Polyfluoroalkylthiopoly(ethylimidazolium) compounds, preparation process and their use as biocidal agents

The invention relates to compounds of formula: ##STR1## in which: w is 0, 1 or 2; PA1 x is between 2 and 10; PA1 y is between 0 and 5; PA1 R denotes a methyl, ethyl, hydroxyethyl or benzyl radical; PA1 X.crclbar. denotes an inorganic or organic anion; and PA1 n is an integer or decimal number between 1 and 15; PA1 the [C.sub.5 H.sub.6 N.sub.2 R.sup.+ ] group representing the following structures, taken as a mixture or individually: ##STR2## as well as their use as a biocidal agent or preservative.

The present invention relates to new compounds of the 
polyfluoroalkylthiopoly(ethylimidazolium) type, a process for their 
preparation and their use as biocidal agents in diverse industrial fields 
such as cosmetics, human and veterinary pharmacy, agriculture, paints and 
varnishes and papermaking. 
In cosmetics, products are required which have bactericidal and/or 
fungicidal properties and a good tolerance with respect to the skin and 
hair, in particular in anti-dandruff products and in products for 
cleansing the skin. 
In pharmacy, the use of bactericidal and/or fungicidal products is also of 
great interest, in particular in the treatment of diseases affecting the 
horny layer of the epidermis in man or in animals, such as acne, in the 
treatment of the mucosa or in the treatment of mycoses. 
Cationic compounds of the quaternary ammonium type are commonly used as 
bactericidal agents in cosmetics or pharmacy. However, these compounds 
show tolerance problems. 
Cetyltrimethylammonium bromide, better known under the name "CETAVLON", is 
known from the prior art. 
The Applicant has discovered new compounds derived from imidazole which 
have a good biocidal activity, as well as a lower toxicity when compared 
with the known compounds. They also have good cosmetic properties with 
respect to the hair, the skin and the nails. 
These compounds also have valuable surfactant properties. 
The subject of the present invention is new cationic compounds of the 
imidazolium type. 
Another subject of the invention is a process for the preparation of these 
compounds. 
The invention also relates to the use of these compounds as biocidal agents 
in numerous fields in the chemical industry, and more particularly in 
cosmetics and dermopharmacy. 
Further subjects will become apparent in the light of the description and 
the examples which follow. 
The compounds according to the present invention correspond to the 
following formula (I): 
##STR3## 
in which: w is 0, 1 or 2; 
x is between 2 and 10; 
y is between 0 and 5; 
R denotes a methyl, ethyl, hydroxyethyl or benzyl radical; 
X.crclbar. denotes an inorganic or organic anion; and 
n is an integer or decimal number between 1 and 15; the [C.sub.5 H.sub.6 
N.sub.2 R.sup.+ ] group representing the following structures, taken as a 
mixture or individually: 
##STR4## 
The anion X.crclbar. denotes halides, alkyl sulfates, alkylsulfonates or 
arylsulfonates. 
In particular it may denote Cl.sup.-, Br.sup.-, I.sup.-, CH.sub.3 
OSO.sub.3.sup.-, C.sub.2 H.sub.5 OSO.sub.3.sup.-, CH.sub.3 SO.sub.3.sup.- 
or 
##STR5## 
The preferred compounds according to the present invention are chosen from 
those of formula (I) in which w is 0. 
A further subject of the invention consists of a process for the 
preparation of the cationic surfactants of the invention. 
The compounds according to the invention may be prepared by a radical 
addition reaction of a mercaptan of formula: 
EQU CF.sub.3 --(CF.sub.2).sub.x --(CH.sub.2).sub.y --SH 
in which x and y have the same meaning as indicated above, with one or more 
molecule(s) of 1-vinylimidazole in order to obtain a compound of the 
following formula (II) 
EQU CF.sub.3 --(CF.sub.2).sub.x --(CH.sub.2).sub.y --S--(C.sub.5 H.sub.6 
N.sub.2).sub.n H (II) 
in which the ((C.sub.5 H.sub.6 N.sub.2) group represents the following 
structures, taken as a mixture or individually: 
##STR6## 
The compound of formula (II) thus obtained is then quaternized by 
alkylation with a compound of the formula RX, in which R and X have the 
meanings indicated above. 
In the case where w=1 or 2, the products thus obtained are oxidized with 
hydrogen peroxide using a known process, at a temperature of between 
20.degree. and 50.degree. C. 
The process for the preparation of the compounds of the invention may be 
represented by the following reaction scheme: 
##STR7## 
The radical reaction takes place in a solvent medium in the presence of a 
free radical initiator. 
Free radical initiators which may be mentioned are hydroperoxides, such as 
tert-butyl hydroperoxide, peroxides, such as dibenzoyl peroxide, 
peresters, such as tert-butyl peroxybenzoate, or azo derivatives and in 
particular azobisisobutyronitrile. 
The solvents which may be used must be inert with respect to the reagents 
and may be chosen from C.sub.1 -C.sub.4 alcohols, such as methanol or 
isopropanol, alkyl ethers, glycol ethers, cyclic ethers, such as 
tetrahydrofuran, or C.sub.6 -C.sub.8 aliphatic or aromatic hydrocarbons, 
such as toluene. 
The starting mercaptan is dissolved in the solvent in the presence of 
1-vinylimidazole and the free radical initiator is then added, the 
reaction being carried out under an inert atmosphere. The compounds of 
formula (II) thus obtained are then alkylated using an alkylating agent RX 
in the presence of an inert solvent, such as those mentioned above. 
The alkylating agents RX used according to the invention are chosen, for 
example, from methyl halides, ethyl halides, methyl sulfates, ethyl 
sulfates, methylsulfonate, methyl para-toluenesulfonate or bromoethanol. 
The compounds of formula (II) are novel and are another subject of the 
invention. 
The cationic polyfluoroalkylthiopoly-(ethylimidazolium) compounds of 
formula (I) of the invention have good biocidal properties. 
A good biocidal activity of these compounds has been observed using 
conventional methods on the following strains:Pseudomonas aeruginosa, 
Staphylococcus aureus and Candida albicans. These strains may be regarded 
as representing the main bacteria and fungi responsible for cutaneous 
disorders of bacterial or mycobacterial origin or disorders due to the 
implantation of pathogenic yeasts. 
The low toxicity of the compounds of the invention has been observed by 
hemolysis of the erythrocytes from blood samples. 
The compounds according to the present invention may be used as biocidal 
agents or as preservatives in the chemical industry sector, in particular 
in cosmetic products, and the pharmaceutical industry for human or 
veterinary use, in agricultural products, products for plant treatment, 
paints and varnishes and papermaking. 
The compounds of the invention have valuable surfactant properties. 
Moreover, they have the characteristic of attaching themselves to 
keratinous materials, such as the skin, the hair and the nails. 
Their cationic amphophilic character additionally imparts to them 
disentangling, softness, sheen and suppleness characteristics with respect 
to hair and softness characteristics with respect to the skin. 
On the other hand, the presence of a perfluorinated chain in their 
structure makes it possible to impart a hydrophobic character and an 
oleophobic character to the treated skin or hair. 
The compounds according to the invention permit rapid drying of the hair or 
prevent excessive regreasing of the skin and the hair. 
The compounds of the invention are therefore particularly valuable for 
cosmetic care of keratinous materials. They are also particularly valuable 
for the treatment of cutaneous disorders of bacterial or mycobacterial 
origin or disorders due to the implantation of pathogenic yeasts. They 
may, in particular, be used in pharmaceutical compositions which are able 
to be applied topically to the skin or to the mucosa, for the treatment of 
acne or of mycoses, or in cosmetic compositions, in particular body 
deodorants or mouthwashes. 
The invention therefore also relates to pharmaceutical or cosmetic 
compositions for the treatment or the care of human keratinous materials, 
said compositions containing, in a physiologically acceptable medium, an 
effective amount of compounds of formula (I) as defined above. 
The compounds of formula (I) are present in concentrations of preferably 
between 0.1 and 10% by weight, with respect to the total weight of the 
composition, and preferably between 0.2 and 5% by weight. 
These compositions may be aqueous, alcoholic or aqueous-alcoholic 
solutions, or emulsions in the form of a milk or cream, foam, gel, paste 
or stick or in the form of a spray. 
These compositions may be pressurized in aerosol devices in the presence of 
a propellant, optionally in the presence of foam generators or 
emulsifiers. 
Propellants which may be mentioned are agents of the freon type, C.sub.3 
-C.sub.5 alkanes, chlorinated solvents, such as methylene chloride, or 
ethers, such as dimethyl ether. 
The compositions may also be in the form of a vesicular dispersion based on 
ionic lipids (liposomes) or non-ionic lipids. 
These compositions contain water, a physiologically acceptable solvent or a 
mixture of water and said solvent, the solvent being chosen from C.sub.1 
-C.sub.4 lower alcohols, such as ethanol, isopropanol or propanol, or 
polyalcohols, such as polyethylene glycol or glycerin, these solvents 
being present in proportions of between 0 and 50%. 
The compositions according to the invention may also contain oils, natural 
or synthetic waxes, fatty alcohols, silicones, nonionic, cationic, weakly 
anionic, amphoteric or zwitterionic surfactants, foaming agents, 
emulsifiers or dispersants, polymers of natural origin, such as cellulose, 
guar or chitosan derivatives, peptides, synthetic polymers, conditioners, 
foam stabilizers, thickeners, agents for imparting a sheen, sterols, 
salts, sunscreens, perfumes, coloring agents, moisturizers and 
preservatives other than those of formula (I), in particular those of the 
isothiazolone family, such as 2-methylisothiazolone, 2-octylisothiazolone, 
5-chloro-2-methylisothiazoline, benzoisothiazolone or those described in 
French Patent FR-2,492,376. 
A particular form of cosmetic application according to the invention 
consists of compositions for washing and/or cosmetic treatment of hair 
with rinsing and rapid drying, said compositions containing at least one 
compound of formula (I) in the presence of detergents and foaming agents 
or conventional treatment agents compatible with the compounds of the 
invention. 
These compositions may be in the form of a shampoo, an after-shampoo or a 
composition for rinsing the hair. They are applied in effective amounts 
for washing and/or treating the hair, then followed by rinsing with water. 
The invention also relates to compositions for treatment of the skin, 
containing at least one compound of formula (I) in the presence of 
conventional treatment agents compatible with the compounds of the 
invention, so as to prevent excessive regreasing of the skin after 
application. 
Another embodiment of the invention also consists of hair compositions in 
the form of a shampoo or lotion for the elimination of dandruff. 
Another subject of the invention comprises a process for the cosmetic 
treatment of hair for the elimination of dandruff, using the composition. 
The invention also relates to the use of the compounds of formula (I) for 
the preparation of a medicament for the treatment of cutaneous disorders 
of bacterial or mycobacterial origin or disorders due to implantations of 
pathogenic yeasts. 
The examples which follow serve to illustrate the invention, without, 
however, any limitation being implied.

PREATION EXAMPLES 
EXAMPLE 1 
Preparation of a compound of formula (I) in which: x=5y=2n=1 R=CH.sub.3 
X=CH.sub.3 OSO.sub.3 .crclbar. 
STEP 1 
Preparation of a compound of formula (II) in which: x=5y=2n=1 
76 g of 2-F-hexylethanethiol (0.2 mol) in solution in 80 g of methanol are 
placed in a reactor. The mixture is stirred under a nitrogen atmosphere. 
18.8 g of 1-vinylimidazole are then added in the course of 5 minutes. 
Heating is then started. When the temperature of the reaction mixture 
reaches 55.degree. C., a solution of 0.752 g of azobisisobutyronitrile in 
40 g of methanol is then added dropwise in the course of 1 h 30 while 
continuing to raise the temperature. When the addition is complete, the 
temperature of the reaction mixture is close to 66.degree. C. The methanol 
refluxes. 
Stirring, heating and the stream of nitrogen are maintained for 14 hours. 
The reaction mixture then consists of monoaddition and diaddition products. 
The monoaddition product is isolated by filtering through silica 60 H 
(eluent CH.sub.2 Cl.sub.2 /CH.sub.3 OH:95/5) with a yield of 80% (m=76 g). 
Alkali number:2.07 meq/g (theoretical:2.10 meq/g) 
Thioether index:2.05 meq/g (theoretical:2.10 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 32.92 32.69 
H 2.34 2.45 
N 5.91 5.84 
S 6.76 7.10 
F 52.08 51.84 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1. 
23.7 g (0.05 mol) of the compound from Step 1 are dissolved in 25 ml of 
methanol in a reactor. 
6.19 g of dimethyl sulfate are added dropwise at 25.degree. in the course 
of 1 hour, whilst ensuring that the temperature of the reaction mixture 
does not rise above 35.degree. C. 
The mixture is stirred for 14 hours at ambient temperature. The solvent is 
then evaporated under reduced pressure. 30.70 g of a light brown paste are 
obtained. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 30.01 29.74 
H 2.85 3.05 
N 4.67 4.41 
S 10.68 10.34 
F 41.14 40.83 
______________________________________ 
EXAMPLE 2 
Compound of Formula (I) in which: x=5 y=2 n=2 X=CH.sub.3 OSO.sub.3 
.crclbar. 
STEP 1 
Compound of formula (II) in which: x=5 y=2 n=2 
This compound is prepared using the method of Example 1, Step 1. 
The dicondensation product is isolated from the reaction mixture by 
filtering through silica 60 H (eluent CH.sub.2 Cl.sub.2 /CH.sub.3 
OH:95/5). 
In parallel to 76 g of 2-(2'-F-hexylethylthio)ethylimidazole (Example 1), 5 
g of dicondensation product, 
2-[2'-(2"-(2-F-hexylethylthio)ethylimidazole]-ethylimidazole, are 
obtained. 
The product is in the form of a light brown paste. 
Alkali number:3.45 meq/g (theoretical:3.52 meq/g) 
Thioether index:1.70 meq/g (theoretical:1.76 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 38.03 37.16 
H 3.01 3.25 
N 9.86 9.58 
S 5.64 5.56 
F 43.45 41.30 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1 
The method is analogous to that of Example 1, Step 2, using: 
3.15 g of the compound from Step 1 dissolved in 5 g of methanol; 
1.37 g of dimethyl sulfate. 
4.5 g of quaternized product are obtained, which product is in the form of 
a beige paste. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 32.20 31.48 
H 3.56 3.78 
N 6.83 6.50 
S 11.72 10.90 
F 30.10 31.86 
______________________________________ 
EXAMPLE 3 
Preparation of a Compound of Formula (I) in which: x=5 y=2 n=3 R=CH.sub.3 
X=CH.sub.3 OSO.sub.3 .crclbar. 
STEP 1 
Preparation of a compound of formula (II) in which: x=5 y=2 n=3 
The method is analogous to that of Example 1, Step 1, using: 
38 g of 2-F-hexylethanethiol (0.1 mol) dissolved in 40 g of methanol; 
29.61 g (0.3 mol) of 1-vinylimidazole; 
1.12 g of azobisisobutyronitrile in 40 g of methanol. 
After reaction, the solvent is evaporated under reduced pressure and 67.5 g 
of a light beige paste are obtained. 
Alkali number:4.47 meq/g (theoretical:4.53 meq/g) 
Thioethane index:1.60 meq/g (theoretical:1.51 meq/g) 
STEP 2 
Quaternization of the compound from Step 1 
The method is analogous to that of Example 1, Step 2, using: 
20 g of the compound from Step 1 dissolved in 50 ml of methanol; 
11.26 g of dimethyl sulfate. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 33.61 33.34 
H 4.02 4.49 
N 8.22 8.36 
S 12.39 12.15 
F 23.00 21.55 
______________________________________ 
EXAMPLE 4 
Preparation of a Compound of Formula (II) in which: x=7 y=2 n=1 R=CH.sub.3 
X=CH.sub.3 OSO.sub.3 .crclbar. 
STEP 1 
Preparation of a compound of formula (II) in which: x=7 y=2 n=1 
The method is analogous to that of Example 1, Step 1, using: 
96 g of 2-F-octylethanethiol (0.2 mol) dissolved in 80 g of methanol; 
18.8 g of 1-vinylimidazole (0.2 mol); 
0.752 g of azobisisobutyronitrile in 40 g of methanol. 
The reaction mixture consists of monoaddition and diaddition products. 
The monoaddition product, 2-(2'-F-octylethylthio)ethylimidazole is isolated 
by filtration through Merck 60 H silica under the same conditions as for 
Example 1, Step 1. 
Yield=85% (m=98 g) 
Alkali number:1.69 meq/g (theoretical:1.74 meq/g) 
Thioether index:1.75 meq/g (theoretical 1.74 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 31.36 31.09 
H 1.92 1.90 
N 4.88 4.89 
S 5.57 5.45 
F 56.27 55.86 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1. 
The method is analogous to that of Example 1, Step 2, using: 
43.05 g (0.075 mol) of the compound from Step 1 dissolved in 40 ml of 
methanol; 
9.45 g of dimethyl sulfate. 
52.50 g of a light chestnut paste are obtained. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 29.14 28.89 
H 2.43 2.59 
N 4.00 3.74 
S 9.14 9.11 
F 46.14 45.84 
______________________________________ 
EXAMPLE 5 
Preparation of a Compound of Formula (I) in which: x=7 y=2 n=1.5 R=CH.sub.3 
X=CH.sub.3 OSO.sub.3 .crclbar. 
STEP 1 
Preparation of a compound of formula (II) in which: x=7 y=2 n=1.5 
The method is analogous to that of Example 1, Step 1, using: 
96 g of 2-F-octylethanethiol (0.2 mol) dissolved in 80 g of methanol; 
28.2 g (0.3 mol) of 1-vinylimidazole; 
1.15 g of azobisisobutyronitrile in 40 g of methanol. 
124 g of a beige-colored pasty product are obtained. 
Alkali number:2.41 meq/g (theoretical:2.41 meq/g) 
Thioether index:1.60 meq/g (theoretical:1.61 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 33.83 33.69 
H 2.27 2.40 
N 6.76 6.81 
S 5.16 4.95 
F 41.98 42.08 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1. 
The method is analogous to that of Example 1, Step 2, using: 
30 g of the compound from Step 1, dissolved in 37 ml of methanol; 
9.11 g of dimethyl sulfate. 
39 g of a light beige-colored pasty product are obtained. 
Alkali number:0.1 meq/g. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 30.38 30.31 
H 2.86 2.86 
N 5.18 5.06 
S 9.89 10.09 
F 39.95 39.55 
______________________________________ 
EXAMPLE 6 
Preparation of a Compound of Formula (II) in which: x=7 y=2 n=3 R=CH.sub.3 
X=CH.sub.3 OSO.sub.3 .crclbar. 
STEP 1 
Preparation of a compound of formula (II) in which: x=7 y=2 n=3 
The method is analogous to that of Example 1, Step 1, using: 
96 g (0.2 mol) of 2-F-octylethanethiol dissolved in 76 g of isopropanol; 
56.4 g (0.6 mol) of 1-vinylimidazole; 
2.24 g of azobisisobutyronitrile in 150 g of isopropanol. 
Alkali number:3.83 meq/g (theoretical:3.93 meq/g) 
Thioether index:1.34 meq/g (theoretical:1.31 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 39.59 39.34 
H 2.72 3.18 
N 10.31 10.74 
S 3.92 4.30 
F 39.46 40.87 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1. 
The method is analogous to that of Example 1, Step 2, using: 
40 g of the compound from Step 1, dissolved in 30 ml of methanol; 
19.3 g of dimethyl sulfate. 
59.3 g of light beige product are obtained. 
______________________________________ 
ELEMENTAL ANNLYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 32.63 32.42 
H 3.62 3.76 
N 7.37 7.21 
S 11.24 10.99 
F 28.31 28.58 
______________________________________ 
EXAMPLE 7 
Preparation of a Compound of Formula (I) in which: x=7 y=2 n=5 X=CH.sub.3 
OSO.sub.3 .crclbar.R=CH.sub.3 
STEP 1 
Preparation of a compound of formula (II) in which: x=7 y=2 n=5 
The method is analogous to that of Example 1, Step 1, using: 
48 g of 2-F-octylethanethiol (0.1 mol) dissolved in 85 ml of methanol; 
47 g (0.5 mol) of 1-vinylimidazole; 
1.88 g of azobisisobutyronitrile in 60 ml of methanol. 
103.2 g of a beige colored product are obtained. 
Alkali number:4.62 meq/g (theoretical:5.26 meq/g) 
Thioether index:1.11 meq/g (theoretical:1.05 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 44.21 44.56 
H 3.71 4.74 
N 14.73 14.96 
S 3.37 4.04 
F 33.97 32.01 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1. 
The method is analogous to that of Example 1, Step 2, using: 
30 g of the compound from Step 1, dissolved in 100 ml of methanol; 
17.47 g of dimethyl sulfate. 
47.5 g of light beige product are obtained. 
EXAMPLE 8 
Preparation of a Compound of Formula (I) in which: x=7 y=2 n=2 X=CH.sub.3 
OSO.sub.3 .crclbar. R=CH.sub.3 
STEP 1 
Preparation of a compound of formula (II) in which: x=7 y=2 n=2 
The method is analogous to that of Example 4, Step 1. 
The dicondensation product is isolated from the reaction mixture by 
filtration through silica 60 H (eluent CH.sub.2 Cl.sub.2 /CH.sub.3 
OH:95/5). 
In parallel to the 98 g of 2-(2'-F-octylethylthio)ethylimidazole (Example 
4), 7 g of dicondensation product, 
2-[2'-F-octylethylthio)ethylimidazole]ethylimidazole, are obtained. 
The product is in the form of a deep brown paste. 
Alkali number:2.79 meq/g (theoretical:2.99 meq/g) 
Thioether index:1.37 meq/g (theoretical:1.49 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 35.95 35.14 
H 2.50 2.70 
N 8.38 7.89 
S 4.79 4.72 
F 48.35 47.54 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1. 
The method is analogous to that of Example 1, Step 2, using: 
6.5 g of the compound from Step 1, dissolved in 10 g of methanol; 
2.22 g of dimethyl sulfate. 
8.7 g of quaternized product are obtained, which product is in the form of 
a deep beige paste. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 31.30 30.59 
H 3.15 3.43 
N 6.09 5.78 
S 10.43 10.04 
F 35.15 33.91 
______________________________________ 
EXAMPLE 9 
Preparation of a Compound of Formula (I) in which: x=7 y=2 n=10 X=CH.sub.3 
OSO.sub.3 .crclbar. R=CH.sub.3 
STEP 1 
Preparation of a compound of formula (II) in which: x=7 y=2 n=10 
The method is analogous to that of Example 1, Step 1, using: 
20 g of 2-F-octylethanethiol (0.0417 mol) dissolved in 100 ml of methanol; 
39.17 g of 1-vinylimidazole; 
1.57 g of azobisisobutyronitrile. 
After reaction, the solvent is evaporated under reduced pressure and 59 g 
of a light beige paste are obtained. 
Alkali number:6.08 meq/g (theoretical:7.04 meq/g) 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 50.70 48.22 
H 4.61 5.37 
N 19.71 18.55 
S 2.26 2.02 
F 22.72 22.88 
______________________________________ 
STEP 2 
Quaternization of the compound from Step 1. 
The method is analogous to that of Example 1, Step 2, using: 
20 g of the compound from Step 1, dissolved in 60 ml of methanol; 
15.32 g of dimethyl sulfate. 
34.5 g of product are obtained. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 35.82 34.25 
H 4.70 5.29 
N 10.44 10.05 
S 13.15 11.80 
F 12.04 11.99 
______________________________________ 
EXAMPLE 10 
Preparation of a Compound of Formula (I) in which: x=5, y=2, n=1, R=benzyl, 
X=Cl.sup.- 
100 g (0.211 mol) of the compound obtained in Step 1 of Example 1 are 
dissolved in 270 ml of dimethylacetamide in a 500 ml reactor. 26.7 g of 
benzyl chloride are added dropwise in the course of 5 minutes. 
The mixture is heated at 70.degree. C. for 20 hours. 
After returning to ambient temperature, the solution is added dropwise in 
the course of 10 minutes to 800 ml of tetrahydrofuran. A pale yellow 
precipitate is obtained, which is filtered off and washed with twice 300 
ml of tetrahydrofuran heated to 60.degree. C. 
After drying under vacuum in an oven, 88 g (70%) of a white solid are 
obtained, the .sup.13 C NMR spectrum of which is consistent with the 
expected structure. 
The melting point of the N-(3-thio-5-F-hexyl)pentyl-benzylimidazolium 
chloride is 124.degree. C. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 39.98 39.87 
H 3.02 3.07 
N 4.66 4.62 
S 5.34 5.32 
Cl 5.90 5.88 
F 41.10 41.05 
______________________________________ 
EXAMPLE 11 
Preparation of a Compound of Formula (I) in which: x=5, y=2, n=1, R=C.sub.2 
H.sub.5, X=Br.sup.- 
40 g (0.84 mol) of the compound obtained in Step 1, Example 1 are dissolved 
in 160 ml of tetrahydrofuran in a 500 ml reactor. When the reagent has 
dissolved completely, 18.4 g (0.168 mol) of ethyl bromide are added in the 
course of 5 minutes. This mixture is then heated for 36 hours with the 
solvent under reflux. 
Heating is then stopped. When the temperature of the mixture has returned 
to 25.degree. C., the presence of two phases is observed. 
The upper phase is removed by decanting off. After three successive washes 
with 100 ml of tetrahydrofuran followed by removal of the solvent by 
decanting off and then drying of the residue under vacuum in an oven, 32 g 
(70%) of a water-soluble orange-colored paste are obtained, the .sup.13 C 
NMR spectrum of which is consistent with the expected structure. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 30.89 30.05 
H 2.77 2.81 
N 4.80 4.73 
S 5.50 5.68 
Br 13.70 13.37 
F 42.35 40.65 
______________________________________ 
EXAMPLE 12 
Preparation of a Compound of Formula (I) in which: x=5, y=2, n=3, R=benzyl, 
X=Cl.sup.- 
40 g of the random compound obtained in Step 1 of Example 3 are dissolved 
in 200 ml of dimethylacetamide at 80.degree. C. 
When all of the product has dissolved, 61.3 g of benzyl chloride are added 
in the course of 15 minutes at 80.degree. C. The mixture is then heated at 
80.degree. C. for 24 hours and then brought to 25.degree. C., at which 
temperature the product is precipitated, with stirring, by dropwise 
addition to 900 ml of tetrahydrofuran. 
The product is then filtered off, washed with tetrahydrofuran (twice 300 
ml) and then dried. 
The precipitate, which is hygroscopic, is taken up in 600 ml of water. 
After it has been chilled in an ethanol+solid carbon dioxide bath, the 
solution is then lyophilized. 
After this operation 44 g of a dry beige powder are obtained. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 50.70 49.40 
H 4.26 4.98 
N 8.06 8.35 
S 3.08 1.90 
Cl 10.21 10.21 
F 23.70 21.87 
______________________________________ 
EXAMPLE 13 
Preparation of a Compound of Formula (I) in which: x=5, y=2, n=1, 
R=CH.sub.3, X=Cl.sup.- 
200 g of the compound obtained in Step 1 of Example 1, dissolved in 500 ml 
of dimethylacetamide, are introduced into a 1500 ml reactor. The reactor 
is then hermetically sealed and the solution is then heated to 75.degree. 
C., with stirring. When this temperature is reached, gaseous methyl 
chloride is introduced into the reactor until the pressure inside the 
system reaches 1500 mbar. 
When this pressure is obtained, the methyl chloride feed is stopped until 
all of the gas introduced has been consumed (return to atmospheric 
pressure inside the reactor). When the system consumes no further methyl 
chloride, the installation is purged with nitrogen. After the temperature 
has returned to 25.degree. C., the product is precipitated in 1.5 liters 
of ethyl acetate, with vigorous stirring. 
After removal of the solvent by decanting off, the residue obtained is 
washed with three times 200 ml of ethyl acetate. After drying in an oven, 
153 g (70%) of a beige paste are obtained, the .sup.13 C NMR spectrum of 
which is consistent with the expected structure. 
______________________________________ 
ELEMENTAL ANALYSIS 
THEORETICAL 
FOUND 
______________________________________ 
C 32.04 30.59 
H 2.69 3.25 
N 5.33 5.33 
S 6.11 5.91 
Cl 16.76 5.88 
F 47.06 46.96 
______________________________________ 
EXAMPLE 14 
Preparation of a Compound of Formula (I) in which: x=5, y=2, n=1, 
R=hydroxyethyl, X=Br.sup.- 
47.4 g of the compound obtained from Step 1 of Example 1 are dissolved in 
135 ml of dimethylacetamide in a 500 ml reactor. 50 g (0.4 ml) of 
bromoethanol are added dropwise in the course of 10 minutes. 
The mixture is heated at 70.degree. C. for 48 hours. 
After the temperature has returned to 25.degree. C., the solution is 
precipitated in 200 ml of ethyl acetate. A pasty beige precipitate is 
obtained. The supernatant phase is removed by decanting off and the 
residue is washed with twice 200 ml of ethyl acetate. 
The product is reprecipitated from 100 ml of ethyl acetate at 70.degree. C. 
After the temperature has returned to 25.degree. C., the solvent is 
removed by decanting off. 
After drying in an oven, 35 g (50%) of a beige pasty product are obtained. 
The product is purified by liquid phase chromatography on Merck 60 H 
silica (eluent CH.sub.2 Cl.sub.2 /CH.sub.3 OH:90/10) 
The .sup.13 C NMR spectrum is in accordance with the expected structure. 
EXAMPLE A 
______________________________________ 
OIL-IN-WATER EMULSION 
______________________________________ 
Hydrogenated polyisobutene 
6.5 g 
Octyl palmitate 5.0 g 
Cyclomethicone 5.0 g 
Cetyl alcohol 4.0 g 
Glycerol stearate 3.0 g 
Glyerol 3.0 g 
Oxyethylenated polyethylene glycol stearate 
2.0 g 
containing 40 mol of ethylene oxide, sold 
under the name "MYRJ 52" name by ICI 
Myristyl myristate 2.0 g 
Sorbitan tristearate 0.9 g 
Dipotassium salt of ethylene- 
0.05 g 
diaminetetraacetic acid 
Compound from Example 5 5.0 g 
Preservative qs 
Water qs 100.0 g 
______________________________________ 
EXAMPLE B 
______________________________________ 
OIL-IN-WATER EMULSION 
______________________________________ 
Hydrogenated polyisobutene 
6.5 g 
Octyl palmitate 5.0 g 
Cyclomethicone 5.0 g 
Cetyl alcohol 4.0 g 
Glycerol stearate 3.0 g 
Glyerol 3.0 g 
Oxyethylenated polyethylene glycol stearate 
2.0 g 
containing 40 mol of ethylene oxide, sold 
under the name "MYRJ 52" by ICI 
Myristyl myristate 2.0 g 
Sorbitan tristearate 0.9 g 
Dipotassium salt of ethylene- 
0.05 g 
diaminetetraacetic acid 
Compound from Example 7 2.5 g 
Preservative qs 
Water qs 100.0 g 
______________________________________ 
EXAMPLE C 
______________________________________ 
WATER-IN-OIL EMULSION 
______________________________________ 
Vaseline 14.2 g 
Vaseline oil 12.2 g 
Hydrogenated lanolin 6.3 g 
Isopropyl palmitate 4.5 g 
Mixture of ketearyl octanoate 
2.85 g 
and isopropyl myristate, marketed 
under the name "PCL Liquide huile 
2/066210" by DRAGOCO 
Magnesium lanolate 2.7 g 
Octoxyglyceryl palmitate 1.9 g 
Palm oil 0.5 g 
5-chloro-2-(2,4-dichlorophenoxy)- 
0.5 g 
phenol, marketed under the name 
"TRICLOSAN" by CIBA-GEIGY 
Lanolin alcohol sold under the 
0.43 g 
name "HARTOLAN" by CRODA 
Compound from Example 5 5.0 g 
Perfume qs 
Preservative qs 
Water qs 100.0 g 
______________________________________ 
EXAMPLE D 
______________________________________ 
WATER-IN-OIL EMULSION 
______________________________________ 
Vaseline 14.2 g 
Vaseline oil 12.2 g 
Hydrogenated lanolin 6.3 g 
Isopropyl palmitate 4.5 g 
Mixture of ketearyl octanoate 
2.85 g 
and isopropyl myristate, marketed 
under the name "PCL Liquide huile 
2/066210" by DRAGOCO 
Magnesium lanolate 2.7 g 
Octoxyglyceryl palmitate 1.9 g 
Palm oil 0.5 g 
5-chloro-2-(2,4-dichlorophenoxy)- 
0.5 g 
phenol, marketed under the name 
"TRICLOSAN" by CIBA-GEIGY 
Lanolin alcohol sold under the 
0.43 g 
name "HARTOLAN" by CRODA 
Compound from Example 7 2.5 g 
Perfume qs 
Preservative qs 
Water qs 100.0 g 
______________________________________ 
EXAMPLE E 
______________________________________ 
DEODORANT SPRAY 
______________________________________ 
Compound from Example 7 1.0 g 
Water 50.0 g 
Perfume 1.0 g 
95.degree. ethyl alcohol qs 
100.0 g 
______________________________________ 
EXAMPLE F 
______________________________________ 
AQUEOUS STICK DEODORANT 
______________________________________ 
Compound from Example 3 0.23 g 
Sodium stearate 7.5 g 
Propylene glycol 65.0 g 
Perfume 1.0 g 
Water qs 100.0 g 
______________________________________ 
EXAMPLE G 
______________________________________ 
SHAMPOO 
______________________________________ 
Alkylpolyglycoside sold under the 
15.0 g AS 
name "APG 300 CS" as a solution 
containing 50% of active 
substance (AS) 
Compound of Example 9 5.0 g 
Water qs 100.0 g 
Spontaneous pH = 5 
______________________________________ 
EXAMPLE H 
______________________________________ 
SHAMPOO 
______________________________________ 
Sodium laurylsarcosinate sold 
15.0 g 
under the name "ORAMIX L30" by 
SEPPIC 
Cocobetaine sold under the 
3.75 g 
name "DEHYTON AB30" by HENKEL 
Compound from Example 3 0.2 g 
Water qs 100.0 g 
Spontaneous pH = 7.2 
______________________________________ 
EXAMPLE I 
______________________________________ 
SHAMPOO 
______________________________________ 
Compound from Example 4 2 g 
Alkylpolyglycoside sold under the 
15.0 G AS 
name "APG 300" by HENKEL 
Disodium salt of ethylenediamine- 
0.5 g AS 
tetraacetic acid 
Preservatives 0.3 g 
Perfume 0.5 g 
pH = 6 qs 
Purified water qs 100.0 g 
______________________________________ 
The shampoo permits rapid drying of damp hair. 
EXAMPLE J 
______________________________________ 
AFTER-SHAMPOO RINSE 
______________________________________ 
Compound from Example 5 1.0 g 
Mixture of cetyl stearyl alcohol 
3.0 g 
and oxyethylenated cetyl stearyl 
alcohol containing 33 mol of 
ethylene oxide, sold under the 
name "SINNOWAX AO" by HENKEL 
Dimethyldialkylammonium chloride 
2.3 g 
Colorant 0.017 g 
Preservative 0.04 g 
pH = 3.5 qs 
Purified water qs 100.0 g 
______________________________________ 
This after-shampoo rinse permits rapid drying of damp hair. 
EXAMPLE K 
______________________________________ 
OIL-IN-WATER EMULSION 
______________________________________ 
Hydrogenated polyisobutene 
6.5 g 
Octyl palmitate 5.0 g 
Cyclomethicone 5.0 g 
Cetyl alcohol 4.0 g 
Glycerol stearate 3.0 g 
Glycerol 3.0 g 
Oxyethylenated polyethylene 
2.0 g 
glycol stearate containing 40 mol 
of ethylene oxide, sold under the 
name "MYRJ 52" by ICI 
Myristyl myristate 2.0 g 
Sorbitan tristearate 0.9 g 
Dipotassium salt of ethylene- 
0.09 g 
diaminetetraacetic acid 
Compound from Example 10 2.5 g 
Preservative qs 
Water qs 100.0 g 
______________________________________ 
The compound from Example 10 may be replaced by the compound from Example 
12. 
EXAMPLE L 
______________________________________ 
WATER-IN-EMULSION 
______________________________________ 
Vaseline 14.25 g 
Vaseline oil 12.20 g 
Hydrogenated lanolin 6.3 g 
Isopropyl palmitate 4.5 g 
Mixture of ketearyl octanoate 
2.85 g 
and isopropyl myristate, marketed 
under the name "PCL LIQUIDE HUILE 
2/066210" by DRAGOCO 
Magnesium lanolate 2.7 g 
Octoxyglyceryl palmitate 1.9 g 
Palm oil 0.5 g 
5-chloro-2-(2,4-dichlorophenoxy)- 
0.5 g 
phenol, marketed under the name 
"TRICLOSAN" by CIBA-GEIGY 
Lanolin alcohol sold under the 
0.43 g 
name "HARTOLAN" by CRODA 
Compound from Example 12 0.5 g 
Perfume qs 
Preservative qs 
Water qs 100.0 g 
______________________________________ 
The compound from Example 12 may be replaced by the compound from Example 
10.