Compound 3) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =NHCHO, R.sup.4 ==CH.sub.3, R.sup.5 
=OCH.sub.3, X=O, Y=O, m=1, n=0) 
A portion of 2,6-dichloro-3',4'-dimethoxy-2'-nitrobenzophenone (Compound 2; 
3.56 g, 10 mmol) is added to a mixture of water (50 ml), glacial acetic 
acid (1 ml) and powdered iron (3.30 g, 60 mmol) within 15 min at 
70.degree. C. The reaction mixture is stirred at 95.degree. C. for another 
3 h. After cooling, toluene (50 ml) is added and the solid material 
removed by vacuum filtration. The filter cake is washed with toluene. The 
filtrate and washings are combined and washed with water, dried and then 
applied onto a flash chromatography column (silica gel, 50 g). The column 
is consecutively eluted with toluene, and toluene containing 1%, 2%, 5% 
and 10% of acetone (250 ml each). The fraction eluted by 10% acetone is 
concentrated in vacuo to a final volume of 10 ml whereby Compound 3 
crystallizes yielding yellow crystals, 1.61 g, (49% y) mp 181.degree. C. 
C) 2,6-Dichloro-4',5'-dimethoxy-2'-formylamino-benzophenone (Compound 4) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =NHCHO, R.sup.4 =CH.sub.3, R.sup.5 
=OCH.sub.3, X=O, Y=O, m=1, n=0) n=0) 
A mixture of 2'-amino-2,6-dichloro-4',5'-dimethoxybenzophenone (Compound 3; 
0.82 g, 2.5 mmol) and formic acid (30 ml) is heated at reflux temperature 
for 24 h, and evaporated in vacuo. The residue is dissolved in a small 
amount of toluene, Compound 4 crystallizes upon addition of cyclohexane 
giving colorless crystals, 0.64 g, (72% y) with mp 152.degree. C. 
D) 2,6-Dichloro-5'-hydroxy-4'-methoxy-2'-methylbenzophenone (Compound 5) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =CH.sub.3, R.sup.4 CH.sub.3, R.sup.5 
=OH, X=O, Y=O, m=1, n=0) 
A mixture of 2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone (Compound 
1; 2.5 g, 7.7 mmol), hydrogen bromide/acetic acid (33%, 10 ml) and glacial 
acetic acid (10 ml) is stirred for 1.5 h at 75.degree. C., poured into 
water (100 ml) and twice extracted with dichloromethane (50 ml each). The 
extracts are combined, dried, and concentrated in vacuo. The resulting oil 
is applied onto the top of a flash chromatography column (silica gel, 30 
g). Elution is carried out with toluene and toluene/acetone, 9:1 (500 ml 
each). The fractions containing the material with an R.sub.f =0.54 (silica 
gel; toluene/acetone, 9:1) are combined and the solvent is evaporated in 
vacuo until a final volume of 20 ml is reached. The solution is then 
extracted three times with aqueous sodium hydroxide (2N; 30 ml each). The 
aqueous layer is acidified with hydrochloric acid (6M) and the precipitate 
is collected by vacuum filtration and dried to give Compound 5 as 
colorless crystals, 1.1 g, (45.9% y) mp 152.degree. C. 
E) 2,6-Dichloro-4'-methoxy-2 '-methyl-5 h-propoxy-benzophenone (Compound 6) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =CH.sub.3, R.sup.4 =CH.sub.3, R.sup.5 
=O-n-C.sub.3 H.sub.7, X=O, Y=O, m=1, n=0) 
A mixture of 2,6-dichloro-5'-hydroxy-4'-methoxy-2'-methylbenzophenone 
(Compound 5; 1.0 g, 3.2 mmol), n-propyl bromide (0.5 g, 4 mmol), potassium 
carbonate (2.8 g, 20 mmol) and ethanol (10 ml) is stirred for 6 h at 
80.degree. C., filtered and the filtrate is evaporated in vacuo. The 
residue is applied onto a flash chromatography column (silica gel, 30 g). 
Elution with toluene (750 ml) yields Compound 6 as a brown oil, 800 mg, 
(70.7% y) which slowly crystallizes (mp 73.degree.-75.degree. C.) 
F) 2,6-Dichloro-4',5'-dimethoxy-2'-methyl-benzophenthione (Compound 7) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =CH.sub.3, R.sup.4 =O-CH.sub.3, 
R.sup.5 =O-CH.sub.3, X=S, Y=O, m=1, n=0) 
A mixture of 2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone (Compound 
1; 3.25 g, 10.0 mmol), phosphorus pentasulphide (2.22 g, 10.0 mmol) and 
toluene (50 ml) is stirred at 110.degree. C. for 5 h, treated with 
p-dioxane, stirred at 100.degree. C. for a further 24 h. The supernatant 
is decanted from black, tarry reaction products, silica gel (15 g) is 
added and the solvent is evaporated in vacuo. A flash chromatography 
column is packed with silica gel (100 g) and the charged silica gel is 
layered on top of it. The column is subsequently eluted with petrol 
ether/acetone (500 ml, 98:2, v/v) and petrol ether/acetone (750 ml, 95:5, 
v/v) yielding Compound 7 as a dark green oil 40 mg, (1.2% y), which slowly 
solidifies. When the oil is triturated with cyclohexane three times, it 
gives a solid, mp 142.degree. C. 
EXAMPLE 3 
Using essentially the same procedures described hereinabove for Examples 1 
and 2 and employing standard derivatization techniques where appropriate, 
the following compounds are prepared and shown in Table I. 
3 TABLE I 
- 
##STR21## 
C 
omp 
No. R.sup.1 R.sup.2 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 Y Mp 
.degree.C. 
8 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.2 H.sub.5 H O 
87 9 Cl 6-Cl H CH.sub.3 C.sub.2 H.sub.5 OCH.sub.3 H O 
106 
10 Cl 6-Cl H CH.sub.3 CH.sub.3 Cl H O 168 
11 Cl 6-Cl 3-NO.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
12 Br H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 69-71 
13 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)C.sub.2 H.sub.5 H O 142-145 
14 Cl 6-Cl H CH.sub.3 CH.sub.3 H H O 
89 15 I H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 
66-68 
16 Cl 6-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 
56 17 Cl 6-CH.sub.3 H F CH.sub.3 OCH.sub.3 H O 95 
18 (CHCH).sub.2 6-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O 
19 I 3-I 5-I CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
20 Br 5-Br H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
21 Cl 4-NO.sub.2 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 126-128 
22 Cl 6-Cl H CH.sub.3 CH.sub.3 SCH.sub.3 H S 105 
23 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OCH.sub.3 O 
92 24 Cl 6-Cl H CH.sub.3 CH.sub.2 
O H O 142 25 Cl 6-Cl H CH.sub.3 CH.sub.3 I H S 
26 Br 5-OCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
27 Cl 5-Br H CH.sub.3 CH.sub.3 OCH.sub.3 H O 94-96 
28 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)CH(CH.sub.3).sub.2 H O 132-135 
29 Cl 5-Cl 6-OCH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
30 Cl 6-Cl H CF3 CH.sub.3 Cl H O 
31 Cl 6-Cl H CH.sub.3 CH.sub.3 OCHF.sub.2 H O 126-128 
32 CF.sub.3 5-CF.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 98-101 
33 Cl 6-Cl H CH.sub.3 CH.sub.3 H 3-OCH.sub.3 O 100-125 
34 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)C(CH.sub.3).sub.3 H O 167 
35 Cl 6-Cl H CH.sub.3 H OH H O 201-203 
36 Cl 6-Cl H SCH.sub.3 CH.sub.3 OCH.sub.3 H O 185 
37 Cl 6-Cl H S(O.sub.2)CH.sub.3 CH.sub.3 OCH.sub.3 H O 163 
38 Cl 6-Cl H CH.sub.3 CH.sub.3 CH.sub.3 3-CH.sub.3 O 
78 39 Cl 6-Cl H S(O)CH.sub.3 CH.sub.3 OCH.sub.3 H O 178 
40 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 
CHCH.sub.2 H O oil 41 Cl 3-Cl 5-Cl CH.sub.3 CH.sub.3 
OCH.sub.3 H O 
99-101 42 Cl 6-Cl H C 
H.sub.3 (CH.sub.2).sub.2 
O H O oil 43 Cl 6-Cl H CH.sub.3 
CHF.sub.2 OCHF.sub.2 H O 65-68 
44 CF.sub.3 6-CF.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 105-107 
45 Cl 6-Cl H CHCH.sub.2 CH.sub.3 OCH.sub.3 H O 
46 I 6-F H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
47 Cl 3-Cl H CH.sub.3 CH.sub.3 OC.sub.2 
H.sub.5 H O 97 48 Cl 6-Cl H CH.sub.3 C.sub.2 H.sub.5 
OC.sub.2 H.sub.5 H O 
77 49 Cl 6-Cl H CHCHCN 
CH.sub.3 OCH.sub.3 H O 
50 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 3-Br O 
86 51 Cl 4-Cl 5-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O 
160 
52 Cl 6-Cl H CH.sub.3 CH.sub.3 C.sub.4 H.sub.9 
-t H O 124 53 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.4 
H.sub.9 -n H O 
51 54 Cl 6-Cl H 
CH.sub.3 CH.sub.3 OC.sub.4 H.sub.9 
-i H O oil 55 Cl 6-Cl H CH.sub.3 CH.sub.3 H 
H S 
56 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C.sub.6 H.sub.5 H O 119-121 
57 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.5 H.sub.11 -n H O 46-48 
58 Cl 6-Cl H CH.sub.3 CH.sub.3 OC.sub.3 H.sub.7 -i H O oil 
59 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OH O 161 
60 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C(O)OC.sub.2 H.sub.5 H O 
105-108 
61 Cl 6-Cl H CH.sub.3 CH.sub.3 H 2-OCH.sub.3 O 135 
62 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OC.sub.2 H.sub.5 O 72 
63 Cl 6-Cl H CH.sub.3 CH.sub.3 Cl H S 
64 Cl 4-Cl 6-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O 108-109 
65 Cl 6-Cl H CH.sub.3 CH.sub.3 Br H S 
66 F 6-F H CH.sub.3 CH.sub.3 OCH.sub.3 H O 75 
77 67 Cl H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 
oil 
68 Cl 4-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
69 Cl 6-Cl H CH.sub.3 CH.sub.3 CH.sub.3 H O 135-138 
70 Cl 6-Cl H CF.sub.3 CH.sub.3 Br H O 
71 Cl 5-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 H O 100-102 
72 Cl 6-Cl H C.sub.2 
H.sub.5 CH.sub.3 OCH.sub.3 H O oil 73 Cl 3-Cl H 
CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
74 Cl 6-Cl H CN CH.sub.3 OCH.sub.3 H O 120 
75 F 6-CF.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 
76 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 
CN H O 127 77 Cl 6-F H CH.sub.3 CH.sub.3 OCH.sub.3 
H O 72-73 
78 Cl 6-Cl H I CH.sub.3 OCH.sub.3 H O 101 
79 Cl 6-Cl H C.sub.3 H.sub.7 -n CH.sub.3 OCH.sub.3 H O 
72 80 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)CH.sub.3 H O 
156-159 
81 Cl 6-Cl H Br CH.sub.3 OCH.sub.3 H O 124 
82 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 CH H O 
87 83 Cl 6-Cl H H CH.sub.3 H 3-OCH.sub.3 O 127 
84 Cl 6-Cl H CH.sub.3 H H 3,6-di-CH.sub.3 O 122 
85 Cl 6-Cl H CH.sub.3 CH.sub.3 H 3,6-di-CH.sub.3 O 111 
86 Cl 6-Cl H CF.sub.3 C(O)-2,6-C.sub.12 C.sub.6 H.sub.3 H H O 186 
87 CH.sub.3 6-CH.sub.3 H H CH.sub.3 H 3-OCH.sub.3 O 
84 88 Cl 6-Cl H H CH.sub.3 H 3-Br O 129 
89 Cl 6-Cl H H CH.sub.3 Br 3-OCH.sub.3 O 140 
90 Cl 6-Cl H OCH.sub.3 CH.sub.3 OCH.sub.3 H O 124 
91 Cl 6-Cl H CH.sub.3 CH.sub.3 OC(O)H H O 156 
92 OCH.sub.3 6-OCH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 113 
93 Cl 6-Cl H COOH CH.sub.3 OCH.sub.3 H O 174 
94 Cl 6-Cl H CH.sub.3 CH.sub.3 S(O).sub.2 CH.sub.3 H SO.sub.2 233 
95 Cl 6-Cl H CH.sub.3 CH.sub.3 SOCH.sub.3 H SO 227 
96 Cl 6-Cl H CH.sub.3 CH.sub.3 O.sub.n -C.sub.7 H.sub.15 H O oil 
97 Cl 6-Cl H CH.sub.3 CH.sub.3 O.sub.n -C.sub.8 H.sub.17 H O oil 
98 Cl 6-Cl H CH.sub.3 CH.sub.3 O.sub.n -C.sub.10 H.sub.21 H O oil 
99 CH.sub.3 4-CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 H O 
74 
100 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -c-C.sub.3 H.sub.5 H O oil 
101 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -c-C.sub.6 H.sub.11 H O 
108 
102 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.2CH(CH.sub.3).sub.2 H 
O oil 
103 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 CHC(CH.sub.3).sub.2 H O oil 
104 CH.sub.3 6-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 H O 90-92 
105 Cl 6-c1 H CH.sub.3 CH.sub.3 Oc-C.sub.5 H.sub.9 H O oil 
106 Cl 6-Cl H CH.sub.3 CH.sub.3 Oc-C.sub.6 H.sub.11 H O oil 
107 Cl 6-Cl H H CH.sub.3 3!-(CHCH).sub.2 2! H O 155-157 
108 
Cl 6-Cl H CH.sub.3 CH.sub.3 ONa H O glass 109 Cl 
6-Cl H CH.sub.3 CH.sub.3 OSi(CH.sub.3).sub.3 H O oil 
110 
Br 6-Br H CH.sub.3 CH.sub.3 OCH.sub.3 H O 102 
111 Cl 6-Cl H CH.sub.3 CH.sub.3 OK H O 
98 112 Cl 6-Cl H OCH.sub.3 CH.sub.3 Br 
2-OCH.sub.3 O 183 
113 CN H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 
76 114 Cl 6-Cl H CH.sub.3 CH.sub.2 
O 2-OCH.sub.3 
98 115 Cl 6-Cl H N 
HCH.sub.3 CH.sub.3 OCH.sub.3 H 163 
116 Cl 6-Cl H OH CH.sub.3 OCH.sub.3 H O 
80 117 Cl 6-Cl H CH.sub.3 CH.sub.3 
OCH.sub.2 
Si(CH.sub.3).sub.3 H O oil 118 Cl 
H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 62-64 
119 
Cl 3-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2-OCH.sub.3 O oil 
120 
Cl 4-Cl 6-Cl CH.sub.3 CH.sub.3 OCH.sub.3 H O 126 
121 F 6-F H CH.sub.3 CH.sub.3 OCH.sub.3 H O 
84 122 Cl 5-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 
H oil 
123 
Cl 6-Cl H OCH.sub.3 CH.sub.3 CH.sub.3 6-OCH.sub.3 O 115 
124 
I H H CH.sub.3 CH.sub.3 OCH.sub.3 2-OCH.sub.3 O oil 
125 Br H H CH.sub.3 CH.sub.3 OCH.sub.3 H O 
34 126 
Cl 6-Cl H CH.sub.3 CH.sub.3 On-C.sub.6 
H.sub.13 H O oil 127 Cl 6-Cl H CH.sub.3 CH.sub.3 
OCH.sub.3 2On-C.sub.3 H.sub.7 O 
46 128 Cl 6-Cl H CH.sub.3 
CH.sub.3 OCH.sub.3 2On-C.sub.7 
H.sub.15 O oil 129 Cl 6-Cl H CH.sub.3 
CH.sub.3 OCH.sub.3 2On-C.sub.10 
H.sub.21 oil 130 Cl 6-Cl H CH.sub.3 
CH.sub.3 OCH.sub.3 2-OC(O)CH.sub.3 O 164 
131 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.5 H.sub.11 O oil 
132 
Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.2CH(CH.sub.3).su 
b.2 O 101 
133 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2 CHCH.sub.2 O 73 
134 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2 CCH O 123 
135 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2Oc-C.sub.5 H.sub.9 O 
89 
136 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 6OCH.sub.2 C.sub.6 H.sub.5 O 
80 
137 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.12 H.sub.25 O oil 
138 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2 -c-C.sub.6 
H.sub.11 O 
88 139 Cl 
6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2On-C.sub.6 
H.sub.13 O oil 140 Cl 6-Cl H CH.sub.3 CH.sub.3 On-C.sub.12 
H.sub.25 H O oil 
141 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C(O)N(C.sub.2 H.sub.5).sub.2 
H O 
97 
142 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 
C(O)NH.sub.2 H O 136 143 Cl 6-Cl H CH.sub.3 CH.sub.3 
OCH.sub.3 2O(CH.sub.2).sub.2OCH.sub.3 O 
84 144 Cl 6-CL H CH.sub.3 CH.sub.3 
OCH(C.sub.2 
H5 ).sub.2 H O oil 145 Cl 
6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.2 OH H O 
87 146 
Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.3 OH H O 
86 147 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -p-C.sub.6 
H.sub.4 
-CH.sub.3 H O oil 148 
Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -p-C.sub.6 H.sub.4 
C(CH.sub.3).sub.3 H O 119 
149 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2OCH.sub.2 C(O)-morpholide O 
oil 
150 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.2 OCH.sub.3 H O oil 
151 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C(O)-morpholide H O 163 
152 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 -p-C.sub.6 
H.sub.4OCH.sub.3 H O oil 
153 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.3 OC.sub.6 H.sub.5 H O 
oil 
154 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.3 
-morpholinyl .times. 
HCl O 225 155 Cl 6-Cl H 
CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.2N(CH.sub.3).sub.2 .times. 
HCl O 103 
156 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH2).sub.2 N(C.sub.2 
H.sub.5).sub.2 .times. 
HCl O 144 157 Cl 6-Cl H 
CH.sub.3 CH.sub.3 OC.sub.2 H.sub.5 2-OCH.sub.3 O 
68 158 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 
2O(CH.sub.2).sub.3 O 
87 159 Cl 6-Cl H 
CH.sub.3 CH.sub.3 OCH.sub.3 2O(CH.sub.2).sub.3 -piperidy 1 .times. HCl O 
70 
160 Cl 6-Cl H CH.sub.3 n-C.sub.7 H.sub.15 OCH.sub.3 H O 
51 161 Cl 6-Cl H CH.sub.3 n-C.sub.3 H.sub.7 OCH.sub.3 H O 
80 
162 Cl 6-Cl H CH.sub.3 n-C.sub.4 H.sub.9 OCH.sub.3 H O 
89 163 Cl 6-Cl H CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 H O 
96 
164 CH.sub.3 3-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3 O 
82 
165 CH.sub.3 5-CH.sub.3 H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3 O 
oil 
166 
Cl 6-Cl H Cl CH.sub.3 OCH.sub.3 H O 114 
167 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.3- CO.sub.2 C.sub.2 
H.sub.5 H O oil 
168 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 C.sub.6 H.sub.4CF.sub.3 -p H 
O 115-117 
169 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 SiC.sub.2 H.sub.5 
(CH.sub.3).sub.2 H O 
85 170 Cl 6-Cl H 
CH.sub.3 CH.sub.3 OC(CH.sub.3).sub.3 H O 102 
171 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 
OCH H O oil 
172 Cl 6-Cl H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.4 
Br H O oil 173 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 
6-O(CH.sub.2).sub.3 N(C.sub.2 
H.sub.5).sub.2 O oil 174 Cl 6-Cl H CH.sub.3 
CH.sub.3 OCH.sub.3 6-OCH(CH.sub.3).sub.2 O 108 
175 Cl 6-Cl H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.2 CH.sub.2 
OCH.sub.2 CH.sub.2 
OCH.sub.3 O oil 176 Cl 6-Cl H 
CH.sub.3 CH.sub.3 OCOC.sub.6 H.sub.3 C.sub.2 -2,6 6-OCH.sub.3 O 186-189 
177 Cl 6-Cl H H CH OCH.sub.3 6-OCH.sub.3 O 
97 178 Cl 6-Cl H CH.sub.3 CH.sub.3 CH.sub.3 
6-OCH.sub.3 O 106 
179 Cl 6-Cl H OCH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3 O 121-123 
180 
Cl 6-Cl H CH.sub.3 CH.sub.3 NHCOCH.sub.3 H O 155 181 Cl 
6-Cl H CH.sub.3 CH.sub.3 OH 6-OH O 182 
182 CF.sub.3 H H CH.sub.3 CH.sub.3 OCH.sub.3 6-OCH.sub.3 O oil 
183 
CF.sub.3 H H CH.sub.3 CH.sub.3 OCH.sub.3 H O oil 184 Cl 
6-Cl H CH.sub.3 CH.sub.3 OC.sub.4 H.sub.9 -n 6-OC.sub.4 H.sub.9 -n O oil 
185 
Cl 6-Cl H CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 H O 110 
186 
Cl 6-Cl H CH.sub.3 H NO.sub.2 H O 170 
195 OCF.sup.2 
O H CH.sub.3 CH.sub.3 OCH.sub.3 H O 
EXAMPLE 4 
2'-n-Butoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone (Compound 
187) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =CH.sub.3, R.sup.4 =CH.sub.3, R.sup.5 
=OCH.sub.3, R.sup.6 =2-O-(CH.sub.2).sub.3 -CH.sub.3, X=O, Y=O, m=1, n=1) 
a) 2.6-Dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methylbenzothenone (Compound 
59) 
Aluminum chloride (14.67 g, 0.1 mol), 2,6-dichlorobenzoyl chloride (20.95 
g, 0.1 mol) and a solution of 3,4,5-trimethoxytoluene (18.22 g, 0.1 mol) 
in dichloromethane (50 ml), are slowly and consecutively added to 
dichloromethane stirred at 0.degree. C., stirred for 1 h at ice bath 
temperatures and for 16 h at room temperature, and poured into ice. The 
organic layer is separated, washed with dilute hydrochloric acid and 
water, dried, and, after addition of silica gel (100 g), concentrated in 
vacuo. A flash chromatography column is packed with silica gel (400 g) and 
the charged silica gel is layered on top of that. Elution with petrol 
ether/ethyl acetate (90/10, 1 l; 80/20, 1 l; 50/50, 1 l ) yields 
2,6-dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methylbenzophenone, 10.35 g, 
(30% y), mp. 161.degree. C. 
b) 2 6-Dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methylbenzophenone, potassium 
salt (Compound 188) 
(R.sup.1 =Cl, R.sup.2 =6-Cl, R.sup.3 =CH.sub.3, R.sup.4 =CH.sub.3, R.sup.5 
=OCH.sub.3, R.sup.6 =2-OK, X=O, Y=O, m=1, n=0) 
A solution of 
2,6-dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methyl-benzophenone (10.24 g, 
30 mmol) is dissolved in ethanolic potassium hydroxide (1.98 g, 30 mmol; 
85% in ethanol (100 ml)) and stirred at 70.degree. C. for 15 min. The 
solvent is then evaporated in vacuo. The residue is dissolved in hot 
ethanol (50 ml), toluene is added and the solvent is evaporated in vacuo 
giving Compound 188, 11.7 g. 
c) 2'-n-Butoxy-2,6-dichloro-3',4'-dimethoxy-6'-methylbenzophenone (Compound 
187) 
A mixture of 
2,6-dichloro-3',4'-dimethoxy-2'-hydroxy-6'-methyl-benzophenone, potassium 
salt (1.13 g; 3 mmol), 1-bromobutane (0.69 g, 5 mmol) and dimethyl 
formamide (5 ml) are stirred at 100.degree. C. for 8 h, and concentrated 
in vacuo. The residue is dissolved by shaking with a toluene/water 
mixture, after separation, the organic layer is collected washed with 
water and dried. After addition of silica gel (5 g), the solvent is 
evaporated. A flash chromatography column is packed with silica gel (25 g) 
and the charged silica gel is layered on top of that. Elution with petrol 
ether/ethyl acetate (95/5, 500 ml) gives the title compound, 0.82 g, (69% 
y) as colourless crystals, mp. 70.degree. C. 
EXAMPLE 5 
Using essentially the same procedures described in Examples 1, 2 and 4 
hereinabove and employing, if required, standard derivativatization 
methods, the following compounds shown in Table II are prepared 
TABLE II 
__________________________________________________________________________ 
##STR22## 
Comp. 
No. R.sup.1 
R.sup.2 
m R.sup.3 
YR.sup.4 
R.sup.5 R.sup.6 
n mp .degree.C. 
__________________________________________________________________________ 
189 CH.sub.3 
3,5,6-CH.sub.3 
3 CH.sub.3 
OCH.sub.3 
OCH.sub.3 H 0 103 
190 CH.sub.3 
CH.sub.3 
4 CH.sub.3 
OCH.sub.3 
OCH.sub.3 H 0 142-144.5 
191 CH.sub.3 
3,5,6-CH.sub.3 
3 CH.sub.3 
OCH.sub.3 
OCH.sub.3 6-OCH.sub.3 
1 113 
192 CH.sub.3 
3,5,6-CH.sub.3 
3 CH.sub.3 
OCH.sub.3 
OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 
H 0 73 
193 CH.sub.3 
3,5,6-CH.sub.3 
3 CH.sub.3 
OCH.sub.3 
OCH.sub.2 CH.sub.2 CH.sub.3 
H 0 85 
194 CH.sub.3 
3,5,6-CH.sub.3 
3 CH.sub.3 
OCH.sub.3 
OCH.sub.3 6-OH 
1 137 
__________________________________________________________________________ 
EXAMPLE 6 
2,6-Dichloro-3',4'-dimethoxybenzophenone oxime (Compound 195) 
(R.sup.1 =Cl; R.sup.2 =6-Cl, R.sup.3 =H; Y=O; R.sup.4 CH3; R.sup.5 =H, 
R.sup.6 =4-OCH.sub.3 ; R=H 
A stirred dispersion of anhydrous aluminum chloride (2.93 g, 22 mmol) in 
methylene chloride at ice-bath temperatures is treated sequentially with a 
solution of 2,6-dichlorobenzonitrile oxide (3.76 g, 20 mmol) in methylene 
chloride and, dropwise, with a solution of veratrole (3.32 g, 24 mmol) in 
methylene chloride, stirred for 0.5 hour, allowed to warm to room 
temperature, stirred for 4-5 hours and poured into a mixture of ice and 
HCl. The resultant phase mixture is separated. The organic phase is washed 
with 2M HCl, treated with silica gel and evaporated to dryness in vacuo. 
The residue is placed on top of a column of silica gel and eluted with 
mixtures of petroleum ether and ethyl acetate (5%, 10% and 20% pet ether, 
respectively) to give the title product as a white solid, 1.25 g (19% y) 
mp 153.degree. C. 
EXAMPLE 7 
2,6-Dichloro-4',5'-dimethoxy-2'-methylbenzophenone n-propyloxime (Compound 
196) 
R.sup.1 =Cl; R.sup.2 =6-Cl; R.sup.3 =CH.sub.3 ; Y=O; R.sup.4 =CH.sub.3 ; 
R.sup.5 =OCH.sub.3 ; R.sup.6 =H; R=CH.sub.2 CH.sub.2 CH.sub.3 
A stirred solution of 2,6-dichloro-4',5'-dimethoxy-2'-methylbenzophenone 
oxime (1.5 g, 4.4 mmol) in anhydrous tetrahydrofuran is treated with a 60% 
dispersion of sodium hydride in mineral oil (0.2 g, 4.8 mmol NaH). After 
the cessation of hydrogen gas evolution, the reaction mixture is treated 
with n-propyliodide (0.82 g, 5.3 mmol), allowed to stand at room 
temperature for 12 hours, and diluted with water. The resultant phase 
mixture is extracted with ethyl acetate. The organic phases are combined 
and concentrated in vacuo to give a residue. The residue is 
chromatographed using silica gel and petroleum ether/ethyl acetate, 8/2, 
to give the title product as a yellow oil, 0.4 g (23.8% y) identified by 
NMR (67:23, E/Z isomer ratio). 
EXAMPLE 8 
2,6-Dichloro4',5'-dimethoxy-2'-methylbenzophenone-O-acetyloxime (Compound 
197) 
R.sup.1 =Cl; R.sup.2 =6-Cl; R.sup.3 =CH.sub.3 ; Y=O; R.sup.4 =OCH.sub.3 ; 
R.sup.5 =OCH.sub.3 ; R.sup.6 =H; R=COCH.sub.3 
A stirred solution of 2,6-dichloro-4',5'-dimethoxy 2'-methylbenzophenone 
oxime (2.3 g, 6.8 mmol) in anhydrous tetrahydrofuran is treated with a 60% 
dispersion of sodium hydride in mineral oil (0.3 g, 7.5 mmol NaH). After 
the cessation of hydrogen gas evolution, the reaction mixture is treated 
with acetylchloride (0.55 g, 7.5 mmol) at room temperature, allowed to 
exotherm to 30.degree. C., stirred at ambient temperatures for 2 hours, 
concentrated in vacuo, treated with water, and filtered. The filtercake is 
washed with water, dried and recrystallized from methanol to give the 
title product as white crystals, 1.0 g (38.5% y), mp 
158.degree.-149.degree. C., identified by NMR (100% E isomer). 
EXAMPLE 9 
Using essentially the same procedures described for Examples 6-8 
hereinabove the following compounds are obtained and shown in Table III. 
TABLE III 
______________________________________ 
##STR23## 
Compound 
No. R R3 R6 mp .degree.C. 
______________________________________ 
198 H F H oil 
199 H H H 153 
200 H CH.sub.3 H 60-70 
201 H CH.sub.3 6-OCH.sub.3 
219-220 
202 CH.sub.3 CH.sub.3 H 112-115 
203 CH(CH.sub.3).sub.2 
CH.sub.3 H 117 
204 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 
CH.sub.3 H oil 
______________________________________ 
EXAMPLE 10 
2,6-Dichloro-2',3',4'-trimethoxy-6'-methyl-benzophenone 
A mixture of 3,4,5-trimethoxytoluene (9.11 g; 50 mmol), octane (25 ml) and 
iron(III)chloride (50 mg) is stirred at 105.degree. C., and percolating 
nitrogene 2,6-dichlorobenzoylchloride (12.04 g; 57.5 mmol) is added 
dropwise within 15 minutes. The mixture is kept at 105.degree. C. and 
stirred for another 15 minutes. After cooling to 50.degree. C. 
ethylacetate (50 ml) is added, the mixture shaken twice with 2N 
hydrochloric acid, once with water and dried. The ethylacetate is 
evaporated (70.degree. C.) and the liquid cooled with stirring. At 
50.degree. C. petrolether (50 ml) is added. The white crystalls formed are 
sucked off, washed with petrolether and dried. Yield 12.55 g (70.7%), mp. 
92.degree. C. 
EXAMPLE 11 
2,6-Dichloro-2',3'-dihydroxy-4'-methoxy-6'-methyl-benzophenone 
A mixture of 2,6-dichloro-2',3',4'-trimethoxy-6'-methyl-benzophenone (1.78 
g; 5 mmol) hydrobromic acid (7.5 ml; 30% in acetic acid) and acetic acid 
(7.5 ml) is stirred at 75.degree. C. for 2 hours. Water is added and the 
mixture extracted with methylenechloride. The extract is washed with water 
and shaken with 2N sodium hydroxide. The alcaline solution is acidified 
with hydrochloric acid, the separated compound dissolved in 
methylenechloride and the solution washed with water. After evaporation of 
the solvent purification is carried out by chromatography (flash column, 
filled with 36 g of silicagel; elution with 500 ml of 
petrolether/ethylacetate (4:1; v/v) and 250 ml of petrolether/ethylacetate 
(1:1; v/v)). the fraction containing the compound is concentrated, the 
compound crystallized. The yellow crystalls are washed with petrolether 
and sucked off; 0.64 g (39% y), mp. 182.degree. C. 
EXAMPLE 12 
2',3'-Di-n-butoxy-2,6-dichloro-4'-methoxy-6'-methyl-benzophenone 
Sodiumhydride (0.4 g; 60%; 10 mmol) is added with stirring to a solution of 
2,6-dichloro-2',3'-dihydroxy-4'-methoxy-6'-methyl-benzophenone (1.64 g; 5 
mmol) in tetrahydrofurane. The solvent is evaporated and the residue 
dissolved in 30 ml of dimethylformamide. 1-iodo-n-butane (4.6 g; 25 mmol) 
is added, the mixture is stirred at 100.degree. C. for 8 hours and then 
the solvent is evaporated. The residue is shaken with toluene/2N 
hydrochloric acid, the organic layer separated, washed with water and the 
solvent evaporated. The residue is purified by chromatography (flash 
column filled with 35 g of silicagel; elution with 500 ml of petrolether 
containing 2% of ethylacetate); yellow oil (0.7 g; 32% y). 
EXAMPLE 13 
7-(2,6-Dichlorobenzoyl)-10-methoxy-8-methyl-2,3,4,5-tetrahydro-1,6-benzodio 
xocin 
(R.sup.5 +R.sup.6 =--O--(CH.sub.2).sub.4 --O--) 
A mixture of 
2,6-dichlorobenzoyl-2',3'-dihydroxy-4'-methoxy-6'-methyl-benzophenone 
(3.27 g; 10 mmol), potassium carbonate (4 g), copper(II)oxide (50 mg), 
1,4-dibromobutane (2.38 g; 11 mmol) and dimethylformamide (25 ml) is 
stirred at room temperature for 15 hours. Water is added and extracted 
twice with ethylacetate. The ethylacetate phase is washed with water, the 
solvent evaporated. The residue is purified by chromatography (flash 
column filled with silicagel, elution with petrolether/ethylacetate (8:2; 
v/v)). From the enriched fractions the product can be crystallized with 
methanol. White crystalls (0.56 g; 14.7% y); mp. 103.degree.-104.degree. 
C. 
EXAMPLE 14 
2,6-Dichloro-3',4'-dimethoxy-6'-methyl-2'-phenylacetoxy-benzophenone 
2,6-Dichloro-3'4'-dimethoxy-2'-dihydroxy-6'-methyl-benzophenone (3.41 g; 10 
mmol) are added to a solution of potassium hydroxide (0.66 g; 85%) in 
methanol (30 ml). The methanol is evaporated, the residue is dissolved in 
dimethylformamide (30 ml), phenylacetylchloride (1.70 g; 11 mmol) is added 
and the mixture is stirred for 15 hours. Then water is added and the 
mixture is extracted three times with ethylacetate. After evaporation of 
the solvent methanol is added to the residue to give white crystalls (1.95 
g; 42.5% y); mp. 106.degree. C. 
EXAMPLE 15 
2,6-Dichloro-5'-difluoromethoxy-4'-methoxy-2'-methyl-benzophenone 
To a solution of 2,6-dichloro-5'-hydroxy-4'-methoxy-2'-methyl-benzophenone 
(1.0 g; 3.2 mmol) in dimethoxyethane (7 ml) a solution of sodium hydroxide 
(0.6 g; 15 mmol) in water (1 ml) is added. The mixture is heated to 
60.degree. C. with stirring, then a stream of chlorodifluoromethane is 
introduced for 20 minutes. After further stirring for 1.5 hours the 
solvent is evaporated. The residue is extracted with a mixture of 
trichloromethane and water. The organic phase is separated, dried and the 
solvent is evaporated. For purification, a flash column with silicagel (30 
g) is used (elution with mixtures of petrolether/ethylacetate 9:1, then 
8:2, then 7:3 (v/v)). The resulting compound forms white crystalls (0.6 g; 
51.8% y); mp. 126.degree.-128.degree. C. 
EXAMPLE 16 
2,6-Dichloro-5'-propionyloxy-4'-methoxy-2'methyl-benzophenone 
A mixture of 2,6-Dichloro-5'-hydroxy-4'-methoxy-2'-methyl-benzophenone and 
propionic acid anhydride (5 ml) is stirred at 100.degree. C. for 5 hours. 
Toluene/water is added. The organic phase is dried and evaporated. The 
residue is purified by chromatography (flash column with silicagel (30 g), 
elution with toluene). The toluene is removed. After treatment with 
cyclohexane the residue forms white crystalls; 0.5 g (42.6% y); mp. 
142.degree.-145.degree. C. 
EXAMPLE 17 
2,6-Dichloro-5'-tert-butoxy-4'-methoxy-2'-methyl-benzophenone 
A solution of 2,6-dichloro-5'-hydroxy-4'-methoxy-2'-methyl-benzophenone 
(3.0 g; 9.6 mmol) in 50 ml of methylenechloride is cooled down to 
-70.degree. C., trifluoromethanesulfonic acid (0.3 ml) is added, then a 
stream of 2-methylpropene (5.5 g; 100 mmol) is introduced within 4 hours. 
Triethylamine (1.2 ml) is added, the temperature goes up to 20.degree. C. 
The solution is shaken twice with diluted sodium hydroxide and the solvent 
is evaporated. The residue is purified chromatographically (flash column 
with 30 g of silicagel, elution with toluene/acetone 20:1 (v/v)). The 
residue is treated with petrolether to give 0.7 g of white crystalls (20% 
y); mp. 102.degree. C. 
EXAMPLE 18 
2,6-Dichloro-4'-methoxy-2'-methyl-5'-phenoxy-benzophenone 
A mixture of 2-methoxy-4-methyl-diphenylether (2.1 g; 10 mmol), 
2,6-dichlorobenzoylchloride (2.5 g; 12 mmol) and iron(III)chloride are 
heated to 100.degree. C. with stirring for 4 hours. After cooling down the 
mixture is shaken with toluene/water. The organic layer is dried and the 
solvent is evaporated. The residue is purified by chromatography (flash 
column filled with 30 g of silicagel, elution with toluene/petrolether 
1:9, changing to 1:1 (v/v). The residue after evaporation crystallises 
when treated with diisopropylether; white crystalls (1.5 g; 39% y); mp. 
113.5.degree. C. 
EXAMPLE 19 
2,6-Dichloro-4'-methoxy-2'-methyl-benzophenone 
A mixture of 2,6-dichlorobenzoylchloride (5.24 g; 25 mmol), 3-methylanisole 
(2.44 g; 20 mmol) and iron(III)chloride (20 mg) is heated to 100.degree. 
C. for 45 minutes with stirring. After cooling, toluene is added, the 
mixture is shaken with water, the organic phase is dried and the solvent 
is evaporated. The reaction product is purified chromatograpically (flash 
column with 70 g of silicagel; elution with petrolether/toluene changing 
from 75:25 to 40:60 (v/v)). After evaporation the residue from the main 
fraction is treated with petrolether to give white crystalls (1.33 g; 
22.5% y); mp. 89.degree. C. 
EXAMPLE 20 
5'-Bromo-2,6-dichloro-4'-methoxy-2'-methyl-benzophenone 
A solution of bromine (0.25 ml in 3 ml of trichloromethane) is added 
dropwise to a stirred solution of 
2,6-Dichloro-4'-methoxy-2'-methyl-benzophenone (1.5 g; 5 mmol in 5 ml of 
trichloromethane), followed by 15 minutes of stirring at 20.degree. C. The 
mixture is shaken with water, sodium hydrogencarbonate solution and water. 
The organic phase is dried and evaporated. The residue is purified by 
chromatography (flash column filled with 30 g of silicagel, elution with 
petrolether/ethylacetate changing from 20:1 to 9:1, 8:2, 7:3 (v/v). After 
evaporation, the residue crystallises when treated with 
petrolether/toluene to give white crystalls (0.45 g; 24% y); mp. 
159.degree. C. 
EXAMPLE 20 
2,6-Dichloro-5'-nitro-4'-methoxy-2'methyl-benzophenone 
2,6-Dichloro-4'-methoxy-2'-methyl-benzophenone (0.75 g; 2.5 mmol) is added 
to nitric acid (10 ml; 65%). The mixture is stirred at 80.degree. C. for 1 
hour. After addition of water the reaction product crystallises and is 
chromatographically purified (flash column filled with 30 g of silicagel, 
elution with toluene). White crystalls (0.35 g; 41% y); mp. 
156.degree.-160.degree. C. 
EXAMPLE 21 
2,6-Dichloro-4'-hydroxy-5'-nitro-2'-methyl-benzophenone 
Aluminumchloride (1.5 g; 11 mmol) is added to a solution of 
2,6-dichloro-5'-nitro-4'-methoxy-2'-methyl-benzophenone (1.8 g; 5.3 mmol) 
in methylenechloride (6 ml). The mixture is stirred for 30 minutes at 
20.degree. C. and for 1 hour at 45.degree. C., 5 ml conc. hydrochloric 
acid/ice are added. After shaking with 20 ml of methylenechloride the 
organic layer is treated with 2N hydrochloric acid and with water. After 
drying the solvent is evaporated, the residue purified by chromatography 
(flash column filled with 30 g of silicagel, elution with toluene). The 
residue from the main fraction is treated with diisopropylether to give 
yellow crystalls; (1.2 g; 73% y); mp. 170.degree. C. 
The compounds of Tables IV to X can be prepared analogously to the examples 
described hereinbefore. 
TABLE IV 
______________________________________ 
Compounds of formula 
##STR24## 
No. R.sup.5 mp. .degree.C.! 
______________________________________ 
1 OC.sub.6 H.sub.5 113.5 
2 Br 159 
3 NO.sub.2 156-60 
4 OCH.sub.2CONH(4-OCH.sub.3 C.sub.6 H.sub.4) 
154 
5 OCH.sub.2CONHC.sub.6 H.sub.5 
133 
6 OCH.sub.2CONHCH.sub.2 C.sub.6 H.sub.5 
150 
7 OCH.sub.2(2-pyridyl) 114 
8 OCH.sub.2(3-pyridyl) 119 
9 OCH.sub.2(4-pyridyl) 142 
10 
##STR25## 134 
11 O(CH.sub.2).sub.4 OC.sub.6 H.sub.5 
86-9 
12 
##STR26## 124 
1 OC.sub.6 H.sub.5 113.5 
2 Br 159 
3 NO.sub.2 156-60 
4 OCH.sub.2CONH(4-OCH.sub.3 C.sub.6 H.sub.4) 
154 
5 OCH.sub.2CONHC.sub.6 H.sub.5 
133 
6 OCH.sub.2CONHCH.sub.2 C.sub.6 H.sub.5 
150 
7 OCH.sub.2(2-pyridyl) 114 
8 OCH.sub.2(3-pyridyl) 119 
9 OCH.sub.2(4-pyridyl) 142 
10 
##STR27## 134 
11 O(CH.sub.2).sub.4 OC.sub.6 H.sub.5 
86-9 
12 
##STR28## 124 
13 
##STR29## 164 
14 
##STR30## 94 
______________________________________ 
TABLE V 
______________________________________ 
Compounds of formula 
##STR31## 
No. (R.sup.2).sub.m 
mp. .degree.C.! 
______________________________________ 
1 3-CH.sub.3 
82 
2 5-CH.sub.3 
oil 
3 5-CH.sub.3 
89 
4 4,6-(CH.sub.3).sub.2 
142 
______________________________________ 
TABLE VI 
______________________________________ 
Compounds of formula 
##STR32## 
No. R mp. .degree.C.! 
______________________________________ 
1 CH.sub.2 CH(CH.sub.3).sub.2 
105 
2 CH.sub.2CH(C.sub.2 H.sub.5).sub.2 
65 
3 CH.sub.2(2-CH.sub.3 C.sub.6 H.sub.4) 
73 
4 CH.sub.2(3-CH.sub.3 C.sub.6 H.sub.4) 
88 
5 CH.sub.2(4-CH.sub.3 C.sub.6 H.sub.4) 
92 
6 CH.sub.2(4-ClC.sub.6 H.sub.4) 
121 
7 CH.sub.2(4-NO.sub.2 C.sub.6 H.sub.4) 
178 
8 CH.sub.2(4-F.sub.3 COC.sub.6 H.sub.4) 
120 
9 CH.sub.2(4-CNC.sub.6 H.sub.4) 
189 
10 
##STR33## 119 
11 CH.sub.2(3-CH.sub.3 OC.sub.6 H.sub.4) 
oil 
12 CH.sub.2(4-H.sub.2 NCOC.sub.6 H.sub.4) 
106 
13 CH.sub.2(4-CH.sub.3 OC.sub.6 H.sub.4) 
77 
14 H 161 
15 CH.sub.2COC.sub.6 H.sub.5 
84 
16 CH.sub.2CHCHC.sub.6 H.sub.5 
oil 
17 CH.sub.2(4-CO.sub.2 CH.sub.3 C.sub.6 H.sub.4 
106 
18 CH.sub.2CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 
79 
19 CH.sub.2(2,5(CH.sub.3).sub.2 C.sub.6 H.sub.3) 
86 
20 CH.sub.2(2,4(CH.sub.3).sub.2 C.sub.6 H.sub.3) 
125 
21 COCH.sub.2 C.sub.6 H.sub.5 
106 
22 CH.sub.2(2-naphthyl) 
84 
23 CH.sub.2CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 
79 
24 CH.sub.2CH.sub.2 C.sub.6 H.sub.5 
110 
25 CH.sub.2CH.sub.2 OC.sub.6 H.sub.5 
oil 
26 CH.sub.2(2-ClC.sub.6 H.sub.4) 
131 
27 CH.sub.2(3-ClC.sub.6 H.sub.4) 
124 
28 CH.sub.2(2-FC.sub.6 H.sub.4) 
88 
29 CH.sub.2(4-FC.sub.6 H.sub.4) 
102 
30 CH.sub.2(2-CNC.sub.6 H.sub.4) 
127 
31 CH.sub.2(3-FC.sub.6 H.sub.4) 
88 
32 CH.sub.2(3-pyridyl) 
84 
33 CH.sub.2(2-NO.sub.2 C.sub.6 H.sub.4) 
140 
34 CH(CH.sub.3)C.sub.6 H.sub.5 
92 
35 CH.sub.2(4-CF.sub.3 C.sub.6 H.sub.4) 
125 
______________________________________ 
TABLE VII 
______________________________________ 
Compounds of formula 
##STR34## 
No k mp. .degree.C.! 
______________________________________ 
1 1 119 
2 2 123-5 
3 3 133 
4 4 103 
______________________________________ 
TABLE VIII 
______________________________________ 
Compounds of formula 
##STR35## 
No. R R' mp. .degree.C.! 
______________________________________ 
1 H n-C.sub.7 H.sub.15 
oil 
2 CH.sub.3 n-C.sub.7 H.sub.15 
oil 
3 H CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 
63 
4 H CH.sub.2 SC.sub.6 H.sub.5 
5 CH.sub.3 CH.sub.2 S-t-C.sub.4 H.sub.9 
______________________________________ 
TABLE IX 
______________________________________ 
Compounds of formula 
##STR36## 
mp. 
No. R R' .degree.C.! 
______________________________________ 
1 OCH.sub.3 n-C.sub.5 H.sub.11 
oil 
2 OCH.sub.2 CH.sub.2 SC.sub.6 H.sub.5 
CH.sub.3 
3 OCH.sub.2 COC(CH.sub.3).sub.3 
CH.sub.3 
4 H CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5 
5 H CH.sub.2 SCH.sub.3 
6 H CH.sub.2 SO.sub.2 C.sub.6 H.sub.5 
7 H CH.sub.2 SC.sub.6 H.sub.5 
8 CH.sub.3 CH.sub.2 S-t-C.sub.4 H.sub.9 
9 OH H 182 
10 OH CH.sub.3 
11 OCH.sub.2 OC.sub.6 H.sub.5 
CH.sub.3 
______________________________________ 
TABLE X 
______________________________________ 
Compounds of formula 
##STR37## 
mp. 
No. R R' .degree.C.! 
______________________________________ 
1 OCH.sub.3 n-C.sub.5 H.sub.11 
2 OCH.sub.2 CH.sub.2 SC.sub.6 H.sub.5 
CH.sub.3 
3 OCH.sub.2 COC(CH.sub.3).sub.3 
CH.sub.3 
4 H CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5 
5 H CH.sub.2 SCH.sub.3 
6 H CH.sub.2 SO.sub.2 C.sub.6 H.sub.5 
7 H CH.sub.2 SC.sub.6 H.sub.5 
8 OCH.sub.3 CH.sub.2 SC.sub.6 H.sub.5 
9 OCH.sub.2 OCH.sub.2 C.sub.6 H.sub.5 
CH.sub.3 
10 OCH.sub.2 OC.sub.6 H.sub.5 
CH.sub.3 
11 H OH 
______________________________________ 
Formulations 
Emulsion Concentrate 
active compound 200 g/l 
ethoxylated castor oil 100 g/l 
tetrahydrofurfuryl alcohol 793 g/l 
Biological Test Results 
The fungicidal activity of the compositions and compounds of the invention 
is investigated by means of the following tests. 
a) Activity Against Cereal Powdery MildewEtysiphe araminis f.sp. hordei and 
f.sp. tritici) 
This test measures the prophylactic activity of test compositions and test 
compounds applied as a foliar spray. Cereal seedlings (barley, cv Golden 
Promise; wheat, cv Kanzler) are grown to the 1 leaf stage. The plants are 
then sprayed with a solution of test compound in water, made up from a 
5,000 ppm stock solution in acetone containing 5,000 ppm of TRITON.RTM. X 
155 (a non-ionic polyoxyethylene ether surfactant). Plants are treated 
using an automated spray line with atomizing nozzles. The spray volume is 
20 ml. One to three days after treatment, the seedlings are inoculated 
with powdery mildew by shaking stock culture plants with sporulating 
pathogen (barley--Erysiphe graminis f.sp. hordei; wheat--Erysiphe graminis 
f.sp. tritici) over them. Thereafter, the plants are kept for 3 h without 
air movement in order to allow the spores to settle on the leaves. The 
plants are then kept in the greenhouse until symptoms occur. Assessment is 
based on the percentage of diseased leaf area compared with that on 
control leaves. 
b) Activity Against Apple Powdery MildewPodosphaera leucotricha 
This test measures the prophylactic activity of test compositions and test 
compounds, applied as a foliar spray. Apple seedlings (cv Morgenduft) are 
grown to the 6-7 leaf stage and then cut back to 3 leaves, taking off the 
oldest and youngest leaves. The plants are sprayed with a solution (20 ml) 
of test compound in water, made up from a 5,000 ppm stock solution in 
acetone containing 5,000 ppm of TRITON.RTM. X 155. The plants are treated 
using an automated spray line with atomizing nozzles. One to three days 
after treatment, the seedlings are inoculated with powdery mildew by 
shaking stock culture plants with sporulating pathogen over them. 
Thereafter, the plants are kept for 3 h without air movement. The plants 
are then kept in the greenhouse until symptoms occur. Assessment is based 
on the percentage of diseased leaf area of treated plants compared with 
that of control plants. 
c) Activity Against Grapevine Powdery Mildew Uncinula necator) 
This test measures the direct protectant activity of test compositions and 
test compounds applied as foliar spray. Cuttings of grapevine (cv 
Muller-Thurgau) are grown to the 6-8 leaf stage and then cut back to 4 
equally sized leaves. The plants are sprayed to run-off in a spray cabinet 
with a solution (20 ml) of test compound in water made up from a 5,000 ppm 
stock solution in acetone containing 5,000 ppm of TRITON.RTM. X 155. Two 
days after treatment, the cuttings are inoculated with conidia of Uncinula 
necator in a special spore setting tower. The spores are blown from 
freshly sporulating grape leaves (U. necator stock culture) into the upper 
hole of the settling tower and are allowed to settle on the leaves for 5 
min. Then the plants are kept in a phytotron at 18.degree. C. night and 
22.degree. C. day temperature at an interval of 12 h night and 12 h day. 
Illumination is accomplished by fluorescent tubes at 11,200 lux. 
Assessment is carried out after 21 days by visual inspection and based on 
the percentage of the diseased leaf area of the three youngest leaves 
compared with that on control plants. The results of the tests are set out 
in Table A and B below, in which the compounds are identified by reference 
to the preceding Compound Nos. allocated in Examples 1 to 9 above or to 
their Nos. in Tables IV to X. Absence of a rating indicates that none of 
the tests described above was carried out. A rating 0 indicates disease as 
untreated control, a rating 100 indicates no disease. 
Table A 
______________________________________ 
Erysiphe graminis 
Podosphaera 
Uncinula 
barley wheat leucotricha 
necator 
Comp. No. 
100 ppm 100 ppm 100 ppm 200 ppm 
______________________________________ 
*1 100 100 96 84 
*2 99 100 0 41 
*3 0 0 0 
4 95 100 41 
5 94 99 41 
6 99 100 
*8 100 100 100 95 
*9 0 70 95 
*10 85 100 44 88 
*11 0 0 0 
*12 23 0 0 
13 87 100 
*14 0 36 0 
*15 99 73 0 
16 100 94 
17 25 5 77 
18 89 57 73 
19 19 26 15 
20 100 100 28 
21 9 19 15 
23 100 100 100 
24 94 100 53 
26 82 79 33 
27 90 100 89 
28 100 98 
29 99 93 97 
31 99 100 
32 1 28 8 
33 39 98 
34 0 0 
35 0 22 9 
36 49 61 
37 70 37 
38 42 77 
39 28 85 
40 100 100 
41 49 99 
43 23 49 
44 89 38 10 
46 100 100 
47 95 100 
48 84 90 100 
50 4 6 94 
51 51 25 
52 0 0 
53 100 100 
*54 100 100 
56 109 100 11 
*57 99 100 
*58 100 100 
*59 0 1 
60 0 32 
62 100 100 
*64 95 99 71 63 
*66 0 0 0 
*67 43 0 0 
*68 0 0 0 
*69 0 28 0 
*71 99 32 10 
*72 55 72 0 
*73 99 94 26 33 
*74 0 0 16 
*75 61 34 0 
76 33 57 
*77 41 99 90 
*78 0 85 0 
*79 0 0 0 
80 76 100 
82 100 100 
84 0 0 
85 33 28 
86 0 17 
91 93 100 
*93 0 17 
*94 0 0 
*95 91 0 
*96 100 100 100 
*97 100 100 100 
*98 100 100 100 
*99 86 6 29 
*100 100 100 100 
*101 100 100 87 
*102 100 100 100 
*103 100 100 10 
*104 100 14 27 
*105 100 100 100 
*106 100 100 
*107 0 21 
*108 100 100 
*109 100 100 
*110 100 100 
*111 95 100 
*112 0 19 
*113 0 28 
*114 0 17 
*115 100 60 
*116 100 64 
*117 100 100 6 
*118 99 13 66 
*119 100 89 98 
*120 100 89 46 
*121 100 100 37 
*122 100 100 28 
*123 0 44 9 
*124 100 100 89 
*125 100 28 8 
*126 100 100 100 
*127 100 100 100 
*128 100 100 100 
*129 100 100 100 
*130 0 78 0 
*131 100 100 100 
*132 100 100 100 
*133 100 100 100 
*134 100 100 100 
*135 100 100 100 
*136 100 100 100 
*137 100 100 97 
*138 100 100 100 
*139 100 100 100 
*140 100 100 100 
*141 97 100 0 
*142 97 100 53 
*143 100 100 100 
*144 100 100 100 
*145 84 97 80 
*146 65 91 
*147 100 100 
*148 100 100 
*149 39 66 
*161 48 77 100 
*162 23 4 100 
*163 97 90 7 
166 100 100 -- 
167 100 97 20 
168 100 100 2 
169 100 100 0 
170 100 100 100 
171 97 100 0 
172 100 97 100 
173 26 53 0 
174 100 100 98 
175 100 100 100 
176 0 0 8 
177 52 0 0 
178 100 100 100 
180 95 19 -- 
181 5 0 6 
182 100 93 0 
183 100 74 0 
184 100 100 100 
185 0 0 0 
186 0 100 100 
189 100 100 100 
190 98 8 68 
191 100 100 99 
196 0 82 87 
197 71 78 1 
199 0 0 -- 
200 100 100 41 
201 98 0 -- 
202 0 92 92 
______________________________________ 
*indicates the infection with Erysiphe graminis and Podosphaera 
leucotricha was carried out 72 h after treatment 
TABLE B 
______________________________________ 
Erisyphe graminis 
Podosphaera 
Compound barley wheat leucotricha 
Table/No. 100 ppm 100 ppm 100 ppm 
______________________________________ 
IV/1 100 100 -- 
2 100 100 0 
3 100 100 48 
4 51 100 5 
5 11 25 -- 
6 26 23 -- 
7 100 100 -- 
8 95 92 -- 
9 98 100 -- 
10 100 100 0 
11 100 100 6 
12 96 100 0 
13 100 90 0 
V/1 100 100 97 
2 100 99 63 
3 100 100 25 
4 100 100 0 
VI/1 100 100 100 
2 100 100 100 
3 100 100 100 
4 100 100 100 
5 100 100 100 
6 100 100 100 
7 100 45 0 
8 100 100 100 
9 74 23 6 
10 100 100 96 
11 100 100 100 
12 100 0 0 
VI/13 100 100 100 
16 100 100 100 
17 100 58 100 
18 100 97 100 
19 100 100 100 
20 100 100 100 
21 100 100 38 
22 100 100 100 
23 100 95 19 
25 100 100 100 
VII/3 100 100 93 
4 100 100 100 
IX/1 100 100 100 
______________________________________