Compounds of the formula ##STR1## wherein R.sub.1 is perfluoroalkyl of 1 to 8 carbon atoms or 2,2,3,3-tetrafluoro-cyclobutyl, PA1 R.sub.2 and R.sub.4, which may be identical to or different from each other, are each hydrogen, alkyl of 1 to 10 carbon atoms, aliphatic acyl of 2 to 18 carbon atoms, benzoyl, salicyloyl or phenylacetyl, and PA1 R.sub.3 and R.sub.5, which may be identical to or different from each other, are each alkyl of 3 to 18 carbon atoms, halogen, nitro, p-toluenesulfonyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclododecyl, methylcyclohexyl, dimethylcyclohexyl, benzyl, methylthio or ##STR2## where R.sub.1, R.sub.2 and R.sub.4 have the meanings previously defined, PA2 Q is --CH.sub.2 -- or --S--, and PA2 G is R.sub.5, as above defined, or PA2 Q is R.sub.3, as above defined, and PA2 G is --CH.sub.2 -- or --S--, PA1 R.sub.3 may, in addition, also be hydroxyl, methoxy, methyl or cyano, and PA1 R.sub.5 may also be methyl, or one of substituents R.sub.3 and R.sub.5 is hydrogen or ethyl when the other has the meanings defined above except hydrogen, or when R.sub.1 has the meanings defined above except trifluoromethyl, or when R.sub.2 and R.sub.4 have the meanings defined above except hydrogen or methyl. The compounds are useful as active ingredients in pharmaceutical, cosmetic and pesticidal compositions.

This invention relates to novel substituted fluoracylresorcinols, as well 
as to various methods of preparing these compounds. 
More particularly, the present invention relates to a novel class of 
substituted fluoracylresorcinols represented by the formula 
##STR3## 
wherein R.sub.1 is perfluoroalkyl of 1 to 8 carbon atoms or 
2,2,3,3-tetrafluoro-cyclobutyl, 
R.sub.2 and R.sub.4, which may be identical to or different from each 
other, are each hydrogen, alkyl of 1 to 10 carbon atoms, aliphatic acyl of 
2 to 18 carbon atoms, benzoyl, salicyloyl or phenylacetyl, and 
R.sub.3 and R.sub.5, which may be identical to or didferent from each 
other, are each alkyl of 3 to 18 carbon atoms, halogen, nitro, 
p-toluenesulfonyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclododecyl, 
methylcyclohexyl, dimethylcyclohexyl, benzyl, methylthio or 
##STR4## 
where R.sub.1, R.sub.2 and R.sub.4 have the meanings previously defined, 
Q is --CH.sub.2 -- or --S--, and 
G is R.sub.5, as above defined, or 
Q is R.sub.3, as above defined, and 
G is --CH.sub.2 -- or --S--, 
R.sub.3 may, in addition, also be hydroxyl, methoxy, methyl or cyano, and 
R.sub.5 may also be methyl, or 
one of substituents R.sub.3 and R.sub.5 is hydrogen or ethyl when the other 
has the meanings defined above except hydrogen, or when R.sub.1 has the 
meanings defined above except trifluoromethyl, or when R.sub.2 and R.sub.4 
have the meanings defined above except hydrogen or methyl. 
The compounds embraced by formula I may be prepared by the following 
methods: 
Method A 
By acylation of a resorcinol compound of the formula 
##STR5## 
wherein R.sub.2 to R.sub.5 have the meanings hereinbefore defined, with a 
carboxylic acid or a reactive derivative thereof of the formula 
EQU R.sub.1 --COY (III) 
wherein R.sub.1 has the defined meanings and Y is hydroxyl, amino, acyloxy, 
alkoxy or halogen, in the presence of a Friedel-Crafts catalyst and of a 
solvent at temperatures between -80.degree. C. and the boiling point of 
the solvent, preferably, however, at room temperature. 
Suitable solvents include aliphatic hydrocarbons, carbon disulfide, 
halogenated, especially chlorinated aliphatic hydrocarbons, ethers, 
aromatic hydrocarbons such as benzene, toluene, chlorobenzene or 
dichlorobenzene, but also inorganic solvents such as phosphorus 
oxychloride, polyphosphoric acid, phosphoric acid or sulfuric acid. 
Suitable catalysts are Lewis-acids such as anhydrous aluminum chloride, 
iron(III)chloride, zinc chloride, boron trifluoride or the etherates 
thereof, tin(IV)chloride, antimony-tri- or penta-halides, phosphorus-tri- 
or penta-halides, phosphorus pentoxide or inorganic acids such as 
hydrochloric acid, hydrofluoric acid, sulfuric acid, polyphosphoric acid 
or chlorosulfonic acid, or strong organic acids such as p-toluenesulfonic 
acid. 
Method B 
By reaction of a resorcinol compound of the formula 
##STR6## 
wherein R.sub.2 to R.sub.5 have the meanings previously defined, under the 
conditions of the ketone synthesis according to Hosch with a 
perfluorocarboxylic acid nitrile of the formula 
EQU R.sub.1 --CN (IV) 
wherein R.sub.1 has the meanings defined above. 
The reaction is carried out at temperatures between -80.degree. C. and the 
boiling point of the solvent in the presence of Lewis-acids as catalysts 
and an organic solvent, preferably at -20.degree. to +80.degree. C. 
Suitable Lewis-acdis are, for example, anhydrous aluminum chloride, zinc 
chloride especially in the presence of hydrochloric acid, further 
iron(III)chloride and tin(IV)chloride, titanium tetrachloride, chromium 
trichloride, boron trifluoride, p-toluenesulfonic acid, phosphoric acid, 
polyphosphoric acid or hydrofluoric acid. Suitable solvents, for example, 
are ethers, chlorobenzene, nitrobenzene, xylene and phosphorus 
oxychloride. 
Method C 
For the preparation of a compound of the formula I wherein R.sub.2 and/or 
R.sub.4 are hydrogen, by rearrangement of a perfluoroacylresorcinol of the 
formula 
##STR7## 
wherein R.sub.3 and R.sub.5 are as hereinabove defined and D is --OR.sub.4 
when E is --O--COR.sub.1, or D is --O--COR.sub.1 when E is --OR.sub.2, or 
both D and E are --O--COR.sub.1, where R.sub.1, R.sub.2 and R.sub.4 have 
the meanings hereinbefore defined. 
The reaction is preferably carried out in the presence of a Lewis-acid as 
catalyst, optionally in the presence of a solvent, at temperatures between 
0.degree. and 150.degree. C. 
Suitable Lewis-acids are, for example, anhydrous zinc chloride, anhydrous 
aluminum chloride, zinc chloride in the presence of a hydrohalic acid, as 
well as iron(III)chloride and tin(IV)chloride. Suitable solvents are, for 
example, ethers or aromatic hydrocarbons, such as chlorobenzene, 
nitrobenzene, toluene, dichlorobenzene or xylene, and phosphorus 
oxychloride. 
Method D 
For the preparation of a compound of the formula I wherein R.sub.3 and/or 
R.sub.5 are halogen, nitro or p-toluenesulfonyl, by reaction of a 
perfluoroacylresorcinol of the formula 
##STR8## 
wherein R.sub.1, R.sub.2 and R.sub.4 have the meanings hereinbefore 
defined, and one of A and B is hydrogen, while the other already has the 
meanings of R.sub.3 or R.sub.5, with a compound of the formula 
EQU R.sub.7 Z (VII) 
wherein R.sub.7 is halogen, nitro or sulfonyl, and Z is halogen or 
hydroxyl. The reaction is carried out in a suitable solvent at 
temperatures between -20.degree. and 150.degree. C. Suitable solvents for 
the reaction with halogens (R.sub.7 and Z are both halogen) are especially 
ethers, such as diethyl ether or dioxane, or glacial acetic acid. For the 
reaction with nitric acid and sulfuric acid, the acids or mixtures thereof 
may simultaneously serve as solvents. 
Method E 
For the preparation of a compound of the formula I, wherein R.sub.3 and/or 
R.sub.5 are alkyl of 3 to 18 carbon atoms, by reaction of a 
perfluoroacylresorcinol of the formula VI, with an unsaturated aliphatic 
hydrocarbon or a secondary alcohol of 3 to 18 carbon atoms. This 
alkylation is either carried out in the presence of an acid, such as 
phosphoric acid, polyphosphoric acid, sulfuric acid, glacial acetic acid 
or phosphorus oxychloride, or of a Lewis-acid, such as anhydrous aluminum 
chloride, iron(III)chloride, tin(IV)chloride, phosphorus pentoxide, zinc 
chloride or phosphorus pentachloride, in a solvent, such as ether, 
chlorobenzene, nitrobenzene or phosphorus oxychloride, at temperatures 
between 30.degree. and 150.degree. C. 
Method F 
For the preparation of a compound of the formula I, wherein R.sub.3 is 
##STR9## 
and R.sub.5 has the meanings hereinbefore defined, or R.sub.5 is 
##STR10## 
and R.sub.3 has the above defined meanings, by condensation of 2 mols of a 
compound of the formula 
##STR11## 
wherein either K is R.sub.5 and L is hydrogen, or L is R.sub.3 and K is 
hydrogen and R.sub.1, R.sub.2 and R.sub.4 are as hereinbefore defined, 
with one mol of formaldehyde. The condensation takes place upon addition 
of the acid after standing for a while at room temperature, or by heating 
a solution of the reaction partners, optionally in an inert solvent, at 
temperatures up to the boiling point of the solvent. 
The compounds of the formula I, wherein R.sub.2 and/or R.sub.4 are 
hydrogen, obtained by the above methods may, if desired, be subsequently 
converted into compounds of the formula I, wherein R.sub.2 and/or R.sub.4 
have the remaining meanings stated above, by means of etherification, for 
instance with an alkyl halide, or by esterification, for instance with an 
acid halide or an acid anhydride. 
The starting compounds of the formula I are either known from the 
literature or may be prepared according to processes known from the 
literature, for example by acylation of a known compound of the formula 
##STR12## 
with a compound of the formula 
EQU R.sub.5 '--COY (IX) 
wherein Y has the meanings hereinbefore defined and R.sub.5 ' is an 
optionally substituted alkyl group as defined for R.sub.5, but which is 
shortened by a --CH.sub.2 -group. The formed acyl compound is subsequently 
catalytically reduced with hydrogen to the corresponding compound of the 
formula II which is alkylated in the 5-position. 
On the other hand, the starting compounds of the formula II wherein R.sub.5 
is halogen, may be obtained by halogenating a compound of the formula 
VIII. 
The compounds of the formulas II and VIII may, when R.sub.3 is alkyl, also 
be obtained from a known compound of the formula 
##STR13## 
wherein R.sub.5 has the meanings hereinbefore defined and R.sub.8 is 
alkyl, by reaction with an aliphaic Grignard-compound of the formula 
R.sub.3 '-MgHal (R.sub.3 ' is alkyl shortened by a --CH.sub.2 -group 
comared with the alkyl group represented by R.sub.3). Subsequently, the 
corresponding compound possessing an aliphatic acyl group in the 
3-position is liberated by means of hydrolysis, the groups R.sub.8 are 
optionally split off with anhydrous aluminum chloride, and the aliphatic 
acyl group is reduced to R.sub.3 having the meaning of an alkyl group. If 
a compound of the formula II, wherein R.sub.2 and R.sub.4 are hydrogen are 
wanted, the correspondingly substituted 4-methyl-7-hydroxy-cumarin of the 
formula 
##STR14## 
wherein R.sub.5 has the meanings hereinbefore defined, are esterified with 
a carboxylic acid or its derivative of the formula R.sub.3 '--COX, wherein 
R.sub.3 ' and X have the above defined meanings, into a compound of the 
formula 
##STR15## 
which is subsequently rearranged into the corresponding compound of the 
formula 
##STR16## 
by means of anhydrous aluminum chloride, whereby a ketone of the formula 
##STR17## 
is formed by heating with sodium hydroxide solution and subsequent 
hydrolysis with sulfuric acid, which is catalytically reduced to a 
compound of the formula II (cf. Organic Synthesis Coll. Vol. 3, 281 ff), 
for example, with amalgamated zinc and hydrochloric acid. The compound 
thus obtained may, if desired, be subsequently converted into the 
corresponding compound of the formula II, wherein R.sub.2 and R.sub.4 are 
other tha hydrogen, for example by etherification or esterification. 
The starting compounds of the formula V, wherein D or E is --O--COR.sub.1, 
are obtained according to known methods by esterification of the 
corresponding compounds wherein D or E is hydroxyl.

The following examples illustrate the present invention and will enable 
others skilled in the art to understand it more completely. It should be 
understood, however, that the invention is not limited solely to examples 
given below. 
EXAMPLE 1 
2,4-Dihydroxy-5-n-hexyl-trifluoroacetophenone by method A 
194 gm (1 mol) of 4-n-hexyl-resorcinol were suspended in 3 liters of 
ethylene chloride. While stirring the suspension at about 20.degree. C., a 
total of 300 gm (2 mols) of aluminum chloride were added in several 
portions, and then 260 gm (1.2 mols) of trifluoroacetic acid anhydride 
were added dropwise over a period of about 11/2 hours to the mixture at 
15.degree.-20.degree. C.; the latter temperature range was maintained by 
cooling the reaction mixture on an ice water bath. Thereafter, the 
reaction mixture was stirred for three hours more, and was then allowed to 
stand for one to two days at room temperature. Subsequently, the reaction 
mixture was poured over about 2.5 kg of ice while stirring and exterior 
cooling, taking care that the temperature of the aqueous mixture did not 
rise above 25.degree. C. The organic phase was separated, and the aqueous 
phase was washed three times with 500 ml each of ethylene chloride. The 
organic solutions were combined, washed with 1 liter of water, dried over 
calcium chloride, and evaporated. The residue was recrystallized from 
heptane, yielding 246 gm (85% of theory) of the compound of the formula 
##STR18## 
which had a melting point of 90.degree. C. 
Using an analogous procedure, the following compounds were also prepared: 
(a) 2,4-Dihydroxy-3-methyl-trifluoroacetophenone from 2-methyl-resorcinol 
in ethylene chloride; m.p. 101.degree. C., yield: 90% of theory. 
(b) 2,4-Dihydroxy-5-n-propyl-trifluoroacetophenone from 
4-n-propyl-resorcinol in ethylene chloride; m.p. 95.degree. C., yield: 87% 
of theory. 
(c) 2,4-Dihydroxy-5-isopropyl-trifluoroacetophenone from 
4-isopropyl-resorcinol in chloroform; m.p. 97.degree. C., yield: 70% of 
theory. 
(d) 2,4-Dihydroxy-3-n-propyl-trifluoroacetophenone from 
2-n-propyl-resorcinol in ethylene chloride; m.p. 114.degree. C., yield: 
88% of theory. 
(e) 2,4-Dihydroxy-3-isopropyl-trifluoroacetophenone from 
2-isopropyl-resorcinol in ethylene chloride; m.p. 145.degree. C., yield: 
85% of theory. 
(f) 2,4-Dihydroxy-5-n-butyl-trifluoroacetophenone from 4-n-butyl-resorcinol 
in ethylene chloride; m.p. 96.degree. C., yield: 82% of theory. 
(g) 2,4-Dihydroxy-5-isobutyl-trifluoroacetophenone from 
4-isobutyl-resorcinol in ethylene chloride; m.p. 90.degree. C., yield: 84% 
of theory. 
(h) 2,4-Dihydroxy-3-isobutyl-trifluoroacetophenone from 
2-isobutyl-resorcinol in ethylene chloride; m.p. 114.degree. C., yield: 
78% of theory. 
(i) 2,4-Dihydroxy-5-tert.butyl-trifluoroacetophenone from 
4-tert.butyl-resorcinol in ethylene chloride; m.p. 159.degree. C., yield: 
80% of theory. 
(j) 2,4-Dihydroxy-5-(2'-methyl-n-propyl)-trifluoroacetophenone of the 
formula 
##STR19## 
from 4-(2'-methyl-n-propyl)-resorcinol in ethylene chloride; m.p. 
90.degree. C., yield: 78% of theory. 
(k) 2,4-Dihydroxy-5-n-pentyl-trifluoroacetophenone from 
4-n-pentyl-resorcinol in ethylene chloride; m.p. 97.degree. C., yield: 86% 
of theory. 
(l) 2,4-Dihydroxy-5-cyclopentyl-trifluoroacetophenone from 
4-cyclopentyl-resorcinol in ethylene chloride; m.p. 94.degree. C., yield: 
75% of theory; 
(m) 2,4-Dihydroxy-3-isopentyl-trifluoroacetophenone from 
2-isopentyl-resorcinol in ethylene chloride; m.p. 101.degree. C., yield: 
84% of theory. 
(n) 2,4-Dihydroxy-3-n-pentyl-trifluoroacetophenone from 
2-n-pentyl-resorcinol in ethylene chloride; m.p. 105.degree. C., yield: 
87% of theory. 
(o) 2,4-Dihydroxy-5-cyclohexyl-trifluoroacetophenone from 
4-cyclohexyl-resorcinol in ethylene chloride; m.p. 80.degree. C., yield: 
78% of theory. 
(p) 2,4-Dihydroxy-5-n-heptyl-trifluoroacetophenone from 
4-n-heptyl-resorcinol in ethylene chloride; m.p. 85.degree. C., yield: 79% 
of theory; 
(q) 2,4-Dihydroxy-5-benzyl-trifluoroacetophenone from 4-benzyl-resorcinol 
in ethylene chloride; m.p. 114.degree. C., yield: 80% of theory. 
(r) 2,4-Dihydroxy-3-(4'-methyl-cyclohexyl)-trifluoroacetophenone from 
2-(4'-methyl-cyclohexyl)-resorcinol in ethylene chloride; m.p. 143.degree. 
C., yield: 76% of theory. 
(s) 2,4-Dihydroxy-5-(3',5'-dimethyl-cyclohexyl)-trifluoroacetophenone from 
4-(3',5'-dimethyl-cyclohexyl)-resorcinol in ethylene chloride; m.p. 
126.degree. C., yield: 79% of theory. 
(t) 2,4-Dihydroxy-5-n-nonyl-trifluoroacetophenone from 4-n-nonyl-resorcinol 
in ethylene chloride; m.p. 87.degree. C., yield: 85% of theory. 
(u) 2,4-Dihydroxy-5-n-dodecyl-trifluoroacetophenone from 
4-n-dodecyl-resorcinol in ethylene chloride; m.p. 92.degree. C., yield: 
84% of theory. 
(v) 2,4-Dihydroxy-5-chloro-trifluoroacetophenone from 4-chloro-resorcinol 
in ethylene chloride; m.p. 110.degree. C., yield: 90% of theory. 
(w) 2,4-Dihydroxy-5-bromo-trifluoroacetophenone from 4-bromo-resorcinol in 
ethylene chloride; m.p. 81.degree. C., yield: 88% of theory. 
(x) 2,3,4-Trihydroxy-trifluoroacetophenone from pyrogallol; m.p. 
134.degree. C., yield: 75% of theory 
(y) 2,4-Dihydroxy-3-methoxy-trifluoroacetophenone from 2-methoxy-resorcinol 
in ethylene chloride; m.p. 79.degree. C., yield: 78% of theory. 
(z) 
2,4-Dihydroxy-5-(2',2',3',3'-tetrafluoro-cyclobutylmethyl)-trifluoroacetop 
henone of the formula 
##STR20## 
from 4-(2',2',3',3'-tetrafluoro-cyclobutyl-methyl)-resorcinol in ethylene 
chloride; m.p. 122.degree. C., yield: 76% of theory. 
(aa) 2,4-Dihydroxy-5-methylthio-trifluoroacetophenone from 
4-methylthio-resorcinol in ethylene chloride; m.p. 57.degree. C., yield: 
68% of theory. 
(bb) 2,3,4-Trihydroxy-5-cyclohexyl-trifluoroacetophenone from 
4-cyclohexyl-pyrogallol in ethylene chloride; m.p. 128.degree. C., yield: 
78% of theory. 
(cc) 2,3,4-Trihydroxy-5-ethyl-trifluoroacetophenone from 4-ethyl-pyrogallol 
in ethylene chloride; m.p. 82.degree. C., yield: 80% of theory. 
(dd) 2,4-Dihydroxy-3-chloro-trifluoroacetophenone from 2-chloro-resorcinol 
in ethylene chloride; m.p. 113.degree. C., yield: 83% of theory. 
(ee) 2,4-Dihydroxy-5-n-octyl-trifluoroacetophenone from 
4-n-octyl-resorcinol in ethylene chloride; m.p. 87.degree. C., yield: 74% 
of theory. 
(ff) 2,4-Dihydroxy-3-cyano-trifluoroacetophenone of the formula 
##STR21## 
from 2,6-dihydroxy-benzonitrile in ethylene chloride; m.p. 210.degree. C., 
yield: 62% of theory. 
(gg) 2,2',4,4'-Tetrahydroxy-5,5'-trifluoroacetyl-diphenylsulfide of the 
formula 
##STR22## 
from 2,2',4,4'-tetrahydroxy-diphenylsulfide in ethylene chloride; m.p. 
172.degree. C., yield: 10% of theory. 
(hh) 2,2',4,4'-Tetrahydroxy-5-trifluoroacetyl-diphenylsulfide of the 
formula 
##STR23## 
from 2,2',4,4'-tetrahydroxy-diphenylsulfide in ethylene chloride; m.p. 
204.degree. C., yield: 20% of theory. 
EXAMPLE 2 
2,4-Dihydroxy-5-n-hexyl-perfluoropropiophenone by method A 
In analogy to Example 1, 1.94 gm of n-hexyl-resorcinol were admixed with 30 
ml of ethylene chloride and 3 gm of aluminum chloride, and then 3.6 gm of 
perfluoropropionic acid anhydride were added dropwise to the mixture. The 
reaction mixture was subsequently stirred for 1 to 2 days at room 
temperature, and was finally worked up as described in Example 1. 72% of 
theory of the compound of the formula 
##STR24## 
having a melting point of 62.degree. C. were obtained. 
In analogous manner, the following compounds were also prepared: 
(a) 2,4-Dihydroxy-perfluoropropiophenone from resorcinol; m.p. 80.degree. 
C., yield: 72% of theory. 
(b) 2,4-Dihydroxy-3-methyl-perfluoropropiophenone from 2-methyl-resorcinol; 
m.p. 69.degree. C., yield: 76% of theory. 
(c) 2,4-Dihydroxy-5-methyl-perfluoropropiophenone from 4-methyl-resorcinol; 
m.p. 140.degree. C., yield: 75% of theory. 
(d) 2,3,4-Trihydroxy-perfluoropropiophenone from pyrogallol; m.p. 
105.degree. C., yield: 60% of theory. 
EXAMPLE 3 
Using a procedure analogous to that described in Example 2, the following 
compounds were prepared from perfluorobutyric acid anhydride and the 
indicated resorcinol compound: 
(a) 2,4-Dihydroxy-perfluorobutyrophenone from resorcinol; m.p. 90.degree. 
C., yield: 66% of theory. 
(b) 2,4-Dihydroxy-3-methyl-perfluorobutyrophenone from 2-methyl-resorcinol; 
m.p. 75.degree. C., yield: 65% of theory. 
(c) 2,4-Dihydroxy-5-n-hexyl-perfluorobutyrophenone from 
4-n-hexyl-resorcinol; m.p. 57.degree. C., yield: 60% of theory. 
EXAMPLE 4 
2,4-Dihydroxy-5-n-hexyl-perfluoropropiophenone by method A 
A solution of 1.94 gm of 4-n-hexyl-resorcinol in 30 ml of ethylene chloride 
was admixed with a catalytic amount of boron trifluoride etherate and 2.2 
gm of perfluoropropionic acid, and the mixture was refluxed for 5 hours. 
Thereafter, the reaction mixture was worked up as described in Example 1, 
yielding 1.4 gm (41% of theory) of 
2,4-dihydroxy-5-n-hexyl-perfluoropropiophenone, m.p. 62.degree. C. 
In analogous manner 2,4-dihydroxy-3-methyl-perfluorocaprylophenone, R.sub.f 
-value=0.87 (eluant: petroleum ether/chloroform/ethyl acetate=3/6/1) was 
prepared. 
EXAMPLE 5 
2,4-Dihydroxy-3-methyl-5-chloro-trifluoroacetophenone by method D 
150 ml of sulfuryl chloride were added to a solution of 220 gm of 
2,4-dihydroxy-3-methyl-trifluoroacetophenone in 3 liters of ethylene 
chloride, and the mixture was stirred for three hours. Thereafter, while 
cooling, 300 ml of water were added to the reaction mixture of decompose 
the excess, unreacted sulfuryl chloride. After separation of the aqueous 
phase, the organic phase was washed three times with 150 ml each of water, 
then dried with sodium sulfate, and evaporated to about 20% of its 
original volume. 150 gm of practically pure 
2,4-dihydroxy-3-methyl-5-chloro-trifluoroacetophenone precipitated out. 
After complete evaporation of the mother liquor, the residue was 
recrystallized from a mixture of methylene chloride and heptane (1:1), 
yielding an additional 46 gm of the reaction product. Total yield: 196 gm 
(76% of theory) of the compound of the formula 
##STR25## 
having a melting point of 96.degree. C. 
In analogous manner, but in the absence of a solvent, the following 
compounds were also prepared with sulfuryl chloride: 
(a) 2,4-Dihydroxy-3,5-dichloro-trifluoroacetophenone from 
2,4-dihydroxy-trifluoroacetophenone; m.p. 101.degree. C. 
(b) 2,4-Dihydroxy-3-chloro-5-n-hexyl-trifluoroacetophenone from 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone; m.p. 40.degree. C. 
EXAMPLE 6 
2,4-Dihydroxy-3-chloro-trifluoroacetophenone by method D 
3 mg (0.015 mol) of 2,4-dihydroxy-trifluoroacetophenone were dissolved in 
25 ml of carbon tetrachloride, and a solution of 2.2 gm (0.02 mol) of 
tert.butyl hypochlorite in 100 ml of carbon tetrachloride was added. After 
standing for 1 hour, the solution was evaporated, and the residue was 
recrystallized from n-hexane, yielding 90% of theory of the compound of 
the formula 
##STR26## 
which had a melting point of 110.degree. C. 
The following compounds were prepared in analogous manner with tert.butyl 
hypochlorite: 
(a) 2,4-Dihydroxy-3-chloro-5-isopropyl-trifluoroacetophenone m.p. 
35.degree. C., from 2,4-dihydroxy-5-isopropyl-trifluoroacetophenone. 
(b) 2,4-Dihydroxy-3-chloro-5-tert.butyl-trifluoroacetophenone m.p. 
40.degree. C., from 2,4-dihydroxy-5-tert.tubyl-trifluoroacetophenone. 
(c) 2,4-Dihydroxy-3-isopropyl-5-chloro-trifluoroacetophenone m.p. 
42.degree. C. from 2,4-dihydroxy-3-isopropyl-trifluoroacetophenone. 
(d) 2,4-Dihydroxy-3-methyl-5-chloro-trifluoroacetophenone m.p. 96.degree. 
C., from 2,4-dihydroxy-3-methyl-trifluoroacetophenone. 
EXAMPLE 7 
2,4-Dihydroxy-3,5-dibromo-trifluoroacetophenone by method D 
2 ml of bromine were added dropwise to a solution of 4 gm of 2,4 
-dihydroxy-trifluoroacetophenone in 5 ml of glacial acetic acid. After 1 
to 2 days of standing, a substance crystallized out which was collected by 
suction filtration and recrystallized from hexane/heptane (1:1), yielding 
3.6 gm (49% of theory) of 2,4-dihydroxy-3,5-dibromo-trifluoroacetophenone, 
m.p. 81.degree. C. 
The following compound was prepared in analogous manner: 
(a) 2,4-Dihydroxy-3-bromo-5-n-hexyl-trifluoroacetophenone from 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone; m.p. 39.degree. C., yield: 
43% of theory. 
EXAMPLE 8 
2,4-Dihydroxy-5-p-toluenesulfonyl-trifluoroacetophenone 
A mixture consisting of 5 gm of 2,4-dihydroxy-trifluoroacetophenone, 10 gm 
of p-toluenesulfonic acid chloride, 10 gm of iron(III)chloride (anhydrous) 
and 10 ml of phosphorus oxychloride was heated at 120.degree. C. for 10 
hours. Subsequently, 100 ml of water were added, and the mixture was 
suctionfiltered. The filtercake was subjected to steam distillation to 
remove unreacted p-toluenesulfonic acid and then recrystallized from 
petroleum ether, yielding 3.6 gm (40% of theory) of the compound of the 
formula 
##STR27## 
which had a melting point of 145.degree. C. 
EXAMPLE 9 
Using a procedure analogous to that described in Example 8, but 
substituting aluminum chloride for ferric chloride as the catalyst, 2 gm 
(22% of theory) of 2,4dihydroxy-3-p-toluenesulfonyl-trifluoroacetophenone, 
m.p. 127.degree. C., were obtained from 
2,4-dihydroxy-trifluoroacetophenone. 
EXAMPLE 10 
2,4-Dihydroxy-3-methyl-5-nitro-trifluoroacetophenone by method D 
6 ml of 26% nitric acid were added dropwise to a solution of 4.5 gm of 
2,4-dihydroxy-3-methyl-trifluoroacetophenone in 20 ml of glacial acetic 
acid, while cooling the mixture on an ice bath. After 20 hours of 
standing, the reaction mixture was poured into water, and the aqueous 
mixture was suction-filtered. The filter cake was recrystallized from 
heptane, yielding 1.1 gm (21% of theory) of the compound of the formula 
##STR28## 
which had a melting point of 104.degree. C. 
Using an analogous procedure, the following compounds were also prepared: 
(a) 2,4-Dihydroxy-5-nitro-trifluoroacetophenone m.p. 81.degree. C., from 
2,4-dihydroxy-trifluoroacetophenone. 
(b) 2,4-Dihydroxy-3,5-dinitro-trifluoroacetophenone m.p. 68.degree. C., 
from 2,4-dihydroxy-trifluoroacetophenone with a mixture of 65% nitric acid 
and concentrated sulfuric acid. 
EXAMPLE 11 
2,4-Dihydroxy-3-(1'-methyl-pentyl)-trifluoroacetophenone 
10 gm of 2,4-dihydroxy-trifluoroacetophenone and 12.6 gm of 1-hexane were 
dissolved in 40 ml of phosphorus oxychloride and 5 gm of phosphorus 
pentoxide were added, while stirring. The mixture was heated at 50.degree. 
C. for 6 hours, while vigorously stirring. The reaction mixture was then 
poured into ice water to decompose the phosphorus oxychloride, and the 
precipitated oil was isolated by extracting the reaction mixture 5 times 
with 100 ml each of n-hexane. In order to remove unreacted 
2,4-dihydroxy-trifluoroacetophenone, the combined n-hexane extracts were 
washed 5 times with 80 ml each of aqueous 60% methanol, and then the 
solution was extracted 5 times with 100 ml each of aqueous 90% methanol. 
The methanol combined extracts were completely evaporated in a rotary 
evaporator, and the residue was recrystallized from n-pentane, yielding 
1.5 gm (30% of theory) of the compound of the formula 
##STR29## 
which had a melting point of 97.degree. C. 
In analogous manner, the following compounds were also prepared: 
(a) 2,4-Dihydroxy-3-isobutyl-trifluoroacetophenone m.p. 114.degree. C. from 
butene and 2,4-dihydroxy-trifluoroacetophenone. 
(b) 2,4-Dihydroxy-3-cyclododecyl-trifluoroacetophenone m.p. 166.degree. C. 
from cyclododecene and 2,4-dihydroxy-trifluoroacetophenone. 
(c) 2,4-Dihydroxy-3-isodecyl-trifluoroacetophenone m.p. 98.degree. C. from 
1-decene and 2,4-dihydroxy-trifluoroacetophenone. 
(d) 2,4-Dihydroxy-3-cyclopentyl-trifluoroacetophenone m.p. 166.degree. C. 
from cyclopentene and 2,4-dihydroxy-trifluoroacetophenone. 
(e) 2,4-Dihydroxy-3-cycloheptyl-trifluoroacetophenone m.p. 174.degree. C. 
from cycloheptene and 2,4-dihydroxy-trifluoroacetophenone. 
(f) 2,4-Dihydroxy-3-isopropyl-trifluoroacetophenone m.p. 145.degree. C. 
from propene and 2,4-dihydroxy-trifluoroacetophenone. 
(g) 2,4-Dihydroxy-3-isododecyl-trifluoroacetophenone m.p. 96.degree. C. 
from 1-dodecene and 2,4-dihydroxy-trifluoroacetophenone. 
(h) 2,4-Dihydroxy-3-isooctadecyl-trifluoroacetophenone m.p. 98.degree. C. 
from 1-octadecene and 2,4-dihydroxy-trifluoroacetophenone. 
EXAMPLE 12 
2,4-Dihydroxy-3-hexyl-trifluoroacetophenone by method E 
10 gm of 2,4-dihydroxy-trifluoroacetophenone and 12.6 gm of 1-hexene were 
dissolved in a mixture of 30 ml of concentrated sulfuric acid and 30 ml of 
glacial acetic acid, and the solution was heated at 60.degree. C. for 5 
hours. Subsequently, the reaction mixture was poured into ice water and 
the precipitated oil was isolated by extracting the aqueous mixture 5 
times with 100 ml each of n-hexane. To remove unreacted 
2,4-dihydroxy-trifluoroacetophenone, the n-hexane solution was washed 5 
times with 80 ml each of aqueous 60% methanol, then the solution was 
extracted 5 times with 100 ml each of aqueous 90% methanol. The combined 
methanol extracts were evaporated in a rotary evaporator, and the residue 
was recrystallized from n-pentane, yielding 2 gm (40% of theory) of 
2,4-dihydroxy-3-hexyl-trifluoroacetophenone, m.p. 97.degree. C. 
EXAMPLE 13 
2,4-Dihydroxy-3-methyl-trifluoroacetophenone monoacetate 
4.4 gm (0.02 mol) of 2,4-dihydroxy-3-methyl-trifluoroacetophenone were 
dissolved in 25 ml of benzene, and 3.2 gm (0.04 mol) of acetyl chloride 
and 3.6 gm (0.045 mol) of pyridine were added to the solution while 
stirring. After stirring at room temperature for 2 hours, the mixture was 
poured into water, and the benzene solution was separated. This solution 
was washed with 50 ml of water and dried with sodium sulfate. After 
evaporation is a rotary evaporator, the residue was recrystallized from 
n-hexane, yielding 4.5 gm (86.5% of theory) of the monoacetate of 
2,4-dihydroxy-3-methyl-trifluoroacetophenone, m.p. 49.degree.-50.degree. 
C. 
The following compounds were prepared in analogous manner: 
(a) 2,4-Dihydroxy-5-chloro-trifluoroacetophenone monoacetate from 
2,4-dihydroxy-5-chloro-trifluoroacetophenone and acetyl chloride; m.p. 
80.degree.-83.degree. C., yield: 71.5% of theory. 
(b) 2,4-Dihydroxy-5-chloro-trifluoroacetophenone monostearate from 
2,4-dihydroxy-5-chloro-trifluoroacetophenone and stearoyl chloride; m.p. 
51.degree. C., yield: 40% of theory. 
(c) 2,4-Dihydroxy-3-methyl-trifluoroacetophenone monoundecylenate from 
2,4-dihydroxy-3-methyl-trifluoroacetophenone and 11-undecylenic acid 
chloride. This compound is purified by distillation. B.p.=165.degree. C. 
at 0.07 mm Hg, yield: 65% of theory. 
(d) 2,4-Dihydroxy-5-chloro-trifluoroacetophenone monoundecylenate from 
2,4-dihydroxy-5-chloro-trifluoroacetophenone and 11-undecylenic acid 
chloride. This compound was purified by distillation. B.p.=168.degree. C. 
at 0.07 mm Hg, yield: 65% of theory. 
(e) 2,4-Dihydroxy-5-n-hexyl-trifluoroacetophenone monoacetate from 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone and acetyl chloride, m.p. 
30.degree. C., yield: 83% of theory. 
(f) 2,4-Dihydroxy-5-n-hexyl-trifluoroacetophenone monostearate from 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone and stearoyl chloride; 
yield: 77% of theory. 
(g) 2,4-Dihydroxy-3-methyl-trifluoroacetophenone di-phenylacetate from 
phenylacetyl chloride and 2,4-dihydroxy-3-methyl-trifluoroacetophenone; 
m.p. 65.degree. C., yield: 90% of theory. 
EXAMPLE 14 
Mixture of mono- and disalicylates of 
2,4-dihydroxy-3-methyl-trifluoroacetophenone 
32 gm of sodium salicylate and 2.2 gm of 
2,4-dihydroxy-3-methyl-trifluoroacetophenone were dissolved in 20 ml of 
benzene, 3.2 gm of phosphorus oxychloride were added, and the mixture was 
refluxed for 2 hours. For decomposition of the phosphorus oxychloride the 
mixture was poured over 150 gm of ice, the benzene solution was separated, 
and the aqueous phase was extracted with 50 ml of benzene. The combined 
benzene solutions were washed with 100 ml of water, dried with sodium 
sulfate and evaporated, and the residue was recrystallized from 75% 
methanol. 40% of theory of a product having a melting point of 
94.degree.-98.degree. C. was obtained which, according to UV-, IR- and 
NMR-spectra, was a mixture of mono- and disalicylate of 
2,4-dihydroxy-3-methyl-trifluoroacetophenone. 
EXAMPLE 15 
2-Hydroxy-4-decyloxy-trifluoroacetophenone and 
2,4-Didecyloxy-trifluoroacetophenone 
A mixture consisting of 10.3 gm (0.05 mol) of 
2,4-dihydroxy-trifluoroacetophenone, 7 gm (0.05 mol) of potassium 
carbonate (dried), 26.8 gm (0.1 mol) of decyl iodide and 100 ml of acetone 
was refluxed for 5 hours. The acetone was subsequently evaporated in a 
rotary evaporator, and 100 ml of water were added to the residue. The 
mixture was extracted with 100 ml of ethyl acetate, and the extract 
solution was dried with sodium sulfate. After evaporation in a rotary 
evaporator, the residual mixture of mono- and diether was fractionally 
distilled. In the first fraction at 0.1 mm Hg and 80.degree. C. the 
unreacted decyl iodide was contained. The ethers were then recrystallized 
in methanol. 
Monoether: B.p. 150.degree. C. at 0.1 mm Hg, m.p. 27.degree.-28.degree. C., 
yield: 9.2 gm (53.2% of theory) 
Diether: B.p. 200.degree. C. at 0.1 mm Hg, m.p. 37.degree.-38.degree. C., 
yield: 5.6 gm (23.0% of theory) 
The following compounds were prepared in analogous manner: 
(a) 2-Hydroxy-4-butoxy-trifluoroacetophenone from 
2,4-dihydroxy-trifluoroacetophenone and butyl iodide; m.p. 66.degree. C., 
yield: 28.5% of theory. 
(b) 2,4-Dimethoxy-5-n-hexyl-trifluoroacetophenone from 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone and methyl iodide; m.p. 
52.degree. C., yield: 30.5% of theory. 
EXAMPLE 15 
2,4-Dimethoxy-trifluoroacetophenone 
3 gm (0.015 mol) of 2,4-dihydroxy-trifluoroacetophenone were dissolved in 
75 ml of methylene chloride. 0.6 gm (0.002 mol) of tetrabutylammonium 
bromide, a solution of 2 gm (0.05 mol) of sodium hydroxide in 75 ml of 
water, as well as 5 gm (0.04 mol) of dimethyl sulfate were added. After 
stirring vigorously for 5 hours, the mixture was poured into 100 ml of 
water, the aqueous mixture was acidified with 15% hydrochloric acid, and 
the organic phase was separated and evaporated after drying with sodium 
sulfate. The residue was recrystallized from n-pentane, yielding 2 gm (57% 
of theory) of the compound of the formula 
##STR30## 
which had a melting point of 49.degree. C. 
EXAMPLE 16 
Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-ethylbenzene by method F 
A mixture consisting of 2.4 gm of 
2,4-dihydroxy-5-ethyl-trifluoroacetophenone and 2 gm of paraformaldehyde 
was heated at 140.degree. C. for 1 hour, and subsequently the mixture was 
recrystallized from heptane, yielding 2.3 gm (92% of theory) of the 
compound of the formula 
##STR31## 
which had a melting point of 170.degree. C. 
The following compounds were prepared in analogous manner: 
(a) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-methylbenzene) from 
2,4-dihydroxy-5-methyl-trifluoroacetophenone; m.p. 234.degree. C. yield: 
92% of theory. 
(b) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-n-propylbenzene) from 
2,4-dihydroxy-5-n-propyl-trifluoroacetophenone; m.p. 153.degree. C., 
yield: 90% of theory. 
(c) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-n-butylbenzene) from 
2,4-dihydroxy-5-n-butyl-trifluoroacetophenone; m.p. 145.degree. C., yield: 
91% of theory. 
(d) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-n-pentylbenzene) from 
2,4-dihydroxy-5-n-pentyl-trifluoroacetophenone; m.p. 131.degree. C., 
yield: 90% of theory. 
(e) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-n-hexylbenzene) from 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone; m.p. 120.degree. C., yield: 
93% of theory. 
(f) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-n-dodecyl-benzene) 
from 2,4-dihydroxy-5-n-dodecyl-trifluoroacetophenone; m.p. 110.degree. C., 
yield: 85% of theory. 
(g) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-isopropyl-benzene) 
from 2,4-dihydroxy-5-isopropyl-trifluoroacetophenone; m.p. 140.degree. C., 
yield: 89% of theory. 
(h) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-benzyl-benzene) from 
2,4-dihydroxy-5-benzyl-trifluoroacetophenone; m.p. 183.degree. C., yield: 
90% of theory. 
(i) Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-cyclohexyl-benzene) 
from 2,4-dihydroxy-5-cyclohexyl-trifluoroacetophenone; m.p. 206.degree. 
C., yield: 85% of theory. 
(j) Methylene-bis-(2,4-dihydroxy-3-isopropyl-5-trifluoroacetyl-benzene) 
from 2,4-dihydroxy-3-isopropyl-trifluoroacetophenone; m.p. 123.degree. C., 
yield: 90% of theory. 
EXAMPLE 17 
Methylene-bis-(2,4-dihydroxy-3-methyl-5-trifluoroacetylbenzene) by method F 
2.2 gm of 2,4-dihydroxy-3-methyl-trifluoroacetophenone were dissolved with 
2 gm of paraformaldehyde in 10 ml of methanol. 7 ml of concentrated 
sulfuric acid were added to the solution, while stirring and cooling with 
ice, and the mixture was allowed to stand at room temperature for 5 hours. 
Then, water was added, the mixture was suction-filtered, and the filter 
cake was recrystallized from methanol/water (1:1), yielding 1.9 gm (87% of 
theory) of the compound of the formula 
##STR32## 
which had a melting point of 195.degree. C. 
The following compound was prepared in analogous manner: 
Methylene-bis-(2,6-dihydroxy-3-trifluoroacetyl-5-chlorobenzene) from 
2,5-dihydroxy-5-chloro-resorcinol, m.p. 205.degree. C., yield: 87% of 
theory. 
We have further discovered that the compounds of the formula I exhibit 
useful pharmacological and/or pesticidal properties. In particular, they 
are active against bacteria, dermatophytes, yeasts, molds and 
phytopathogenic fungi; they have an inhibitory effect on various key 
enzymes of carbohydrate metabolism and on cell cultures, and thus they 
delay accelerated processes of mitosis in and on the skin. Therefore, they 
are suitable for the treatment of acne, dandruff, bacterial skin 
infections, mycoses, psoriasis, ichthyosis, hyperkeratotic states of the 
skin, for combatting damping off diseases in plant cultures as well as for 
herbicidal use, e.g. against wild oats. Various compounds of the formula I 
also exhibit anthelmintic activity. 
For example, the following known compounds were tested comparatively for 
their inhibitory effects on bacteria and fungi, cell cultures and enzyme 
activities: 
______________________________________ 
2,4-Dihydroxy-trifluoroacetophenone 
= A 
5-Ethyl-2,4-dihydroxy-trifluoroacetophenone 
= B 
3-Ethyl-2,4-dihydroxy-trifluoroacetophenone 
= C 
2,4-Dimethoxy-trifluoroacetophenone 
= D 
with the following compounds of this invention: 
2,4-Dihydroxy-5-n-hexyl-trifluoroacetophenone 
= E 
2,4-Dihydroxy-3-iso-butyl-trifluoroacetophenone 
= F 
2,4-Dihydroxy-5-iso-pentyl-trifluoroacetophenone 
= G 
2,4-Dihydroxy-3-(4'-methyl)-cyclohexyl-trifluoro- 
acetophenone = H 
2,4-Dihydroxy-5-(3',5'-dimethyl)-cyclohexyl-tri- 
fluoroacetophenone = I 
2,4-Dihydroxy-5-n-nonyl-trifluoroacetophenone 
= J 
2,4-Dihydroxy-3-iso-hexyl-trifluoroacetophenone 
= K 
2,4-Dihydroxy-3-cyclododecyl-trifluoroacetophenone 
= L 
2,4-Dihydroxy-3-isodecyl-trifluoroacetophenone 
= M 
2,4-Dihydroxy-3-cyclopentyl-trifluoroacetophenone 
= N 
2,4-Dihydroxy-3-cycloheptyl-trifluoroacetophenone 
= O 
2,4-Dihydroxy-3-isopropyl-trifluoroacetophenone 
= P 
Methylene-bis-(2,6-dihydroxy-3-isopropyl-5-trifluoro- 
acetyl)-benzene = Q 
Methylene-bis-(2,6-dihydroxy-3-ethyl-5-trifluoro- 
acetyl)-benzene = R 
Methylene-bis-(2,4-dihydroxy-3-methyl-5-trifluoro- 
acetyl)-benzene = S 
2,4-Dihydroxy-3-methyl-trifluoroacetophenone 
= T 
2,4-Dihydroxy-5-chloro-trifluoroacetophenone 
= U 
2,4-Dihydroxy-3-methyl-pentafluoropropiophenone 
= V 
2,4-Dihydroxy-5-n-decyl-trifluoroacetophenone 
= W 
2,4-Dihydroxy-3-n-pentyl-trifluoroacetophenone 
= X 
2,4-Dihydroxy-3-n-propyl-trifluoroacetophenone 
= Y 
Methylene-bis-(2,4-dihydroxy-3-isopropyl-5-trifluoro- 
acetyl)-benzene = Z 
______________________________________ 
The inhibitory effect on bacteria and fungi was examined by the serial 
dilution test and the agar diffusion test (hole-test). As bacteria were 
used: Staphylococcus aureus SG 511, Streptococcus Aronson, Streptococcus 
pyogenes At CC 86 68; as fungi: Candida albicans AT CC 10231, Trichophyton 
mentagrophytes AT CC 9129 and Aspergillus niger. 
Serial dilution test: 
Nutrient media 
1. Meat extract broth: for St. aureus SG 511 
______________________________________ 
Recipe: 
Peptone 10 gm 
Meat extract 8 gm 
Sodium chloride 3 gm 
Sec. sodium phosphate (Na.sub.2 HPO.sub.4) 
2 gm 
ad 1,000 ml of distilled water 
(pH 7.2-7.4) 
______________________________________ 
Sterilization: 15 min. at 120.degree. C. in the autoclave 
2. Glucose broth: for Sc. Aronson and St. pyogenes Recipe see meat extract 
broth. After sterilization 1 weight percent of glucose is added as a 
sterile 50% solution. 
3. Sabouraud broth: for C. alb., Trich. mnt., A. niger 
______________________________________ 
Recipe: 
Peptone from Casein 10 gm 
Glucose 40 gm 
Sodium chloride 1 gm 
Sec. sodium phosphate (Na.sub.2 HPO.sub.4) 
1 gm 
______________________________________ 
Sterilization: 5-10 min. at 120.degree. C., a pH was not adjusted. 
Standardization of the density of microorganisms 
The age of the primary cultures is 24 hours for bacteria and 14 days for 
fungi. The standardization of the suspension of microorganisms is effected 
using a photometer according to Eppendorf (test tube .phi.14 mm, filter 
546 nm) and a suspension for comparison consisting of barium sulfate, this 
suspension being created by adition of 3.0 ml of 1% barium chloride 
solution to 97 ml of 1% sulfuric acid. After the standardization the 
bacteria were further diluted to a concentration of 1:1000 by means of 
sodium chloride solution, the fungi were used in an undiluted state. 
Preparation of the substance concentration 
40 mgm of the substance were put into a 10 ml measuring flask and filled up 
to the mark with the solvent (corresponds to a dilution of 1:250=4000 
.mu.g/ml). The further dilution series was standardized with distilled 
water or the respective solvent and the following substance concentrations 
were prepared: 1000; 250; 62.5 .mu.g/ml. 
Execution of the test 
The tubes were filled with 4.9 ml of the corresponding liquid nutrient 
medium. Then 0.1 ml of the substance dilution prepared above was added to 
each tube, so that the mentioned final concentrations were present. 
Finally each tube was inoculated with 0.1 ml of the standardized 
suspension of microorganisms. Control tests merely using the solvent are 
to be carried out simultaneously. 
Incubation 
Bacteria were incubated at 37.degree. C. for 18-20 hours and fungi at 
27.degree. C. for 7 days. 
Evaluation 
The measurement is carried out macroscopically defining the minimal 
inhibitory concentration (the lowest still microbiostatically effective 
concentration). 
Agar diffusion test: 
Nutrient media 
1. Meat extract agar: for St. aureus SG 511 
______________________________________ 
Recipe: 
Peptone 10 gm 
Meat extract 8 gm 
Sodium chloride 3 gm 
Sec. sodium phosphate (Na.sub.2 HPO.sub.4) 
2 gm 
Pronagar 15 gm 
ad 1,000 ml of distilled water 
(pH 7.2-7.4) 
______________________________________ 
Sterilization: 15 min. at 120.degree. C. in the autoclave 
2. Glucose agar: for Sc. Aronson and St. pyogenes Recipe see meat extract 
agar. After sterilization 1 weight percent of glucose is added as a 
sterile 50% solution. 
3. Sabouraud agar: for C. alb., Trich. ment., A. niger 
______________________________________ 
Recipe: 
Peptone from Casein 10 gm 
Glucose 40 gm 
Sodium chloride 1 gm 
Sec. sodium phosphate (Na.sub.2 HPO.sub.4) 
1 gm 
Pronagar 15 gm 
ad 1,000 ml of distilled water 
______________________________________ 
Sterilization: 5-10 min. at 120.degree. C., a pH was not adjusted. 
Standardization of the density of microorganisms 
The age of the primary cultures is 24 hours for bacteria and 14 days for 
fungi. The standardization of the suspension of microorganisms is effected 
using a photometer according to Eppendorf (test tube .phi.14 mm, filter 
546 nm) and a suspension for comparison consisting of barium sulfate, this 
suspension being created by addition of 3.0 ml of 1% barium chloride 
solution to 97 ml of 1% sulfuric acid. After the standardization St. 
aureus SG 511 was diluted 1:1000 and Sc. pyogenes and Aronson 1:100 by 
means of sodium chloride solution. The fungi were used in an undiluted 
state. 
Preparation of the substance concentration 
40 mgm of the substance were put into a 10 ml measuring flask and filled up 
to the mark with the solvent (corresponds to a dilution of 1:250=4000 
.mu.g/ml). 
The dilutions to the concentrations under test were effected with distilled 
water or the respective solvent. 
Execution of the test 
19 ml of the nutrient medium were filled into sterile Petri dishes of a 
diameter of 8 cm and dried. Subsequently the agar plates were charged with 
4 ml of seed agar. 100 ml of seed agar contain 1.25 ml of the suspension 
of microorganisms, an agar plate thus containing 0.05 ml of the suspension 
of microorganisms. After solidification of the agar, 5 holes of a diameter 
of 5 mm were punched into the plates and filled with 0.05 ml of the 
correspondingly concentrated substance solution. 
Control tests merely using the solvent are to be carried out 
simultaneously. 
Incubation 
Bacteria were incubated at 37.degree. C. for 18-20 hours and fungi at 
27.degree. C. for 7 days. 
Evaluation 
The diameter of the area of inhibition in mm was measured after having 
deducted the diameter of the hole. If instead of a growth free zone only 
considerably reduced growth has taken place, these values were put into 
brackets. 
Serial dilution test for Corynebacterium acnes and Pityrosporum ovale 
Nutrient medium 
For Corynebacterium acnes: thioglycolate-broth for Pityrosporum ovale: 
Littmann's broth, 5 ml per tube. 
Density of microorganisms 
Suspension of microorganisms in 0.9% sodium chloride solution, standardized 
using a photometer according to Eppendorf by means of a suspension for 
comparison consisting of barium sulfate, for Corynebacterium acnes in a 
dilution of 1:100, for Pityrosporum ovale in an undiluted state. 0.1 ml of 
the suspensions was used per test tube. Dimethyl sulfoxide served as a 
solvent for the substances. 
The suspension with Corynebacteria acnes was incubated at 37.degree. C. for 
48 hours, the suspension of Pityrosporum ovale at 27.degree. C. for 7 
days. The reading was effected by macroscopic evaluation of the growth of 
microorganisms and registration of the minimal inhibitory concentration. 
Agar diffusion test for Pityrosporum ovale CBS 1878 Nutrient medium 
Littmann's agar, 23 ml per Petri dish, diameter of dish 100 mm. 
Density of microorganisms 
Suspension of microorganisms in 0.9% sodium chloride solution, standardized 
using a photometer according to Eppendorf by means of a suspension for 
comparison consisting of barium sulfate. 0.05 ml per plate were used. The 
test substances were dissolved in dimethyl sulfoxide. The incubation time 
was 7 days at 27.degree. C.; the area of inhibition in mm was measured, 
0.05 ml of the solution of the substance were used for each punch-hole of 
a diameter of 6 mm. The results of these tests are recorded in the 
following tables 1 and 2: 
TABLE I 
__________________________________________________________________________ 
Activity on grampositive bacteria and Corynebacterium acnes: 
MIC-values in .mu.g/ml 
Staphylococcus Streptococcus Streptococcus Corynebacterium 
aureus SG 511 Aronson pyogenes acnes 
Substance 
A.D.T. S.D.T. A.D.T. S.D.T. A.D.T. S.D.T. S.D.T. 
__________________________________________________________________________ 
A 1000 80 1000 80 nt nt 80 
B 250 20 250 20 250 20 20 
C 62.5 5 62.5 5 62.5 1.25 1.25 
D &gt;4000 &gt;80 &gt;4000 &gt;80 &gt;4000 &gt;80 &gt;80 
E .ltoreq.15.6 
1.25 .ltoreq.15.6 
0.31 .ltoreq.15.6 
0.31 0.08 
F 62.5 0.08 .ltoreq.15.6 
1.25 .ltoreq.15.6 
1.25 0.31 
G .ltoreq.15.6 
0.31 .ltoreq.15.6 
1.25 .ltoreq.15.6 
0.31 1.25 
H .ltoreq.15.6 
0.31 .ltoreq.15.6 
1.25 .ltoreq.15.6 
0.31 1.25 
I .ltoreq.15.6 
0.31 .ltoreq.15.6 
0.08 .ltoreq.15.6 
0.31 0.08 
J .ltoreq.15.6 
5(1.25) 
.ltoreq.15.6 
5 .ltoreq.15.6 
1.25(0.08) 
0.02 
K .ltoreq.15.6 
1.25 .ltoreq.15.6 
1.25 .ltoreq.15.6 
0.31 0.08 
L 62.5 0.31 .ltoreq.15.6 
0.31 62.5 0.08 1.25(0.31) 
M 250 1.25 .ltoreq.15.6 
20(1.25) 
.ltoreq.15.6 
1.25 0.31 
N .ltoreq.15.6 
1.25 .ltoreq.15.6 
1.25 62.5 0.31 0.31 
O .ltoreq.15.6 
0.31 .ltoreq.15.6 
0.31 .ltoreq.15.6 
0.08 1.25(0.31) 
P 62.5 1.25 .ltoreq.15.6 
1.25 62.5 1.25 5(1.25) 
Q .ltoreq.15.6 
0.08 .ltoreq.15.6 
1.25 .ltoreq.15.6 
0.001 0.02 
R .ltoreq.15.6 
0.08 .ltoreq.15.6 
0.31 .ltoreq.15.6 
0.005 0.005 
S .ltoreq.15.6 
1.25 .ltoreq.15.6 
1.25 .ltoreq.15.6 
1.25 0.31 
__________________________________________________________________________ 
Values in brackets mean that reduced growth has taken place at this 
concentration; nt=not tested; MIC=minimal inhibitory concentration; 
A.D.T.=agar diffusion test; S.D.T.=serial dilution test 
TABLE II 
__________________________________________________________________________ 
Activity on yeasts, dermatophytes, molds and Pityrosporum 
ovale: 
MIC-values in .mu.g/ml 
Trichophyton 
Candida mentagro- 
Aspergillus 
Pityrosporum 
Sub- 
albicans phytes niger ovale 
stance 
A.D.T. 
S.D.T. 
A.D.T. 
S.D.T. 
A.D.T. 
S.D.T. A.D.T. 
S.D.T. 
__________________________________________________________________________ 
A 1000 80 250 20 250 20 1000 80 
B 1000 20 250 5 250 20 1000 80 
C 1000 20 62.5 
1.25 
1000 5 1000 &gt;80 
D &gt;4000 
&gt;80 &gt;4000 
&gt;80 &gt;4000 
&gt;80 &gt;4000 
&gt;80 
U 1000 20 250 5 250 20 1000 10 
V 4000 80 250 20 &gt;4000 
&gt;80 4000 20 
F 250 20 .ltoreq.15.6 
1.25 
250 20 250 80 
H 1000 (80) 
.ltoreq.15.6 
1.25 
62.5 (80) 
1000 &gt;80 
W 1000 (20) 
.ltoreq.15.6 
1.25 
250 5 250 80 
__________________________________________________________________________ 
Measurement of the inhibition of the glucose-6-phosphatedehydrogenase 
The equilibrium was observed: 
EQU Glucose-6-phosphate+NADP.sup.+ G6-DH gluconic 
acid-6-phosphate+NADPH+H.sup.+ 
(NADP=nicotinamide-adenine-dinycleotide-phosphate, G6P-DH=gluconic 
acid-6-phosphate-dehydrogenase) 
The formation velocity of NADPH is a measure for the enzyme activity; it 
may be observed by means of the extinction increase at 340, 334 or 366 nm 
per unit of time. 
Method 
0.025 ml of glucose-6-phosphate-dehydrogenase (Boehringer Mannheim) were 
filled up to 10 ml of distilled water (solution I). 100 mgm of 
nicotinamide-adenine-dinucleotide-phosphate were dissolved in 13 ml of 
distilled water (solution II). 47.2 mgm of glucose-6-phosphate were 
dissolved in further 10 ml of distilled water (solution 3). Simultaneously 
a buffer solution (solution IV) was prepared as follows: 0.28 gm of 
triethanolamine-hydrochloride and 1.461 gm of ethylene diaminotetraacetic 
acid-disodium salt were dissolved in 1 liter of distilled water and 
adjusted to a pH of 7.6 with sodium hydroxide solution. The substance 
under test was dissolved in dimethyl formamide or ethanol (solution V). 
Tested concentrations: 50; 25; 12.5; 6.25; 3.125; 1.56 and 0.78 .mu.g/ml. 
Determination of the immediate inhibition 
0.1 ml of solution I, 0.1 ml of solution II, 2.67 ml of solution IV and 
0.03 ml of solution V were mixed and kept at 25.degree. C. for 5 minutes. 
Then 0.1 ml of solution III was added, mixed and the alteration of 
extinction was determined spectrophotometrically at 366 nm for 3 minutes. 
Determination of the inhibition of incubation 
0.1 ml of solution I, 0.1 ml of solution II, 2.67 ml of solution IV and 
0.03 ml of solution V were mixed and kept at 37.degree. C. for 60 minutes. 
Then 0.1 ml of solution III was added, mixed and the alteration of 
extinction was measured spectrophotometrically at 366 nm for 3 minutes. 
The inhibitory values were calculated from the average values of three 
measurements (alteration of extinction per minute) compared with controls, 
which received the pure solvent as the inhibitory solution. Then the 
ED.sub.50 was calculated according to Reed and Muench from the inhibitory 
values for the various concentrations. 
The following table contains the results: 
TABLE III 
______________________________________ 
G6PDH-inhibition 
Ed.sub.50 [.mu.g/ml] 
Substance 
Immediate Inhibition 
Inhibition of Incubation 
______________________________________ 
A &gt;50 33 
B 34.5 30 
C 37.5 20 
D &gt;50 &gt;50 
E 24.1 22.3 
F 37.7 27.7 
J 8.5 3.62 
L 4.0 3.25 
M 2.8 2.9 
N 10.6 6.5 
O 10.2 6.9 
P 14.8 9.9 
Z 0.58 0.13 
______________________________________ 
Measurement of the inhibition of cell cultures 
Method 
HeLa-cell culture was treated with trypsin and adjusted to a cell number of 
150,000 cells/ml of fresh medium. The substance was always dissolved in 
the same quantity of dimethyl sulfoxide and then further diluted with 
growth medium. 0.1 ml of the substance-dilutions were added to each well 
of microtiter plates and then 0.2 ml of cell suspension were added (4 
wells per dilution). Several growth controls containing 0.1 ml of growth 
medium instead of 0.1 ml of substance dilution were put up. After careful 
mixing, the cultures were incubated at 37.degree. C. for 3 days in a 5% 
carbon dioxide atmosphere. The reading was effected in comparison with 
these controls. The results were given as the percentage of the deficiency 
and degeneration compared to the growth control. The minimal inhibitory 
concentration was determined from these results and the ED.sub.50 was 
calculated according to Reed and Muench. The statements are referred to 
.mu.g of substance per ml of total medium. 
The results are recorded in the following table: 
TABLE IV 
______________________________________ 
Minimal inhibitory concentration 
ED.sub.50 
Substance 
.mu.g/ml .mu.g/ml 
______________________________________ 
A 3.13 12.5 
B 6.25 9.75 
D 25 90.1 
E 0.78 5.81 
V .ltoreq.0.78 1.5 
F 0.78 7.7 
G 0.78 5.8 
H .ltoreq.0.78 4.2 
K 0.78 2.27 
N 3.13 5.32 
P 1.56 3.52 
S .ltoreq.0.78 3.8 
______________________________________ 
The compounds of this invention are chemically stable, show a good 
lipophilic behavior (distribution-coefficient n-octanol/water&gt;1000) and 
may well be incorporated into ointments, creams, tinctures, sprays, 
powders etc., which are suitable for topical application. 
The good compatibility on the skin (a cream containing 10% of compound E 
was tolerated without irritation for over 24 hours under occlusion) and 
the low toxicity are of special advantage. 
The acute toxicity was determined with mice. The LD.sub.50, the dose 
leading to the death of 50% of the animals within 14 days, was calculated. 
LD.sub.50 in the mouse: 
______________________________________ 
Compound E p.o. &gt;3,200 mgm/kg 
s.c. &gt;4,000 mgm/kg 
i.p. 82 mgm/kg 
Compound Q p.o. &gt;4,000 mgm/kg 
s.c. &gt;2,0000 mgm/kg 
i.p. 400 mgm/kg 
______________________________________ 
In the general pharmacologic screening of the substances, which indicates 
an influence on essential body functions, e.g. heart/circulation or 
central nervous system, no considerable effects were shown. Systemic 
side-effects are, therefore, not expected with local application. 
Because of the good lipophilic behavior at simultaneous presence of polar 
groups the compounds penetrate well into the skin, however, they are only 
absorbed to a small extent as could be shown by analysis of the excretion. 
The examination on the compatibility on the skin and sensitization, which 
were carried out with guinea pigs, showed that the weak sensitizing 
properties of some resorcinols disappear by the introduction of the 
trifluoroacetyl group. As resorcinols, such as hexyl-resorcinol, in some 
cases cause allergies in humans, this is a considerable advantage. 
At present an effective therapy of acne is only possible systemically with 
strong antibiotics (tetracycline, erythromycin) and locally with peeling 
agents such as vitamin-A-acid and benzoyl peroxide. The application of 
antibiotics for a disease by no means endangering life is problematic in 
principle because of the resistance formation, when peeling agents are 
applied one must expect considerable irritation of the skin. 
In the acne-therapy with antibiotics the gram-positive bacteria important 
for acne, above all Corynebacterium acnes, are dimished, which leads to a 
reduction of the content of free fatty acids, which were split off from 
triglycerides by these bacteria, in the sebum. 
As table I shows, the above-mentioned compounds are strongly active against 
Corynebacterium acnes. In addition, it could be shown that after local 
application a considerable reduction of the content of free fatty acids is 
possible. Thus, a local therapy is possible, which may be compared in its 
effect with the oral therapy with antibiotics. 
The exact cause of dandruff formation is unknown up to now. However, a 
hyperkeratosis may be found with dandruff, i.e. mitosis in the epidermis 
is accelerated; additionally the hyperkeratosis is disturbed. According to 
the statements of some authors, e.g. R. A. Gosse, R. W. VanderWyck, J. 
Soc. Cosmet. Chem. 20, 603 (1969), the yeast Pityrosporum ovale plays a 
role for the genesis of dandruff. 
Table II shows that some of the above-mentioned compounds have a strong 
effect against Pityrosporum ovale. 
It may be seen in Tables III and IV that these and other compounds can 
delay accelerated mitosis processes. Thus, a therapy of dandruff is 
possible with compounds showing a good activity in Tables II, III and IV. 
At present an effective therapy of psoriasis is only possible topically 
with dithranol, tar preparations and highly active corticoides and 
systemically with antimetabolites such as methothrexate, corticosteroids 
and cytostatics. Additionally, the physical treatment with UV-light, 
X-rays and the combined application of psoralens (systemically and 
locally) and UV-light are used. All these treatment methods are either 
circumstantial or accompanied by considerable side-effects. Therefore, a 
simple effective local therapy is of advantage. Tables III and IV show 
that some of the abovementioned compounds may be used for 
psoriasis-therapy. 
Mycoses of the skin are becoming more frequent. As the kind of 
microorganism causing an irritation often cannot be determined, the 
application of broad spectrum antimycotics against dermatophytes, yeasts 
and bacteria is of special advantage. 
Tables I and II show that the above-mentioned compounds are strongly active 
against these microorganisms and may, therefore, be used for therapy of 
mycoses and bacterial skin infections. 
The compounds of the formula I may be incorporated into the usual 
pharmaceutical preparations, such as foam aerosols, powder-sprays, 
powders, throat sprays, shampoos, creams, ointments, tinctures, pastes or 
gels. The dosage of the active ingredients is between 0.05 and 1% by 
weight, preferably 0.1 to 0.8 percent by weight. 
EXAMPLE I 
Foam aerosol (filling/can: 60 gm) containing 0.5% by weight of 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone (quickly breaking foam) 
______________________________________ 
Active ingredient 0.30 gm 
Cremophor EL = reaction product of castor 
oil with ethylene oxide (1 mol:40 mol) 
0.50 gm 
Tween 80 = polyethoxylated sorbitanmono- 
oleate 0.80 gm 
Texapon N 25 = sodium laurylether sulfate 
0.50 gm 
French brandy essence 0.25 gm 
Ethanol 96% 12.75 gm 
Water 35.00 gm 
Propellant mixture ad 60.00 gm 
(Frigen 12/114 in the proportion of 
60:40 parts by volume) 
______________________________________ 
(a) Solution of active ingredient 
The active ingredient, Cremophor EL and the French brandy essence were 
successively dissolved in ethanol at room temperature. 
Tween 80 and Texapon N 25 were dissolved in water, also at room 
temperature, combined with the ethanolic solution and filtered. 
(b) Preparation of aerosol 
50.1 gm of the solution of active ingredient were filled into an 
alu-monobloc can of suitable size provided in the inside with a double 
protecting coat of lacquer. The can closed with a valve was subsequently 
filled with 9.9 gm of propellant mixture by means of a propellant filling 
equipment. 
EXAMPLE II 
Powder spray (filling/can: 100 gm) containing 0.5% by weight of 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone 
______________________________________ 
Active ingredient 0.50 gm 
Aerosil (colloidal silicic acid) 
0.50 gm 
ANM-maize (corn starch) 2.00 gm 
Isopropyl myristate 0.50 gm 
Propellant mixture ad 
(Frigen 11/12 in the proportion of 
50:50 parts by volume) 
______________________________________ 
(a) Powder of active ingredient 
The active ingredient was ground in a pinned disk mill together with the 
aerosil and the corn starch and triturated with the isopropyl myristate in 
a mortar. 
(b) Preparation of aerosol 
3.5 gm of the powder of active ingredient were filled into an alu-monobloc 
can of suitable size. The can closed with a valve was subsequently filled 
with 96.5 gm of propellant mixture by means of a propellant filling 
equiment. 
EXAMPLE III 
Powder containing 0.5% by weight of 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone 
______________________________________ 
Active ingredient 0.50 gm 
Aerosil 200 0.50 gm 
Magnesium stearate 0.20 gm 
Lactose 48.80 gm 
ANM-maize (corn starch) 50.00 gm 
______________________________________ 
The micronized active ingredient was mixed with Aerosil 200, magnesium 
stearate, lactose and corn starch and subsequently ground in a pinned disk 
mill. 
EXAMPLE IV 
Throat spray containing 0.5% by weight of 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone 
______________________________________ 
Active ingredient 0.50 gm 
Glycerin 20.00 gm 
Sodium saccharin 0.02 gm 
Ethanol 96% 10.00 gm 
Cremophor RH 40 = reaction product of 
hydrogenated castor oil with ethylene oxide 
1.00 gm 
Menthol 42.degree.-44.degree. C. 
0.05 gm 
Flavoring 0.04 gm 
Dyestuff blue q.s. 
Distilled water ad 100.00 gm 
______________________________________ 
The active ingredient was dissolved in ethanol together with menthol and 
aroma and subsequently glycerin was added. In a portion of the water 
Cremophor RH 40, sodium saccharin and dyestuff were dissolved 
successively, this solution was combined with the ethanol-glycerin 
solution, filled up with water and filtered. Spraying is effected by means 
of a mechanical pump metering valve. 
EXAMPLE V 
Shampoo containing 0.1% by weight of 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone 
______________________________________ 
Active ingredient 0.10 gm 
Comperlan KD = coconut fat acid diethanol- 
amide 3.00 gm 
Zetesol 856 T = fatty alcohol ether sulfate 
25.00 gm 
Lamepon S-TR = condensation product of 
protein hydrolyzates with vegetable 
fatty acids 5.00 gm 
Euperlan PK 771 = fatty alcohol ether 
sulfates 10.00 gm 
Cetiol HE = polyol fatty acid esters 
2.50 gm 
Chemoderm = perfume oil composition 
0.50 gm 
Dyestuff (yellowish orange 11963) 
0.012 gm 
Nip-Nip (8/2) = methyl p-hydroxybenzoate 
+ n-propyl p-hydroxy-benzoate 
0.20 gm 
Distilled water ad 100.00 gm 
______________________________________ 
Nipagine/Nipasol (Nip/Nip) were dissolved in a portion of the water while 
heating; subsequently Comperlan, Zetesol 856 T, Lamepon S-TR, Euperlan, 
Cetiol HE and dyestuff were successively stirred in at room temperature. 
After addition of the active ingredient and homogenizing well the perfume 
was added. 
EXAMPLE VI 
Gel containing 0.5% by weight of 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone 
______________________________________ 
Active ingredient 0.50 gm 
Tween 80 = polyethoxylated sorbitan- 
mono-oleate 0.10 gm 
Carbopol 940 = acrylic acid polymerizate 
0.75 gm 
Nip-Nip (8/2) 0.30 gm 
Silicone oil AK 350 3.00 gm 
Triethanolamine solution 10% 
3.70 gm 
Water ad 100.00 gm 
______________________________________ 
Nipagine and Nipasol were dissolved in a portion of the water while 
heating, and Carbopol was added at about 50.degree. C. while stirring 
vigorously. 
The micronized active ingredient was suspended in the remaining water, 
mixed with Tween and added to the Carbopol suspension. Subsequently the 
silicone oil was stirred in, and the viscosity was adjusted while further 
stirring with triethanolamine. 
EXAMPLE VII 
Cream containing 0.8% by weight of 
2,4-dihydroxy-5-n-hexyl-trifluoroacetophenone 
______________________________________ 
Active ingredient 0.8 gm 
Isopropyl myristate 7.0 gm 
Silicone oil AK 350 0.5 gm 
Tween 60 2.0 gm 
Span 60 2.0 gm 
Lanette 0 7.0 gm 
Propylene glycol 1.2 7.0 gm 
Nip-Nip (8/2) 0.3 gm 
Distilled water 73.4 gm 
______________________________________ 
Isopropyl myristate, silicone oil, Tween, Span and Lanette were melted at 
75.degree. C. and kept at this temperature. Propylene glycol, Nip/Nip 
(8/2) and water were boiled for a short time and cooled to 75.degree. C. 
The active ingredient was stirred into the isopropyl myristate melt; this 
mixture was stirred into the propylene glycol mixture, the finished 
mixture was allowed to cool. 
For use in plant protection the compounds according to the invention are 
processed into conventional formulations, especially into solution- or 
emulsion-concentrates, dusts, granulates, spray powders, seed-treatment 
powders and -solutions. The content of active substance in the sprays and 
dusts amounts from 0.01 to about 3% by weight. The seed-treatment 
solutions (about 10 to 50% by weight) and seed-treatment powders (about 20 
to 90% by weight) as well as the concentrates (up to about 95% by weight) 
comprise higher concentrations of active substance. 
Examples for formulation: 
1. Suspension Powder: 
30 parts by weight of 2,4-dihydroxy-3-methyl-5-chloro-trifluoroacetophenone 
9 parts by weight of sodium lignin sulfonate 
1 part by weight of sodium naphthalene sulfonate 
60 parts by weight of colloidal silicic acid 
The components are ground homogeneously. For use as herbicide there is 
produced an aqueous spray with a content of active ingredient of 0.01 to 
3% by weight. The spray may be used for the control of undesired 
monocotyledons, such as wild oats, as well as weeds (dicotyledons) in 
cereal and other cultures. When applying higher doses, the use as total 
herbicide is possible too. 
The other compounds of the formula I may be used in a corresponding way. 
2. Seed-treatment Solution: 
20 parts by weight of 2,4-dihydroxy-5-tert.butyl-trifluoroacetophenone 79 
parts by weight of dimethyl formamide 
3. Seed-treatment Powder: 
80 parts by weight of 2,4-dihydroxy-5-tert.butyl-trifluoroacetophenone 
3 parts by weight of magnesium stearate 
17 parts by weight of talcum 
The agents for seed-treatment are sprayed on (solution) or admixed with the 
seeds (powder). They serve for the control, above all, of the genera of 
fungi tiletia, helmintosporium, ustilago and fusarium. 
The other compounds of the formula I may be used in a corresponding manner. 
While the present invention has been illustrated with the aid of certain 
specific embodiments thereof, it will be readily apparent to others 
skilled in the art that the invention is not limited to these particular 
embodiments, and that various changes and modifications may be made 
without departing from the spirit of the invention or the scope of the 
appended claims.