Original disymmetric bolaforms bearing at least one sulfobetaine head; synthesis and surface properties

Article abstract of DOI:10.1139/v01-083

We describe a simple and efficient method for the synthesis of disymmetric bolaforms bearing at least one sulfobetaine head. In this process, we could introduce successively on α,ω-bis(dialkylamino) alkane a sulfobetaine head and a cationic, a sulfobetaine, or a carboxybetaine head, in excellent yield. This is the first synthesis of disymmetric sulfobetaine bolaforms. The method is easily generalized to various types of head functional groups. The wide range of bolaforms produced by this method has been exploited to study their surface properties and to determine the respective roles of the polar heads and the lengths of the spacers (n) on self-aggregation in aqueous media. A critical micellar concentration (cmc) was observed with the compounds with a spacer of 12 carbon atoms (n = 12). Micellization appeared to be consistent with a "wicket-like" conformation, which did not appear to form with the n = 8 compounds.

Full text of DOI:10.1139/v01-083

1
153
Original disymmetric bolaforms bearing at least
one sulfobetaine head; synthesis and surface
properties
Souad Souirti and Michel Baboulène
Abstract: We describe a simple and efficient method for the synthesis of disymmetric bolaforms bearing at least one
sulfobetaine head. In this process, we could introduce successively on α,ω-bis(dialkylamino) alkane a sulfobetaine head
and a cationic, a sulfobetaine, or a carboxybetaine head, in excellent yield. This is the first synthesis of disymmetric
sulfobetaine bolaforms. The method is easily generalized to various types of head functional groups. The wide range of
bolaforms produced by this method has been exploited to study their surface properties and to determine the respective
roles of the polar heads and the lengths of the spacers (n) on self-aggregation in aqueous media. A critical micellar
concentration (cmc) was observed with the compounds with a spacer of 12 carbon atoms (n = 12). Micellization ap-
peared to be consistent with a “wicket-like” conformation, which did not appear to form with the n = 8 compounds.
Key words: disymmetric bolaform, sulfobetaine, carboxybetaine, cationic amphiphile, synthesis, surface properties.
Résumé : Nous décrivons une simple et efficace méthode d’accés à des dissymmétriques bolaformes ayant au moins
une tête sulfobétaine. Dans ce procédé nous pouvons introduire successivement sur les azotes d’un α,ω-bis(dialkyla-
mino) alkane une tête sulfobétaine et une tête cationique ou sulfobétaine ou carboxybétaine avec d’excellents rende-
ments. C’est la première synthèse de sulfobétaines bolaformes dissymétriques. La méthode décrite est facilement
généralisable à diverses têtes polaires. La diversité des bolaformes ainsi obtenus permet d’aborder, à partir d’une étude
tensiométrique, leurs propriétés de surface et de discuter du rôle des têtes polaires et de la distance entre les deux têtes
(
n) dans le mode d’aggrégation de ces composés en milieu aqueux. Les composés avec n = 12 se prêtent à la détermi-
nation d’une concentration micellaire critique (cmc). Leur micellisation semble en accord avec une conformation “ en
boucle” qui ne se retrouve pas pour les composés avec n = 8.
Mots clés : bolaforme disymmétrique, sulfobétaine, carboxybétaine, amphiphile cationique, synthèse, paramètres de sur-
face.
Souirti and Baboulène 1158
Introduction
encouraging preliminary results prompted us to examine de-
rivatives with a sulfobetaine head. These compounds find
applications as detergents and in cosmetics (5). Recently,
Spencer et al. (6) have reported the inhibitory action of
N,N′-bis[dimethylammonium-1-(4-butylsulfonyl)]dodecane,
a sulfobetaine surfactant, on squalene synthetase. Neverthe-
less, the amphiphilic character of this compound was not
conjured up, and we also know the importance of organized
molecular systems into biological applications. Conse-
quently, the bolaform structure open new perspectives for
the surfactant chemistry. For this purpose, knowledge of the
surface properties and comprehension of the process of vesi-
cle formation will also require a number of derivatives for
studying the self-aggregation behaviour. The interest of dif-
ferent polar heads at the ends of the hydrophobic chain is an
added interest for such investigations.
There have been a large number of descriptions of the
synthesis of amphiphilic molecules, which self-aggregate
into vesicles, as these compounds have a variety of applica-
tion in chemistry and biochemistry (1, 2). Among the nu-
merous families of surfactants,
represented by the bolaform structure has been developed
3). Bolaforms are molecules bearing two polar heads sepa-
a novel architecture
(
rated by a hydrophobic chain of variable length. This struc-
ture lends itself to a modular synthesis of derivatives with
different chains and polar heads. However, despite numerous
reports on bolaforms, to our knowledge there are no descrip-
tions of bolaforms with betaine heads. We have currently
been investigating bolaforms derived from betaine (4). The
Received November 13, 2000. Published on the NRC
Research Press Web site at http://canjchem.nrc.ca on
August 3, 2001.
+
(CH
3
)
2
N -(CH
|
2
)
n
-R
R = cationic, carboxybetaine,
or sulfobetaine group
–
2 3 3
(CH ) -SO
1
S. Souirti and M. Baboulène. Laboratoire des Interactions
Moléculaires et Réactivités Chimiques et Photochimiques,
UMR (CNRS 5623) Université Paul Sabatier 118 route de
Narbonne, 31062 Toulouse cédex 06 France.
Structure A
We present here a simple and general method for prepara-
tion of original disymmetric bolaforms bearing
sulfobetaine head with the other head being either cationic
1Corresponding author (telephone: 33 61 55 62 72; fax:
a
3
3 61 25 17 33; e-mail: mbab@ramses.ups-tlse.fr).
Can. J. Chem. 79: 1153–1158 (2001)
DOI: 10.1139/cjc-79-7-1153
© 2001 NRC Canada

1
154
Can. J. Chem. Vol. 79, 2001
Table 1. Yield and melting points of bolaforms prepared.
Scheme 1.
Br-(CH
2
)
n
-Br
a
(CH
3
)
2
2 n 3 2
N-(CH ) -N(CH )
1
n
R
X
Yield (%)
mp (°C)
2
2
3a
3b
4
4b
4
4
4
4f
5
5
a
b
8
12
8
12
8
12
8
12
8
12
8
12
8
12
—
—
—
—
—
—
—
—
I
95
96
98
98
95
95
87
87
82
80
88
83
78
75
210
218
199
230
225
222
120
105
115
125
188–190
170
230
260
+
+
b
(CH
3
)
2
N - (CH
|
2
)
n
- N (CH
|
3
)
2
–
–
(
CH
2
)
3
SO
3
2 3
(CH ) SO
3
2
a
CH3
CH3
C H
a: HN(CH ) , ethanol/water, reflux;
b: 1,3-propane sultone, acetonitrile, reflux
I
3
2
c
d
e
Br
Br
Br
Br
—
—
—
—
1
2
25
25
C H
12
Scheme 2.
C H
2
5
+
(CH
3
)
2
N-(CH
2
)
n
-N(CH
3
)
2
a
(CH
3
)
2
N-(CH
2
)
n
-N (CH
|
3
)
2
C2H5
—
—
—
—
a
b
–
1
3
(CH
2
)
3
SO
3
b
c
6a
6
b
–
–
X
X
+
+
+
+
(
CH
3
)
2
N - (CH
|
2
)
n
- N (CH
|
3
)
2
(CH
3
)
2
N -(CH
2
)
n
-N (CH
|
3
)
2
Note: Calculated from Gibbs’ equation (8).
|
R
–
–
CH
2
CO
2
CH
3
(CH
2
)
3
SO
3
2 3 3
(CH ) SO
5
4
observed on the chemical shifts of the N-CH and N-CH
3
2
groups are consistent with quaternization of the nitrogen
atom. Furthermore, the disymmetry of the polar heads was
indicated by the differentiation of the C NMR peaks of the
d
1
3
+
+
(CH
3
)
2
N - (CH
2
)
n
- N (CH
|
3 2
)
N-CH groups, which was further support for the proposed
3
|
–
–
3
structures.
CH
2
CO
2
2 3
(CH ) SO
6
Surface properties
a: 1,3-propane sultone, acetone, 15–20°C;
b: BrCH CO C H , methanol, reflux; c: RX, methanol,
reflux, d: resin Amberlist OH , methanol, 20°C, 3 h.
The surfactant properties of these novel bolaforms were
studied by measuring interfacial tension (γ) in water, and
calculated using the Gibbs’ equation (8). The data are illus-
trated in Figs. 1 and 2 and listed in Table 2.
2
2 5
2
TM
–
All compounds tested led to a marked reduction in interfa-
or a betaine (structure A). The surface properties of the com-
pounds prepared was then examined.
–
1
cial tension at the air–water interface (30–35 mN m ).
However, this action was found to depend on the concentra-
tion of the particular compound as a function of polar head
and length of spacer. The compounds with n = 12 exhibited
a break in the interfacial tension vs. concentration plots.
This property of micellization occurred at relatively low val-
ues of critical micelle concentration (cmc), which shows
promise for industrial applications.
Synthesis
The sulfobetaine structure is readily produced by conden-
sation of an amine with an alkylsultone (7). We employed
this method using α,ω-bis(dialkylamino) alkane 1 according
to Scheme 1.
This condensation reaction is quantitative. The
sulfobetaines 2 are readily recovered with a high degree of
purity by filtration because of the absence of by-products
and the crystalline nature of the product. However, if the re-
action mixture is heated, the reaction does not stop at the
monocondensation product, but we did succeed in obtaining
a quantitative yield of the monocondensed product 3 by us-
ing a large excess of sultone at a temperature of 15–20°C
We noted that the cmc value was strongly dependent on
the nature of the polar head. The carboxy-sulfobetaine
bolaform 6b (cmc = 5.5 mM) was a better surfactant than
the symmetrical sulfobetaine 2b (cmc = 8.2 mM) or the
carboxybetaine analogs (cmc = 6.7–8 mM (4)). On the other
hand, the passage of carboxy-sulfobetaine 6b to ammonium-
sulfobetaine 5b led to an increase in cmc (cmc = 18 mM).
This can be accounted for by the stronger repulsion of the
polar heads enhanced by steric interactions. Our findings are
in line with those described for cationic bolaforms (12–
18 mM (9)). Furthermore, these results were in accordance
with those of the general literature; a spacer with n = 8 does
not permit micellization. By contrast, we noted that intro-
duction of a long alkyl chain onto the nitrogen atom led to a
decrease in the cmc value. This was attributed to an in-
creased hydrophobicity. For example, compound 4c
micellized at low concentration (cmc = 5 mM) despite the
short spacer (n = 8), which is not generally compatible with
micellization (9). The surfactants 4c and 4d, thus, represent
(
Scheme 2). We have envisaged to take advantage of this
particular reactivity. The compounds 3, which are readily
isolated in a pure state, can be utilized as intermediates in
the synthesis of the disymmetric bolaforms (Scheme 2). The
insertion of the second polar head is simple and easily gen-
eralized to various types of head.
Table 1 lists typical results that illustrate the possibilities
of these novel synthons. This process should not be difficult
to carry out on an industrial scale.
The bolaforms prepared were characterized from their IR
and NMR spectra. It should be noted that the deshielding
©
2001 NRC Canada

Souirti and Baboulène
1155
Table 2. Surface parameters of compounds in water at 25°C.
Fig. 1. Plots of interfacial tension (obtained by tensiometry) vs.
log [bolaform] at 25°C in water.
–
1 a
Γ (mol m–2)a
2 a
γ (mN m )
cmc (mM)
A (Å )
2
2
3
3
4
4
4
4
4
4
5
5
6
6
a
b
a
b
a
b
c
d
e
f
30c
30
32
30
30.8
29.8b
32
—
8.2
30
10
—
—
5
2.4
—
70
—
18
—
5.5
—
—
1.81 × 10–
6
91.56
125
77.6
—
—
275
188
—
167
—
252
—
92.26
–
6
1.32 × 10
2.16 × 10–6
—
—
b
–
7
6.02 × 10
34.8
8.83 × 10–7
—
b
32
33
34
10 × 10–7
—
b
a
b
a
b
29.5
6.5 × 10–7
—
b
30
32
1.8 × 10–6
a
γ = interfacial tension by the stirrup detachment method.; Γ =
superficial excess; A = area of the polar head.
b
–1
Obtained at [C] = 1 × 10 M.
heads (11, 12). These results are consistent with the length
and flexibility of the spacer, which indicates that these sur-
factants adopt a “ wicket-like” conformation at the air–water
interface. By contrast, the calculated surface areas of the
Fig. 2. Plots of interfacial tension (obtained by tensiometry) vs.
log [bolaform] at 25°C in water.
2
head of the disymmetric bolaforms 4d (A = 188 Å ) and 4f
2
(
A = 167 Å ) is slightly superior as the arithmetic sum of the
2
calculated surface areas of the two polar heads (A ~ 130 Å )
suggests the “wicked-like” conformation undergoes a flat-
tening at the air–water interface. The presence of the methyl
2
acetate group in compound 5b (A = 252 Å ) led significantly
to flattening out of the molecule at the interface. A same ar-
rangement was proposed for the bolaforms with a spacer n =
2
8
(see 4c, A = 275 Å ). This influence of the length of the
hydrophobic chain was also demonstrated by comparison of
the molecular areas of compounds 3a with 3b. This linear
arrangement would be consistent with a more extended oc-
cupation of the interface. This type of molecular organiza-
tion has been described for non-ionic (13) and cationic
2
bolaforms. On the other hand, it can envisage that these
structures lead to a vesicular self-association. Further inter-
pretations will have to await the results of light scattering
and electron microscopic studies (in progress).
Conclusion
We describe here a convenient route to disymmetric
bolaforms bearing at least one sulfobetaine head, which
could be scaled up for industrial applications. The method
lends itself to a modular synthesis enabling preparation of a
variety of derivatives with different polar heads and different
spacers. To our knowledge, this is a first synthesis of
sulfobetaine disymmetric bolaforms.
Our preliminary results on the surface properties of these
bolaforms are encouraging, as they all led to a marked re-
duction in interfacial tension at the air–water interface at low
concentrations. This surfactant action suggests that, by com-
parison with the well-known activity of other betaine surfac-
tants, these bolaforms have potential applications as
a new family of surfactants as a hybrid between bolaforms
and gemini surfactants (10). The synthesis proposed here is
in keeping with the general pattern of the current research
on the access to new potential surfactants. It was noteworthy
that the presence of an iodine atom on the cationic head of
the bolaforms 4a and 4b prevented micellization (at the con-
–
1
centrations studied = 10 M) even with a -(CH ) - spacer
2
12
(
comparison 4b and 4f).
A number of comments can be made on the surface areas
as calculated from the Gibbs’ equation (8). The betaine
bolaforms 6b and 2b occupy a space at the interface that is
the arithmetic sum of the surface areas of the two polar
2
I. Rico-Lattes personal communication.
©
2001 NRC Canada

1
156
Can. J. Chem. Vol. 79, 2001
corrosion inhibitors. The role of the disymmetric head struc-
ture and the length of the spacers were demonstrated in
micellar self-aggregation behaviour. Self-organization into
vesicles is currently under investigation. Comprehension of
their physicochemical properties will be facilitated by this
convenient route to a wide range of derivatives of original
disymmetric bolaform structure.
CH SO ), 3.0 (s, 12H, NCH ), 3.2 (t, 4H, CH N), 3.4 (t, 4H,
2
3
3
2
1
3
CH N). C NMR (200 MHz, D O) δ: 20.7–31.1 ((CH ) ),
2
2
2 6
49.8 (CH -C-SO ), 53.1 (NCH ), 64.4 (NCH ), 66.7
2
3
3
2
(CH SO ). Anal calcd. for C H N O S (444.64): C 48.62,
2
3
18 40
2
6 2
H 9.07, N 6.30, S 14.42; found: C 48.96, H 9.30, N 5.94,
S 13.97.
1
,12-bis(N,N- dimethylammonio-N-propyl-1-
sulfonate)dodecane (2b)
Yield: 95%. White powder, mp 215°C. IR (KBr) (cm ):
Experimental
–
1
+
1
General
1480 (C-N ), 1040 (S=O). H NMR (200 MHz, D O) δ: 1.2
2
Reagents were of commercial quality and were used with-
(m, 20H, (CH ) ), 2.2 (qt, 4H, CH -C-SO ), 2.6 (t, 4H,
2
10
2
3
–
1
out purification. IR spectra (ν, cm ) were recorded on a
CH SO ), 3.0 (s, 12H, NCH ), 3.2 (t, 4H, CH N), 3.3 (t, 4H,
2 3 3 2
1
13
13
PerkinElmer 683 spectrophotometer. H and C NMR spec-
CH N). C NMR (200 MHz, D O) δ: 20.7–31.1 ((CH ) ),
2 2 2 10
tra (δ, ppm) were obtained on Bruker AC 80 or Bruker AC
49.8 (CH -C-SO ), 53.1 (NCH ), 64.4 (NCH ), 66.8
2 3 3 2
2
00 instruments. Surface active properties were calculated
(CH SO ). Anal calcd. for C H N O S (500.75): C 52.77,
2 3 22 48 2 6 2
H 9.66, N 5.29, S 12.8; found: C 52.13, H 9.42, N 5.39,
S 12.23.
using Gibbs’ equation with the data obtained from measure-
ments carried out Prolabo No. 3 tensima.
Typical procedure for the synthesis of compounds 1
Typical procedure for the synthesis of compounds 3
A solution of dimethylamine (33% of ethanol) (3 ×
Sulfobetaine 3 was prepared by the addition of α,ω-
2
–2
1
0− mol) and dibromoalkane (1 × 10 mol) were added to
–
2
bis(N,N-dimethylamino) alkane (1 × 10 mol) to a stirred
–
2
a solution of sodium carbonate (2 × 10 mol) in ethanol
60 mL) and water (15 mL). The reaction mixture was
–
3
solution of 1,3-propane sultone (2 × 10 mol) in anhyd ace-
tone (50 mL). The reaction mixture was stirred at room tem-
perature for 3 h, cooled, and filtered. The amphiphilic
product was purified by recrystallization from methanol–
ether (1:9), and dried in vacuo over phosphorus pentoxide.
(
heated at reflux and stirred for 24 h. Then the resulting com-
pound was isolated by evaporating of the solvent under re-
duced pressure. The crude product washed with water (1 ×
1
0 mL) was extracted with EtO .The organic phase was
2
dried on anhyd Na SO and evaporated in vacuo. The crude
oil was purified by distillation.
2
4
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-8-(N′,N′-
dimethylamino)octane (3a)
1
,8-bis(N,N- dimethylamino)octane (1a)
Yield: 98%. White powder, mp 198–200°C. IR (KBr)
1
–1
+
1
Yield: 98%. Colourless oil, bp 60°C, 0.06 mm Hg. H
NMR (200 MHz, CDCl ) δ: 1.1 (m, 12H, (CH ) ), 2.3 (t, 4H,
NCH ), 1.9 (s, 12H, NCH ). C NMR (200 MHz, CDCl ) δ:
(cm ): 1480 (C-N ), 1040 (S=0). H NMR (80 MHz, D O)
2
δ: 1.2 (m, 12H, (CH ) ), 2.0–2.2 (m, 10H, NCH , NCH ,
3
2 6
2 6
2
3
1
3
+
+
−
CH -C-SO ), 2.7–3.2 (m, 12H, N CH , N CH , CH SO ).
2
3
3
2 3 3 2
2 3
1
3
2
7.2–28.3 ((CH ) ), 45.2 (NCH ), 59.7 (NCH ). Anal calcd.
C NMR (200 MHz, D O) δ: 20.7–31.6 ((CH ) ), 46.5
2 2 6
2
6
3
2
+
for C H N (200.37): C 71.86, H 13.97, N 13.97; found:
C 71.66, H 14.15, N 14.13.
(NCH ), 49.8 (CH -C-SO ), 53.2 (N CH ), 61.4 (NCH ),
1
2
28
2
3 2 3 3 2
+
−
64.5 (N CH ), 66.7 (CH SO ). Anal. calcd. for
2
2 3
C H N O S (322.5): C 55.86, H 10.63, N 8.69, S 9.94;
found: C 55.50, H 10.46, N 8.46, S 9.62.
1
5
34
2
3
1
,12-bis(N,N-dimethylamino)dodecane (1b)
1
Yield: 98%. Colourless oil, bp 80–82°C, 0.05 mm Hg. H
NMR (200 MHz, CDCl ) δ: 1.1 (m, 20H, (CH ) ), 2.1 (t,
3
2 10
1-(N,N-dimethylammonio-N-propyl-1-sulfonate)-12-(N′,N′-
dimethylamino)dodecane (3b)
1
3
4
H, NCH ), 1.9 (s, 12H, NCH ). C NMR (200 MHz,
2
3
CDCl ) δ: 27.4–28.5 ((CH ) ), 45.4 (NCH ), 59.9 (NCH ).
–1
3
2 10
3
2
Yield: 98%. White powder, mp 230°C. IR (KBr) (cm ):
Anal calcd. for C H N (256.47): C 74.86, H 14.03,
N 10.92; found: C 74.73, H 13.90, N 11.62.
+
1
1
6
36
2
1
480 (C-N ), 1040 (S=0). H NMR (80 MHz, D O) δ: 1.2
2
(
m, 20H, (CH ) ), 1.9–2.2 (m, 10H, NCH , NCH , CH -C-
2 10 2 3 2
−
+
+
−
13
SO ), 2.9–3.2 (m, 12H, N CH , N CH , CH -CH SO ).
C
3
3
2
2
2
3
Typical procedure for the synthesis of compounds 2
NMR (200 MHz, D O) δ: 20.7–31.6 ((CH ) ), 46.5 (NCH ),
2
2 10
3
Compounds 2 were prepared by the addition of diamine 1
+
4
(
(
9.8 (CH -C-SO ), 53.2 (N CH ), 61.4 (NCH ), 64.5
–
2
–2
2 3 3 2
(
1 × 10 mol) to 1,3-propane sultone (2.2 × 10 mol) in
+
−
N CH ), 66.7 (CH SO ). Anal. calcd. for C H N O S
2 2 19 49 2 3
3
anhyd acetonitrile (100 mL). The solution was stirred at re-
flux for 4 h, then cooled and filtered. After crystallization
from methanol–acetone (1:9), pure compounds 2 were ob-
tained as solid, which decomposed during melting point de-
termination.
378.61): C 60.27, H 11.18, N 7.40, S 8.47; found: C 59.93,
H 11.02, N 7.07, S 8.54.
Typical procedure for the synthesis of compounds 4
–
2
A mixture of sulfobetaine 3 (1 × 10 mol) and of
–
2
1
(
,8-bis(N,N- dimethylammonio-N-propyl-1-sulfonate)octane
2a)
Yield: 95%. White powder, mp 210°C. IR (KBr) (cm ):
haloalkane (1 × 10 mol) in absolute MeOH (50 mL) was
heated at reflux for 4 h. After removing the solvent in vacuo,
the residual oil was purified by trituration with anhyd ether,
and then evaporated in vacuo and dried over phophorus
pentoxide.
–
1
+
1
1
480 (C-N ), 1040 (S=O). H NMR (200 MHz, D O) δ: 1.2
2
(
m, 12H, (CH ) ), 1.9 (qt, 4H, CH -C-SO ), 2.9 (t, 4H,
2 6 2 3
©
2001 NRC Canada

Souirti and Baboulène
1157
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-8-(N′-
trimethylammonium iodid)octane (4a)
Yield: 95%. Yellow powder, mp 225°C. IR (KBr) (cm ):
CH -C-SO ), 2.9–3.2 (m, 14H, N-CH , CH SO ), 3.3 (m,
2
3
3
2
3
1
3
8H, NCH ), 3.6 (t, 2H, NCH -C-S). C NMR (200 MHz,
2
2
–
1
D O) δ: 10.03 (CH ), 20.7–31.1 ((CH ) ), 49.8 (CH -C-S),
2
3
2 8
2
+
1
1
480 (C-N ), 1040 (S=0). H NMR (80 MHz, D O) δ: 1.2
52.4 (NCH ), 53.2 (CH N-S), 62.0, 64.48, 66.1 (NCH ),
2
3 3 2
−
(
m, 12H, (CH ) ), 2.1 (qt, 2H, CH -C-SO ), 3.0–3.5 (m,
66.6 (CH S). Anal. calcd. for C H BrN O S·H O (505.60):
2 21 47 2 3 2
C 49.88, H 9.77, N 5.54, S 4.08; found: C 50.02, H 9.94,
N 5.28, S 4.42.
2
6
2
3
−
13
2
2
6
3H, NCH , NCH , CH SO ). C NMR (200 MHz, D O) δ:
3
2
2
3
2
0.0–31.0 ((CH ) ), 49.9 (CH -C-SO ), 53.2 and 55.5 (NCH ),
2
6
2
3
3
−
6.3 (NCH (SO )), 66.7 (CH SO ), 69.4 (NCH (I)). Anal.
2
3
2
3
2
calcd. for C H IN O S (464.45): C 41.38, H 8.03, N 6.03,
S 6.91; found: C 40.93, H 8.34, N 5.95, S 6.95.
Typical procedure for the synthesis of compounds 5
1
6
37
2
3
–
2
A mixture of monosulfonate 3 (1 × 10 mol) and
–
2
bromoacetate (2 × 10 mol) in anhyd methanol (40 mL) was
heated at reflux under agitation for 6 h. The solvent was
evaporated in vacuo. The residual oil was precipitated by
ether and purified by washed successively with ether and ac-
etone.
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-12-(N′-
trimethylammonium iodid)dodecane (4b)
–
1
Yield: 95%. Yellow powder, mp 222°C. IR (KBr) (cm ):
480 (C-N ), 1040 (S=0). H NMR (80 MHz, D O) δ: 1.2
2
+
1
1
−
(
2
2
m, 20H, (CH ) ), 2.1 (qt, 2H, CH -C-SO ), 2.8–3.2 (m,
2 10 2
3
−
13
3H, NCH , NCH , CH SO ). C NMR (200 MHz, D O) δ:
1-(N,N-dimethylammonio-N-propyl-1-sulfonate)-8-(N′,N′-
dimethyl-N′-ethylacetate ammonium bromid)octane (5a)
Yield: 88%. White powder, mp 185–190°C. IR (KBr)
3
2
2
3
2
6.7–31.1 ((CH ) ), 49.8 (CH -C-SO ), 53.2 and 55.3
2
10
2
3
−
+
(
NCH ), 64.4 (NCH (SO )), 66.7 (CH SO ), 69.3 (N CH ).
3 2 3 2 2
3
–
1
+
1
Anal. calcd. for C H IN O S (520.56), C 46.15, H 8.71,
(cm ): 1470–1460 (C-N ), 1040 (S=0), 1640 (C=O). H
2
0
45
2
3
N 5.38, S 6.16; found: C 45.96, H 8.93, N 5.18, S 6.00.
NMR (80 MHz, D O) δ: 1.3 (m, 8H, (CH ) ), 1.7 (m, 4H,
2
2 4
−
CH -C-N), 2.1 (qt, 2H, CH -C-SO ), 2.6–3.5 (m, 20H,
2
2
3
−
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-8-(N′,N′-
NCH , NCH , CH SO ), 3.8 (s, 3H, OCH ), 4.2 (s, 2H,
CH CO ). C NMR (200 MHz, D O) δ: 20.8–34.6 ((CH ) ),
2 2 2 2 6
3 2 2 3
3
1
3
dimethyl-N′-dodecylammonium bromid)octane (4c)
–
1
Yield: 87%. White powder, mp 120°C. IR (KBr) (cm ):
50.0 (CH -C-SO ), 53.3 and 54.3 (NCH ), 56.0 (OCH ),
2
3
3
3
+
1
−
1
3
480 (C-N ), 1040 (S=0). H NMR (80 MHz, D O) δ: 0.8 (t,
63.8 and 64.5 (NCH ), 66.8 (CH SO ), 68.5 (CH CO ),
2
2 2 2 2
3
H, CH -C ), 1.3 (m, 32H, (CH ) , (CH ) ), 2.1 (qt, 2H,
168.4 (CO ). Anal. calcd. for C H BrN O S (475.48):
2 18 39 2 5
C 45.47, H 8.27, N 5.89, S 6.74; found: C 45.30, H 8.97,
N 5.91, S 6.86.
3
11
2 10
2 6
−
−
13
CH -C-SO ), 2.6–3.3 (m, 22H, NCH , NCH , CH SO ).
C
2
3
3
2
2
3
NMR (200 MHz, D O) δ: 16.6 (C-CH ), 20.8–34.6 ((CH ) ,
2
3
2 6
(
CH ) ), 49.9 (CH -C-SO ), 53.5 and 54.4 (NCH ), 64.5
2 10 2 3 3
−
+
and 66.3 (NCH ), 66.7 (CH SO ), 69.4 (N CH ). Anal.
calcd. for C H BrN O S·H O (550.63): C 58.84, H 11.07,
N 5.08, S 5.81; found: C 58.95, H 10.95, N 4.80, S 6.00.
1-(N,N-dimethylammonio-N-propyl-1-sulfonate)-12-(N′,N′-
dimethyl-N′-ethylacetate ammonium bromid)dodecane (5b)
2
2
3
2
2
7
59
2
3
2
–
1
Yield: 83%. White powder, mp 170°C. IR (KBr) (cm ):
+
1
1
460 (C-N ), 1040 (S=0), 1640 (C=O). H NMR (80 MHz,
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-12-(N′,N′-
D O) δ: 1.26 (m, 16H, (CH ) ), 1.7 (m, 4H, CH -C-N), 2.1
2
2 8
2
−
dimethyl-N′-dodecylammonium bromid)dodecane (4d)
(qt, 2H, CH -C-SO ), 3.0–3.2 (m, 22H, NCH , NCH ,
2
3
3
2
C
–
1
−
13
Yield: 85%. White powder, mp 105°C. IR (KBr) (cm ):
CH SO ), 3.8 (s, 3H, OCH ), 4.2 (s, 2H, CH CO ).
2
3
3
2
2
+
1
1
3
480 (C-N ), 1040 (S=0). H NMR (80 MHz, D O) δ: 0.8 (t,
NMR (200 MHz, D O) δ: 20.8–31.2 ((CH ) ), 50.0 (CH -C-
2
2 2 10 2
H, CH -C ), 1.3 (m, 40H, (CH ) , (CH ) ), 2.1 (qt, 2H,
SO ), 53.3 and 54.4 (NCH ), 56.0 (OCH ), 63.7 and 64.6
3 3 3
3
11
2 10
2 10
−
−
13
−
CH -C-SO ), 3.0–3.3 (m, 22H, NCH , NCH , CH SO ).
C
(NCH ), 68.5 (CH SO ), 68.7 (CH CO ), 168.4 (CO ).
2
3
3
2
2
3
2 2 2 2 2
3
NMR (200 MHz, D O) δ: 16.6 (C-CH ), 20.6–34.4
Anal. calcd. for C H BrN O S (531.59): C 49.71, H 8.91,
22 47 2 5
N 5.27, S 6.03; found: C 49.67, H 9.03, N 4.98, S 6.02.
2
3
(
(CH ) ), 49.9 (CH -C-SO ), 53.5 and 54.4 (NCH ), 64.2
2
10
2
3
3
−
and 66.1 (NCH ), 66.3 (CH SO ). Anal. calcd. for
2
2
3
C H BrN O S·H O (645.85): C 57.59, H 9.75, N 4.33,
S 4.95; found: C 55.79, H 10.05, N 4.42, S 4.55.
Typical procedure for the synthesis of compounds 6
3
1
61
2
3
2
–
2
A mixture of compound 5 (1 × 10 mol) in methanol and
–
anion-exchange resin (OH ) (amberlist IRA 400) (25 g) was
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-8-(N′,N′-
stirred for 3 h at room temperature. Then, the mixture was
filtered and evaporated in vacuo. The residual oil was
triturated from ether, and recrystallized from ether–methanol
(9:1).
dimethyl-N′-ethylammonium bromid) octane (4e)
1
Yield: 82%.White powder, mp 115°C. H NMR (80 MHz,
D O) δ: 1.1 (t, 3H, CH ), 1.5 (m, 12H, (CH ) ), 2.1 (qt, 2H,
2
3
2 6
CH -C-SO ), 2.9–3.1 (m, 14H, N-CH , CH SO ), 3.3 (m,
2
3
3
2
3
1
3
8
H, NCH ), 3.5 (t, 2H, NCH -C-S). C NMR (200 MHz,
1-(N,N-dimethylammonio-N-propyl-1-sulfonate)-8-(N′,N′-
dimethylammonio-N′-acetate)octane (6a)
2
2
D O) δ: 10.13 (CH ), 21.0–31.0 (CH ) , 47.8 (CH -C-S),
2
3
2 6
2
–
1
5
2.4 (NCH ), 52.2 (CH N-S), 62.0, 63.7, 65.8 (NCH ), 66.5
Yield: 78%. White powder, mp 230°C. IR (KBr) (cm ):
3
3
2
+
1
(
CH S). Anal. calcd. for C H BrN O S·H O (449.49):
1480 (C-N ), 1200 and 1050 (S=0), 1650–1630 (C=O). H
2
17 39
2
3
2
C 45.43, H 9.19, N 6.23, S 7.13; found: C 45.62, H 9.05,
N 5.98, S 7.35.
NMR (200 MHz, D O) δ: 1.4 (m, 8H, (CH ) ), 1.8 (m, 4H,
2
2 4
−
CH -C-N), 2.2 (qt, 2H, CH -C-SO ), 2.9 (t, 2H, CH SO ),
2
2
3
2
3
3
.0 and 3.1 (s, 12H, NCH ), 3.4–3.6 (m, 6H, NCH ), 3.8 (s,
3
2
1
3
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-12-(N′,N′-
2H, CH CO ). C NMR (200 MHz, D O) δ: 20.8–30.4
((CH ) ), 49.9 (CH -C-SO ), 53.2 and 53.9 (NCH ), 64.5
2 6 2 3 3
(NCH ), 66.8 (CH SO ), 68.6 (CH CO ), 171.9 (CO ).
2 2 2
dimethyl-N′-ethylammonium bromid)dodecane (4f)
1
−
Yield: 80%.White powder, mp 125°C. H NMR (80 MHz,
2 2 2 2 2
3
D O) δ: 1.1 (t, 3H, CH ), 1.3 (m, 16H, (CH ) ), 2.2 (qt, 2H,
Anal. calcd. for C H N O S·H O (396.54): C 51.44,
17 36 2 5 2
2
3
2 8
©
2001 NRC Canada

1
158
Can. J. Chem. Vol. 79, 2001
H 9.58, N 7.06, S 8.06; found: C 51.24, H 9.71, N 6.97,
S 8.44.
2. G.H. Escamilla. In Advances in dendrinic macromolecules.
Vol 2. Edited by JAJ Press Inc. 1995. pp. 157–190.
3
. J.H. Fuhrhop and J. Mathieu. J. Chem. Soc. Chem. Commun.
144 (1983).
1
-(N,N-dimethylammonio-N-propyl-1-sulfonate)-12-(N′,N′-
dimethylammonio-N′-acetate)dodecane (6b)
Yield: 75%. White powder, mp 260°C. IR (KBr) (cm ):
4. S. Souirti and M. Baboulène. in press.
5. XXIX CED annual Meeting. Barcelona. 1999. May.
–
1
+
1
6
. T.A. Spencer, T.J. Onofrey, R.O. Cann, J.S. Russel, L.E. Lee,
D.E. Blanchard, A. Castro, P. Gu, G. Jiang, and I. Schechter. J.
Org. Chem. 64, 807 (1999).
1
480 (C-N ), 1200 and 1050 (S=0), 1650–1630 (C=O). H
NMR (200 MHz, D O) δ: 1.3 (m, 16H, (CH ) ), 1.7 (m, 4H,
2
2 8
−
CH -C-N), 2.2 (qt, 2H, CH -C-SO ), 2.3 (t, 2H, CH SO ),
2
2
3
2
3
7
8
9
. E.J. Fendler, C.L. Day, and J.H. Fendler. J. Phys. Chem. 76,
1460 (1972).
. J.W. Gibbs. The collected works of J.W. Gibbs. Vol 1.
Longmans and Green, London. 1928. p. 119.
3
2
.0 and 3.2 (s, 12H, NCH ), 3.4–3.6 (m, 6H, NCH ), 3.7 (s,
3
2
1
3
H, CH CO ). C NMR (200 MHz, D O) δ: 20.7–30.4
2
2
2
(
(
(CH ) ), 49.8 (CH -C-SO ), 53.2 and 53.8 (NCH ), 64.4
NCH ), 67.1 (CH SO ), 68.6 (CH CO ), 171.8 (CO ).
2 10 2 3 3
−
2
2
3
2
2
2
. F.M. Menger and S. Wreen. J. Phys. Chem. 78, 1387 (1974).
Anal. calcd. for C H N O S·H O (454.65): C 55.43,
2
1
44
2
5
2
1
1
0. S. Bhattacharya and S. De. J. Chem. Soc. Chem. Commun.
51 (1995).
H 10.11, N 6.15, S 7.03; found: C 55.42, H 10.43, N 5.82,
S 7.28.
6
1. Y. Chevalier, S. Brunel, and P. Le Perchec. J. Chim. Phys. -
Chim. Biol. 92, 1025 (1995).
References
12. J.B. Le Toumelin and M. Baboulène. Langmuir, 12, 2128
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3. S. Franceschi, N. de Viguerie, M. Rivière, and A. Lattes. New.
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(
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©
2001 NRC Canada