Synthesis and surface properties of a series of surfactants based on O-alkyl and O-perfluoro-N,N′-diisopropylisoureas

Article abstract of DOI:10.1016/j.jfluchem.2011.03.016

O-Dodecyl-N,N′-diisopropylisourea and O-tridecafluorooctyl-N, N′-diisopropylisourea were synthesized by reaction of hydrogenated or fluorinated alcohols onto diisopropylcarbodiimide in quasi-quantitative yields. Adding various hydrogen halides (HCl, HBr, or HI) onto these isoureas enabled one to obtain isoureas hydrohalides with tensioactive properties. The surface properties of both series of hydrogenated and fluorinated surfactants were studied and compared. The influence of the counter-ions onto the surface properties showed that the tensioactive properties were improved in the following increasing order: I < Cl < Br. Fluorinated isourea hydrohalides exhibited better surfactant properties than their hydrogenated homologues.

Full text of DOI:10.1016/j.jfluchem.2011.03.016

Journal of Fluorine Chemistry 132 (2011) 382–388
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis and surface properties of a series of surfactants based on O-alkyl and
O-perfluoro-N,N0-diisopropylisoureas
a
b
a
b
b,
*
´ ´
Leila Badache , Frederic Boschet , Zineb Lehanine , Bernard Boutevin , Bruno Ameduri
a Laboratoire de Synthe`se Organique, Faculte´ de Chimie, Universite´ des Sciences et de la Technologie Houari Boumedie`ne, B.P. 32, Bab-Ezzouar, Alger, Algeria
b Institut Charles Gehrardt, Inge´nie´rie et Architectures Macromole´culaires, UMR CNRS 5253, Ecole Nationale Supe´rieure de Chimie de Montpellier,
8 rue de l’Ecole Normale, 34296 Montpellier Cedex 5, France
A R T I C L E I N F O
A B S T R A C T
O-Dodecyl-N,N0-diisopropylisourea and O-tridecafluorooctyl-N,N0-diisopropylisourea were synthesized
by reaction of hydrogenated or fluorinated alcohols onto diisopropylcarbodiimide in quasi-quantitative
yields. Adding various hydrogen halides (HCl, HBr, or HI) onto these isoureas enabled one to obtain
isoureas hydrohalides with tensioactive properties. The surface properties of both series of
hydrogenated and fluorinated surfactants were studied and compared. The influence of the counter-
ions onto the surface properties showed that the tensioactive properties were improved in the following
increasing order: I < Cl < Br. Fluorinated isourea hydrohalides exhibited better surfactant properties
than their hydrogenated homologues.
Article history:
Received 15 December 2010
Received in revised form 14 March 2011
Accepted 23 March 2011
Available online 30 March 2011
Keywords:
Cationic surfactant
Critical micelle concentration
Fluorinated surfactant
Hydrohalides
ß 2011 Elsevier B.V. All rights reserved.
Isourea
Surface properties
1. Introduction
hydrophobic group and exhibit special properties such as high
thermal and chemical stabilities, high surface activity, and low
Hydrochloride and hydrobromide cationic surfactants in water
exhibit interesting surface properties [1] that showed various
applications as anti-corrosion additives [2–4]. Indeed, corrosion
inhibitors, especially those based on hydrochloride cationic
surfactants, are the most interesting because of the small size of
the chlorine atom, improving their adhesion to metal [5].
Moreover, these surfactants can be used as adhesion agents
between the asphalt, resulting from the crude oil refinery, and
gravels, which is a mixture of acidic (granite and quartz) and basic
(lime and marble) minerals. Scheme 1 illustrates the adhesion
between asphalt and gravels in the presence of surfactants. As the
deterioration of road pavement often arises from a lack of
adhesion, this drawback can be overcome by the use of a small
amount of surfactants in the binder, at a low cost compared to the
pavement itself [6–9].
critical micelle concentration [12,16–23]. The fluorinated chains
are much more hydrophobic than their hydrogenated homo-
logues, and their introduction in surfactants enhances their
amphiphilic character, improving the surface activity, which is
about 27 and 15 mN mꢀ1 for hydrogenated and fluorinated
surfactants, respectively [24–28].
As a matter of fact, a series of O-alkyl-N,N0-dialkylisoureas was
synthesized by Vowinkel [29] from an hydrogenated alcohol and a
carbodiimide (Scheme 2). O-alkylisoureas have also been used for
the preparation of esters and alkyl halides [30–32].
According to the literature [33,34], copper(I) chloride is the
most widely used catalyst for the synthesis of O-alkyl-N,N0-
dialkylisoureas. Palladium salts [35], tin salts [36] and acids [37]
have also been used as catalysts but copper(I) chloride led to the
best yields. In previous works, O-alkyl [38] and O-perfluoroalkyl-
N,N0-dialkylisourea hydrochloride [28] were synthesized and their
surface properties were assessed. Table 1 lists some characteristics
of these hydrogenated and fluorinated isoureas [28,38].
Fluorinated surfactants are well known and currently used in
more than 200 applications (including paints, cosmetics, anti-
misting agents, emulsifiers for aqueous polymerization of
fluorinated monomers, firefighting agents in extinguishers, etc.)
[10–16]. These surfactants contain a perfluorinated chain as
Table 2 lists the values obtained for surface tension and critical
micelle concentration of the N,N0-hydrogenated and N,N0-fluori-
nated diisopropylisourea hydrochlorides [28,38].
The present article deals with the synthesis of new surface
active molecules and the study of their properties, aiming at
developing new synthetic pathways and to optimize the surface
properties. It was worth synthesizing both hydrogenated and
* Corresponding author.
E-mail addresses: lbadache@usthb.dz (L. Badache), bernard.boutevin@enscm.fr
(B. Boutevin), bruno.ameduri@enscm.fr (B. Ameduri).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.03.016

L. Badache et al. / Journal of Fluorine Chemistry 132 (2011) 382–388
383
fluorinated surfactants, comparing their surface properties by
means of surface tension, conductimetry and to assess their critical
micelle concentration (CMC).
The present manuscript describes the synthesis, the spectro-
scopic characterization, and the surface properties of the following
cationic surfactants at various temperatures:
hydrophilic gravel
surfactant
hydrophobic asphalt
-
-
O-Dodecyl-N,N0-diisopropylisourea hydrochloride, hydrobro-
Scheme 1. Sketch of adhesion between asphalt and gravels in the presence of a
mide, and hydroiodide;
surfactant.
O-Tridecafluorooctyl-N,N0-diisopropylisourea
hydrochloride,
hydrobromide, and hydroiodide.
O
N
R
It is worth indicating that O-CH2CH2C10F21-N,N0-diisopropylisourea
hydrochloride is not soluble in water and thus its surface properties
could not be assessed [28]. A study of the effect of the nature of the
counter-ion (chloride, bromide, and iodide) on the surface properties
was also investigated. In addition, to better understand the effect of
the counter-ion, the surface tension and the CMC were assessed at
various temperatures (15, 20, 25, and 30 8C).
Catalyst
R
OH
R'
N
C
H
+
R'
N
C
N
R'
R'
Scheme 2. Synthesis of O-alkyl-N,N0-dialkylisourea from a hydrogenated alcohol
and a carbodiimide.
2. Results and discussion
Table 1
Characteristics of some hydrogenated and fluorinated isoureas.
2.1. Synthesis
–R
CH3
CH3
OR
Cationic surfactants were synthesized under inert atmosphere
from the condensation of an equimolar carbodiimide to alcohol
ratio in the presence of copper(I) chloride as displayed in Scheme 3.
The reaction was monitored by infrared spectroscopy (Fig. 1).
During the reaction, a new vibration frequency at 1660 cmꢀ1
assigned to –N–C55N– was noted while that at 2100 cmꢀ1
characteristic of -N55C55N- function vanished. In Fig. 1, the
intensification of the bands in the 1000–1300 cmꢀ1 range
corresponds to the presence of C–F vibration bands.
CH
N
C
CH3
CH3
NH CH
Time (h)
Treaction (8C)
Boiling point (8C)
Yield (%)
–C10H21
4
5
8
5
6
6
50
50
50
25
25
25
125 @ 0.03 mbar
Undistilled
Undistilled
72
92
–C12H25
98 (Crude)
96 (Crude)
90
–C14H29
–(CH2)2C6F13
–(CH2)2C8F17
–(CH2)2C10F21
87
95
The synthesis of these compounds was carried out in different
conditions:
Undistilled
98 (Crude)
-
At room temperature, for the hydrogenated isoureas, we found
out that the reaction time was about 48 h [28,34]. Rising the
temperature to 50 8C can decrease the reaction time to 4–6 h. In
addition, and when temperature exceeded 80 8C, the correspond-
ing urea formation was favored, thus reducing the yield. This is
Table 2
Critical micelle concentration (CMC) and surface tension (
fluorinated isourea hydrochlorides.
g
) of hydrogenated and
a
higher melting point and from 1H NMR
H
N
CH3
CH3
evidenced by
OR
spectroscopic data. In the 1H NMR spectrum, the methyl,
methyne, and amine protons of diisopropylurea are located at
1.0, 3.15, and 3.4 ppm, respectively.
CH
C
CH3
CH3
Cl
NH CH
-
Addition of dichloromethane as a solvent to the reaction mixture
increased the reaction time to 24 h. Therefore, the reaction was
carried out without any solvent, to achieve the best possible yield
in a minimum of time. When fluorinated alcohols were used, the
reaction was completed in few hours (at room temperature)
instead of several days (reaction with hydrogenated alcohol).
However, the chain length of the alcohol does not much influence
the kinetics of the reaction.
R
g
(mN mꢀ1
)
CMC (mmol lꢀ1
)
–C10H21
31.17
31.05
33.90
20.55
20.85
1.030
0.844
0.841
0.457
0.245
–C12H25
–C14H29
–(CH2)2C6F13
–(CH2)2C8F17
–(CH2)2C10F21
Water insoluble
CH3
CuCl
CH3
CH3
OR
CH3
CH3
CH
C
N N
CH
R
OH
+
CH
N
C
CH3
CH3
CH3
NH CH
HX
CH3
CH3
OR
CH
N
H
C
CH3
CH3
R = -C12H25, -CH2-CH2-C6F13
X = Cl, Br, I
X
N
H
CH
Scheme 3. Synthesis of hydrogenated and fluorinated isoureas and isoureas hydrohalides.

384
L. Badache et al. / Journal of Fluorine Chemistry 132 (2011) 382–388
carbodiimide
νC-H
νC-H
νN=C=N
isourea
νC-H
νN=C-N
νC-F
4000
3500
3000
2500
2000
1500
1000
500
wavelength (cm-1
)
Fig. 1. FTIR spectra before (upper) and after (bottom) the reaction of synthesis of the fluorinated isourea.
Table 3
2.2. Surface properties
Surface tensions (
concentrations (CMC, mmol lꢀ1) deduced from both
dodecyl-N,N0-diisopropylisourea hydrohalides at various temperatures (15, 20, 25,
g
, mN mꢀ1), conductivities (
s
, mS cmꢀ1), and critical micelle
and for the various O-
g
s
All compounds except O-tridecafluorooctyl-N,N0-diisopropyli-
sourea hydroiodide were soluble in water and thus their surface
properties could be assessed. Therefore, the evolution of their
surface tension and conductivity versus the temperature (15–
30 8C) were studied as well as the influence of the nature of the
counter-ion (Clꢀ, Brꢀ and Iꢀ).
and 30 8C).
2.2.1. Surface tension and conductimetry
(mN mꢀ1
)
CMC (mmol lꢀ1
)
s
(mS cmꢀ1
)
CMC (mmol lꢀ1
)
Surface properties of all these surfactants were assessed from
tensiometry using the Wilhemy plate method. The following study
shows that all products exhibit interesting surface properties
(Fig. 2): the surface tension is in the order of 28–30 and 18–
20 mN mꢀ1 for hydrogenated and fluorinated surfactants, respec-
tively, which is in agreement with the literature [12,14,15].
The same measurements were carried out on the fluorinated
homologues. However, the O-tridecafluorooctyl-N,N0-diisopropyli-
sourea hydroiodide is very unstable, and turns into N,N0-diisopro-
pylurea and tridecafluorooctyl iodide (Scheme 4). Fig. 3 represents
the variation of thesurface tension versus the log of theconcentration
for the O-tridecafluorooctyl-N,N0-diisopropylisoureas hydrochloride
and hydrobromide at various temperatures (15, 20, 25, and 30 8C).
X
T (8C)
g
Cl 15
20
32.5
32.0
30.5
30.7
5.5
1.2
1.1
1.0
0.31
0.55
0.54
1.70
25
30
Br 15
20
30.1
29.9
29.5
29.5
2.9
1.3
1.2
1.4
1.56
0.22
25
30
I
15
20
25
30
39.2
38.4
36.0
35.6
0.2
0.2
0.4
0.2
2.2.2. Critical micelle concentration
The critical micelle concentration values were obtained from
the inflection point on both surface tension and conductivity plots.
Tables 3 and 4 show the values of the surface tension,
micelle concentration (CMC), and the conductivity,
temperatures.
O-dodecyl-N,N0-diisopropylisourea hydrochloride exhibits a sur-
face tension of 32.0 mN mꢀ1 at 20 8C, while that of its fluorinated
homologue (O-tridecafluorooctyl-N,N0-diisopropylisourea hydro-
g
s
, the critical
, at various
chloride) worths 19.7 mN mꢀ1
.
The surface tension and the conductivity do not vary
significantly with the temperature, at least in the considered
temperature range (15–30 8C). For example, the surface tension of
the O-dodecyl-N,N0-diisopropylisourea hydrochloride varied from
32.5 to 30.7 mN mꢀ1 while the temperature increased from 15 to
30 8C.
2.2.3. Interpretations
From Tables 3 and 4, the following conclusions can be drawn:
As expected, the fluorinated surfactants exhibit better surface
properties than their hydrogenated homologues. For example, the
C6F13
CH3
O
CH3
CH3
CH3
O
CH3
CH3
+
C6F13
I
H3C
N
H
N
H
H3C
N
H
N
H
I
Scheme 4. Reaction of degradation of O-tridecafluorooctyl-N,N0-diisopropylisourea hydroiodide.

L. Badache et al. / Journal of Fluorine Chemistry 132 (2011) 382–388
385
4
Temp. 15°C
70
60
50
40
30
20
10
Temp. 20°C
Chloride
Chloride
3.5
Temp. 25°C
Temp. 30°C
3
2.5
2
1.5
1
0.5
0
0
0.000001
0.00001
0.0001
0.001
0.01
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
Concentration (moles.l-1
)
-1
)
L
og(C) (C expressed in moles.
l
9
8
7
6
5
4
3
2
1
0
Temp. 15°C
50
40
30
20
10
Bromide
Temp. 20°C
Temp. 25°C
Temp. 30°C
Bromide
0
0.0001
0.001
0.01
0
0.005
0.01
0.015
0.02
0.025
0.03
Log(C) (C expressed in moles.l-1
)
Concentration (moles.l-1
)
1.8
1.6
1.4
1.2
1
70
60
50
40
30
20
10
Temp. 30°C
Temp. 25°C
Temp. 20°C
Temp. 15°C
Iodide
Iodide
0.8
0.6
0.4
0.2
0
0
0.03
0.3
og(C) (C expressed in moles.l -1
0
0.2
0.4
0.6
0.8
1
Concentration (mmoles.l -1
)
L
)
Fig. 2. Variation of the surface tension (left, mN mꢀ1) at various temperatures (15, 20, 25, and 30 8C) and of the electrical conductivity (right, mS cmꢀ1) at 20 8C of O-dodecyl-
N,N0-diisopropylisourea hydro-chloride, -bromide, and -iodide (from top to bottom, respectively) versus the isourea concentration (mol lꢀ1).
Regarding the influence of the nature of the counter-ion, it is
observed that the bigger the counter-ion, the higher its polariz-
ability, the larger the impact of the temperature on the surface
tension value. For example, for O-dodecyl-N,N0-diisopropylisourea
hydrohalides, the surface tension increased from 29.9 (bromide) to
38.4 mN mꢀ1 (iodide) at 20 8C. When the temperature increased,
the surface tension slightly decreased in the considered tempera-
ture range (15–30 8C). For example, surface tension of the O-
dodecyl-N,N0-diisopropylisourea hydroiodide decreased from 39.2
to 35.6 mN mꢀ1 while the temperature increased from 15 to 30 8C.
The influence of the temperature was more pronounced for the
fluorinated surfactants: for example, when the temperature
increased from 15 to 30 8C, the surface tension of the O-
tridecafluorooctyl-N,N0-diisopropylisourea hydrobromide in-
creased from 16.2 to 21.0 mN mꢀ1 (30% increase).
These results confirm what has been reported in the literature
[39]. The movement of the surface-active molecules increases with
temperature. Thus, they tend to go toward the surface, hence
reducing the surface tension value [12].
Moreover, the critical micelle concentrations (CMCs) for both
hydrogenated and fluorinated surfactants is affected to the same
extent by the change of temperature, at least in the considered
temperature range. For example, the CMC of O-tridecafluorooctyl-
N,N0-diisopropylisourea hydrobromide varied from 0.20 to
0.26 mmol lꢀ1 (also 30% increase) in the 15–30 8C temperature
range. The variation of the CMC with the temperature is however
less important for the fluorinated surfactants than for the
hydrogenated ones.
The variations of the CMC values (Table 3) are quite small in the
considered temperature range, especially for surfactants that have

386
L. Badache et al. / Journal of Fluorine Chemistry 132 (2011) 382–388
Table 4
Surface tension (
g
, mN mꢀ1), conductivity (
s
, mS cmꢀ1), and critical micelle concentrations (CMC, mmol lꢀ1) deduced from both
g
and
s
for the various O-tridecafluorooctyl-
N,N0-diisopropylisourea hydrohalides at various temperatures (15, 20, 25, and 30 8C).
X
T (8C)
g
(mN mꢀ1
)
CMC (mmol lꢀ1
)
s
(mS cmꢀ1
)
CMC (mmol lꢀ1
)
Cl
15
20
25
30
19.1
19.7
19.2
17.9
1.364
1.325
1.421
1.715
0.186
1.18
Br
15
20
25
30
16.2
18.2
20.7
21.0
0.258
0.228
0.211
0.204
0.517
0.26
70
60
50
40
30
20
10
0
0.7
0.6
0.5
0.4
0.3
0.2
0.1
Chloride
Chloride
Temp. 25°C
Temp. 30°C
Temp. 20°C
Temp. 15°C
0
0
2
4
6
8
10
12
14
0.01
0.1
1
10
Log(C) (C expressed in moles.l -1
)
Concentration (mmoles.l-1
)
40
35
30
25
20
15
10
5
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
Bromide
Bromide
Temp. 25°C
Temp. 30°C
Temp. 20°C
Temp. 15°C
0
0
0
0.1
1
10
100
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Concentration (mmoles.l-1
)
Log(C) (C expressed in moles.l -1
)
Fig. 3. Variation of the surface tension (left, mN mꢀ1) at various temperatures (15, 20, 25, and 30 8C) and of the electrical conductivity (right, mS cmꢀ1) at 20 8C of O-
tridecafluorooctyl-N,N0-diisopropylisourea hydrochloride and -bromide (upper and lower graphs, respectively) versus the isourea concentration (mol lꢀ1).
low CMC values (i.e. hydroiodide). On the contrary, for surfactants
based on hydrochlorides, which exhibit the highest CMC values,
their CMC decreased to a minimum before increasing again with
temperature. This is not unexpected as it has been previously
observed on cationic surfactants bearing chloride or bromide as
counter-ions [40].
the micelles do not have a surface activity, surface tension is
proportional to the unimers at the surface only. On the other hand,
the conductivity, at a given concentration, is related with bulk
properties and relies on both species: the unimers at the surface
and the micelles in the bulk. The intrinsic differences between both
methods may have a small incidence on the CMC value.
The CMC values obtained from the conductimetry are slightly
different from those assessed via the surface tension. This
difference has been explained by Mukerjee in a detailed study
[41]. Tensiometry, using the Wilhemy plate, measures surface
tension from the interphase air/liquid. Thus, as it is very likely that
3. Conclusions
Two series of O-dodecyl- and O-tridecafluorooctyl-N,N0-diiso-
propylisourea hydrohalides have been synthesized by the reaction

L. Badache et al. / Journal of Fluorine Chemistry 132 (2011) 382–388
387
of a hydrogenated or fluorinated alcohol onto diisopropylcarbo-
diimide in high yields. These products were characterized by the
usual spectroscopic techniques and elemental analysis. The use of
hydrobromic, hydriodic, or hydrochloric acids on these hydroge-
nated and fluorinated isoureas enabled the preparation of products
with surface-active properties. These cationic surfactants contain
either a hydrogenated or a fluorinated hydrophobic chain. The
synthesized fluorinated surfactants exhibit more interesting
surface properties than their hydrogenated homologues. These
compounds were chosen from different hydrogenated or fluori-
nated chains lengths as they exhibit the best surface properties
[28,38]. It was worth focusing on the assessment of the surface
tension and conductivity to study the impact of counter-ion
(chloride, bromide and iodide) as well as the effect of the
temperature (15–30 8C) on the surface properties. For the
hydrogenated series, a 12-carbon alkyl chain was the best choice
while for the fluorinated series, the tridecafluorooctyl group was
chosen.
The results presented in this work show that surface tension,
conductivity and critical micelle concentration values are some-
what affected by a change of temperature, at least in the
considered temperature range (15–30 8C). Considering a wider
temperature range would probably be interesting to show the
impact of temperature on the surface properties and the thermal
stability of these surfactants. However, it was observed that the
higher the polarizability of the counter-ion, the higher the impact
4.2.3. Gas chromatography coupled with mass spectrometry (GC–MS)
GC–MS chromatograms were recorded on an Agilent 6890 N
gas chromatographer integrated with an Agilent 5973A quadru-
pole mass spectrometer. The chromatographer is equipped with a
HP-1 non polar column (polydimethylsiloxane, 25 m ꢂ 0.20 mm,
0.33
mm), a flame ionization detector, the temperature of the
injector is set at 250 8C, and the oven is heated from 50 8C to 250 8C
at 10 8C minꢀ1 during the experiment.
4.2.4. Tensiometry
Surface tensions were measured by means of a Dataphysics
DCAT 21 Tensiometer using the Wilhemy plate method at different
concentrations to assess the critical micelle concentration (CMC) of
the surfactant in water. Each concentration was prepared at least
24 h prior to measurement. The solution was allowed to
equilibrate in the apparatus and the surface tension was
considered stable when the difference is less than 0.03 mN mꢀ1
.
The value for the surface tension was determined as the average of
the last 200 points. The critical micelle concentration (CMC) was
calculated as the intersection between the two straight lines
emerging from high and low concentrations.
4.2.5. Conductimetry
It is also possible to assess the critical micelle concentration by
conductimetry, where an inflection point can be observed on the
conductivity versus concentration curve. Conductivity was mea-
sured on a CDM210 conductimeter from MeterLab equipped
with a two poles conductivity cell (CDC745-9 from Radiometer
Analytical).
of
temperature
on
the
surface
tension
(chlori-
de < bromide < iodide). The variation of the critical micelle
concentration with the temperature was stronger for the
fluorinated surfactants than for the hydrogrenated ones. Further
properties (in acidic and basic media) of these original surfactants
are under investigation. Also, if the counterion is exchanged for
other anions such as PF6ꢀ or BF4ꢀ, it might be possible to use these
compounds as ionic liquids, actually under investigation.
4.3. Synthesis
An example of the preparation of the O-dodecyl-N,N0-diisopro-
pylisourea hydrobromide is provided and such procedure can be
applied to all other molecules.
4. Experimental
The reaction is an equimolar reaction between diisopropylcar-
bodiimide (0.1 mol, 6.1 g) and dodecanol (0.1 mol, 12.6 g) in the
presence of CuCl in catalytic quantity (0.2 g). The reaction mixture
was stirred away from moisture in a round-bottom flask. Once the
reaction completed, the catalyst was eliminated by filtration using
dichloromethane as the solvent. The filtrate was treated with a
solution of ammonia. This will retrieve the copper ions that were
complexed with the isourea [Cu(NH)3]2+ (ammonia is a stronger
ligand than isourea for copper). The filtrate was then washed with
water to eliminate all mineral ions. This treatment was repeated
several times until the aqueous phase was colorless and its pH was
neutral. The organic phase was dried over anhydrous magnesium
or sodium sulfate. After the dichloromethane evaporation, a
colorless oil (0.098 mol, 30.6 g) was obtained. Products were
purified by distillation under reduced pressure.
4.1. Materials
N,N0-diisoproprylcarbodiimide (99%), copper(I) chloride (96%),
hydrogenated alcohols (>95%), hydrochloric acid (37%), hydro-
bromic acid (47%), hydriodic acid (99.5%), dichloromethane
(99.5%), ammonia (32%), sodium sulfate (99.5%) were purchased
from Sigma–Aldrich and used as received. Fluorinated alcohols
were generously provided by Elf Atochem (Paris, France).
Deuterated chloroform used for the nuclear magnetic resonance
spectroscopy was purchased from Euroiso-top (Grenoble, France)
(purity > 99.8%).
4.2. Characterizations
Isourea hydrochlorides were obtained by bubbling gaseous
hydrochloric acid generated from the reaction of sodium chloride
(NaCl) onto sulfuric acid (H2SO4). The preparation of the
hydrobromide and hydroiodide homologues required hydrobro-
mic acid and hydriodic acid, respectively. The reactions were
carried out without solvent, and were quite instantaneous leading
to quantitative yields. All products were waxy.
4.2.1. Nuclear magnetic resonance (NMR)
The NMR spectra were recorded on Bruker AC 200 instruments,
using deuterated chloroform as the solvent and tetramethylsilane
(or trichlorofluoromethane) as the references for 1H (or 19F) nuclei.
Coupling constants and chemical shifts are given in hertz (Hz) and
part per million (ppm), respectively. The experimental conditions
for recording 1H [or 19F] NMR spectra were as follows: flip angle
908 [or 308], acquisition time 4.5 s [or 0.7 s], pulse delay 2 s [or 5 s],
4.3.1. Hydrogenated isoureas
number of scans 32 [or 64], and a pulse width of 5
m
s for 19F NMR.
FTIR 3440 (N–H), 3000–2800 (C–H), 1655 (C–O–C and C55N),
1400 (C–N).
4.2.2. Fourier transform infrared (FTIR) spectroscopy
1H NMR (CDCl3)
d = 4.0 (2 H, triplet of triplets, O–CH2–), 3.7 (1
3
Infrared spectra were recorded on a Nicolet 510P Fourier
transform infrared (FTIR) spectrometer from KBr pellets (10 wt%),
and the intensities of the absorption bands (cmꢀ1) were labeled
strong (s), medium (m), or weak (w). The accuracy was ꢁ2 cmꢀ1
H, heptuplet, (CH3)2CH–N55, JHH = 7.0 Hz), 3.4 (1 H, multiplet, –
NH–), 3.1 (1 H, heptuplet, (CH3)2CH–NH–, 1.26 (2n H, multiplet, O–
CH2–CnH2n–CH3), 1.1 ppm (12 H, d, 2[(CH3)2CH-], JHH = 6.9 Hz),
3
.
1 ppm (3H, triplet, O–CH2–CnH2n–CH3).

388
L. Badache et al. / Journal of Fluorine Chemistry 132 (2011) 382–388
13C NMR (CDCl3)
32.1.
d
= (a) 153.0, (b) 66.1, (c) 47.2, (d) 44.4 and (e)
one of us (L. Badache), the French Fluorine Network (GIS Fluor,
http://gisfluor.univ-lemans.fr/),
CnF2n+1C2H4OH reactants.
and
Elf
Atochem
for
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The authors thank the Algerian Ministry of Education and
Scientific Research (http://www. mesrs.dz/) for the grant offered to