Synthesis of surfactants based on pentaerythritol. II. Anionic gemini surfactants

Article abstract of DOI:10.1139/cjc-2013-0256

Efficient syntheses of three series of anionic gemini surfactants based on pentaerythritol are described. A series of disulfates was prepared by the double displacement of the two cyclic sulfates in the S₄-symmetric compound pentaerythritol spirobicyclic sulfate (1) with linear alkoxides. A second series of disulfates was prepared by reaction of the dialkoxides of di-O-alkylpentaerythritols with ethylene sulfate. The di-O-alkylpentaerythritols can be prepared as previously reported by us or by the acid-catalyzed hydrolysis of the first series of disulfates. A series of disulfonates was prepared by reaction of the dialkoxides of di-O-alkylpentaerythritols with 1,3-propanesultone. This last set of reactions was complicated by the formation of oxetanes, which probably arose from initial reversible displacement on sulfur of the sultone alkoxide by the pentaerythritol alkoxide followed by a second intramolecular displacement of the resulting sulfonate. Changing the order of addition to keep the reaction medium from containing excess base as well as lowering the reaction temperature minimized the amounts of these byproducts. All three series had excellent surfactant properties.

Full text of DOI:10.1139/cjc-2013-0256

1
085
ARTICLE
Synthesis of surfactants based on pentaerythritol. II. Anionic gemini
surfactants
Thomas Tran, Nusrat Jahan, D. Gerrard Marangoni, and T. Bruce Grindley
Abstract: Efficient syntheses of three series of anionic gemini surfactants based on pentaerythritol are described. A series of
disulfates was prepared by the double displacement of the two cyclic sulfates in the S -symmetric compound pentaerythritol
4
spirobicyclic sulfate (1) with linear alkoxides. A second series of disulfates was prepared by reaction of the dialkoxides of
di-O-alkylpentaerythritols with ethylene sulfate. The di-O-alkylpentaerythritols can be prepared as previously reported by us or
by the acid-catalyzed hydrolysis of the first series of disulfates. A series of disulfonates was prepared by reaction of the
dialkoxides of di-O-alkylpentaerythritols with 1,3-propanesultone. This last set of reactions was complicated by the formation of
oxetanes, which probably arose from initial reversible displacement on sulfur of the sultone alkoxide by the pentaerythritol
alkoxide followed by a second intramolecular displacement of the resulting sulfonate. Changing the order of addition to keep
the reaction medium from containing excess base as well as lowering the reaction temperature minimized the amounts of these
byproducts. All three series had excellent surfactant properties.
Key words: gemini surfactants, anionic surfactants, pentaerythritol, cyclic sulfates, disulfates, sulfonates, 1,3-propanesultone.
Résumé : On décrit les synthèses efficaces de trois séries de tensioactifs géminés anioniques a` partir de pentaérythritol. Une série
de disulfates a été préparée par double déplacement de deux sulfates cycliques dans le composé de symétrie S4 sulfate spi-
robicyclique de pentaérythritol (1) par des alkoxydes linéaires. Une deuxième série de disulfates a été obtenue par réaction des
dialkoxydes de di-O-alkylpentaérythritols avec du sulfate d’éthylène. Les di-O-alkylpentaérythritols peuvent être préparés
comme nous l’avons décrit antérieurement ou par hydrolyse de la première série de disulfates catalysée par un acide. Une série
de disulfonates a été préparée par réaction des dialkoxydes de di-O-alkylpentaérythritols avec la 1,3-propanesultone. Ce dernier
ensemble de réactions a été compliqué par la formation d’oxétanes qui ont probablement été produits par le déplacement
réversible initial du soufre de l’alkoxyde de sultone par l’alkoxyde de pentaérythritol, suivi par un deuxième déplacement
intramoléculaire du sulfonate résultant. La modification de l’ordre d’addition afin d’éviter que le milieu de réaction ne con-
tienne un excès de base, de même que la réduction de la température de réaction ont minimisé les quantités de ces sous-produits.
Les séries ont toutes les trois d’excellentes propriétés tensioactives. [Traduit par la Rédaction]
Mots-clés : tensioactifs géminés, tensioactifs anioniques, pentaérythritol, sulfates cycliques, disulfates, sulfonates, 1,3-propanesultone.
Introduction
exclusively. Three procedures have been reported for the prepa-
3
0–32
ration of compound 1 from pentaerythritol,
all based on mod-
Gemini surfactants display critical micellization concentra-
tions that are one to two orders of magnitude lower than those of
the corresponding conventional surfactants with only a single
head group and also are much more efficient at lowering surface
ifications of the Sharpless two stage approach to preparation of
3
3
cyclic sulfates via the cyclic sulfites. We found that the use of a
:1 tetrahydrofuran−dichloromethane mixture as the solvent for
1
tensions of aqueous solutions.1–11
the initial formation of the spirobicyclic sulfite gives an improved
yield for that stage. The only reports of its use are by Gulýas
There has been considerable
interest in exploring how structural variations influence sur-
factant properties, particularly in how head group spacing in-
3
0,34
et al.,
who reported that compound 1 reacted with 2 equiv. of
fluences these properties.1
2–26
27
phosphines in 1997 and 2001, and by Ozturk et al., who reported
In a recent publication, we
3
2
that it reacted twice with a dithiol dianion in 2001. Elimination
described how cationic and zwitterionic gemini surfactants hav-
ing structurally defined head group spacing could be prepared
often competes with substitution in reactions of six-membered
ring cyclic sulfates with basic nucleophiles.35 Compound 1 cannot
2
8
from readily available mono-O-benzylidenepentaerythritol. This
paper describes approaches for the preparation of three series of
pentaerythritol-based anionic gemini surfactants. Both classes of
surfactants have superior properties as will be described in detail
elsewhere.29
undergo elimination with basic nucleophiles because there are no
hydrogen atoms ␤ to the sulfates allowing the employment of any
type of nucleophile with this potentially versatile synthon.
Compound 1 reacted at room temperature with long-chain
alkoxides in DMF to give the expected disulfates, anionic gemini
surfactants (2–8), in good yields (see Scheme 1). Longer reaction
times were required for the longer alkoxides and the yields were
lower for the dodecyl and hexadecyl derivatives. The products
(2–8) could be desulfated in good yield (65%–80%) by adding con-
centrated HCl to a solution of the disulfates in THF−water (2:1)
Results and discussion
The S -symmetric compound pentaerythritol spirobicyclic su-
4
fate (1) is ideal for the selective formation of compounds bearing
two sulfate groups because identical displacements of the two
symmetrically equivalent cyclic sulfates yield these structures
Received 6 June 2013. Accepted 8 July 2013.
T. Tran, N. Jahan, and T.B. Grindley. Department of Chemistry, Dalhousie University, 6274 Coburg Road, P.O. Box 15000, Halifax, NS B3H 4R2, Canada.
D.G. Marangoni. Department of Chemistry, St. Francis Xavier University, Antigonish, NS B2G 2W5, Canada.
Corresponding author: T. Bruce Grindley (e-mail: bruce.grindley@dal.ca).
Can. J. Chem. 91: 1085–1092 (2013) dx.doi.org/10.1139/cjc-2013-0256
Published at www.nrcresearchpress.com/cjc on 17 July 2013.

1086
Can. J. Chem. Vol. 91, 2013
Scheme 1. Synthesis of disulfates by reaction of pentaerythritol spirobicyclic sulfate (1) with alkoxides.
Scheme 2. Synthesis of extended disulfates.
Scheme 3. Synthesis of disulfonate gemini surfactants.
mixtures. Alkoxide addition and hydrolysis can also be performed
in one pot in reasonable yield (39%) as demonstrated in the exper-
imental for compound 11 but we prefer the two-step procedure
because it is more reproducible. We have found that production
of pentaerythritol-derived diols via this route from pentaerythri-
tol is faster than the procedure outlined in our first paper in this
ethers, respectively.36 Sulfation yielded 6 and 7.36 The sequence
reported here eliminates the need for chromatography.
A second series of disulfates was produced by reacting dianions
of the diols 9–12 in THF with ethylene sulfate in THF, normally at
room temperature for about 24 h (see Scheme 2). The diols could
be obtained either by hydrolysis of the disulfates as outlined
above or by the procedures described in our earlier paper on this
series.2 However, the original procedure, where the last step is
hydrogenolysis of a benzylidene acetal, always yields product free
of trace contaminants, partially because the hydrogenolysis does
not work unless the acetal has been highly purified.
7
27
2
7
topic. Reaction times increased with increase in chain length;
compounds 11 and 12 required the addition of more ethylene
sulfate and base and the reaction of compound 12 required heat-
2
7
Two of these compounds, 6 and 7, had been synthesized previ-
ously by a sequence that started with the alkylation of pentaeryth-
ritol in tert-butanol with 2.0 equiv. of potassium tert-butoxide and
ing to 40 °C to go to completion. As always, the longest chain
derivative, compound 12, was obtained in the lowest yield of the
series.
2
.0 equiv. of the alkyl bromide followed by separation of the dial-
The synthesis of a series of disulfonates (17–20) through the
reaction of the dianions of the diols 9–12 with 1,3-propanesultone
is shown in Scheme 3. This reaction was complicated by the for-
kyl ethers from mono and trialkyl ethers by silica gel chromatog-
raphy in 46% and 44% yields for the didodecyl and ditetradecyl
Published by NRC Research Press

Tran et al.
1087
Scheme 4. Possible mechanisms for formation of the byproduct oxetanes. (a) Direct intramolecular displacement of alkoxide from the
monoadduct dianion; (b) reversible formation of sulfonate ester followed by intramolecular displacement, either by the mono- or the
dianions.
mation of byproducts, the oxetanes 21–24. Two possible mecha-
nisms for the formation of these byproducts are shown in
Scheme 4.
Poor yields of the desired disulfonates were obtained initially
when 1,3-propanesultone (2.25 equiv.) was added slowly to a mix-
ture of the diols and NaH (4 equiv.) in THF followed by heating at
the related cationic surfactants.27 Critical micellization concen-
trations of the compounds with C12 tails, 6, 15, and 19, were 0.013,
0.077, and 0.15 mmol/L, respectively, as measured from the
change in surface tension with concentration using a KRUSS K8
tensiometer. For the two series of sulfates, these critical micelliza-
tion concentrations are one to two orders of magnitude lower
than those of most cationic gemini surfactants (see table 1 in
50 °C. Significant amounts of single byproducts were obtained
that were separated and identified as oxetanes (21–24) from their
exact masses in their ESI mass spectra, from the symmetry appar-
44
review by Zana ) and comparable with those of other sulfated
45–47
gemini surfactants.
also promising.
C20 values for these compounds were
1
13
ent in their H and C NMR spectra, and from the similarity of
1
the H NMR chemical shifts to those from 3,3-bis(hydroxymethyl)
3
7
oxetane. Possible mechanisms for its formation are presented
in Scheme 4. The direct displacement mechanism (Scheme 4a)
seems unlikely because oxetane byproducts had not been ob-
served in our previous syntheses of gemini surfactants involving
Experimental
Improved preparation of 2,4,8,10-tetraoxa-3,9-
dithiaspiro[5.5]undecane 3,9-dioxide
Pentaerythritol (68.0 g, 0.499 mol) and molecular sieves (100 g,
S 2 displacements of alkyl bromides and sulfates (e.g., Scheme 2
N
27
type 4 Å) were added to a THF−CH Cl (1:1) solvent mixture and
and earlier ) by dianions of pentaerythritol diols. In addition, it is
very well known that treatment of compounds having quaternary
carbons to which are attached a hydroxymethyl group and a meth-
2 2
refluxed for 20 min. SOCl (110 mL, 2.8 equiv., 1.40 mol) was added
2
and the mixture was refluxed for 8 h at which point all of the
pentaerythritol had been consumed. The light yellow solution
was filtered and concentrated to give a light yellow solid. A satu-
38–40
ylene group bearing a leaving group such as a halide,
a sulfo-
4
1
42
nate, or even a nitrate give oxetanes in good yields. Therefore,
Scheme 4b is the most likely route to the oxetane byproducts.
In this mechanism, the concentration and lifetime of interme-
diate A are key. Its concentration can be reduced by keeping the
concentration of NaH low relative to the concentration of sultone.
Indeed, when NaH was added slowly to the mixture of diol and
excess 1,3-propanesultone in THF, the yield of the desired bissul-
fonates changed from <20% to about 80%. This 4-exo-tet ring clo-
sure is allowed under Baldwin’s rules,43 but the reaction takes
place from an eclipsed conformation and the nucleophile–carbon-
leaving group angle in the transition state must be less than the
ideal 180° angle. Moreover, the product is strained. These consid-
erations suggest that the activation energy for this process will be
considerable. Consistent with this conclusion, lowering the reac-
tion temperatures to room temperature and extending the time
of the reaction to 48 h also increased the yields of the desired
products at the expense of the oxetane byproducts.
rated NaHCO solution (1 L) was added directly to the residue at a
3
rate that minimized effervescence. The resulting suspension was
stirred vigorously for 20 min. The suspension was then filtered
and the solid was added to water (1 L). The mixture was stirred
vigorously for 20 min and the title compound (104.61 g, 0.458 mol,
92%) was collected by suction filtration and allowed to air dry.
1
13
30
H and C NMR spectral data match literature values.
Disodium 2,2-bis(butyloxymethyl)-1,3-propadiyl disulfate (2)
A hexanes-washed 60% oil dispersion of NaH (7.15 g, 0.18 mol,
7.2 equiv.) was added to an ice-cold DMF (100 mL) solution of
1-butanol (4.15 g, 0.056 mol, 2.2 equiv.) and the reaction mixture
3
0
was stirred for 1.5 h. A solution of compound 1 (6.40 g, 0.025 mol)
in DMF (50 mL) was added followed, after 2 h, by an additional
aliquot of a hexanes-washed 60% oil dispersion of NaH (2.06 g,
0.052 mol, 2.0 equiv.). After being stirred for 24 h at 60 °C, the
reaction mixture was cooled to 0 °C and MeOH was added
slowly dropwise until foaming ceased. Twenty percent HCl was
then added dropwise to neutralize (pH paper) the mixture. The
All three series of anionic gemini surfactants had good solubil-
ities in water and had very good surfactant properties. These prop-
2
9
erties will be discussed in detail elsewhere along with those of
Published by NRC Research Press

1088
Can. J. Chem. Vol. 91, 2013
reaction mixture was concentrated to give a brown solid that was
crystallized from 1:19 water−MeOH to give the title compound
in DMF (50 mL) as for compound 4 gave a yellow viscous liquid
that was extracted with boiling MeOH (ϳ1.5 L). A concentrated
extract was allowed to undergo water-promoted crystallization.
The title compound (7.60 g, 58%) was a colorless powder. Complex
melting behavior was observed: at 38.0 °C, it softened and became
slightly transparent, at 62.0 °C, it became a white translucent
paste, at 105.0 °C, it became an opaque white liquid, and at
(7.34 g, 0.016 mol, 65%): recrystallized from methanol-ethyl ace-
tate as colorless opaque needles: mp 200–203 °C, becomes trans-
1
parent at 225 °C, starts turning brown at 245–250 °C. H NMR
(
DMSO-d ) ␦: 0.86 (t, 6H, J = 7.4 Hz, CH ), 1.32 (sextet, 4H, J = 7.3 Hz,
6
3
CH CH CH ), 1.44 (p, 4H, J = 6.9 Hz, OCH CH ), 3.29 (s, 4H, CCH ),
2
2
3
2
2
2
13
3
.33 (t, 4H, J = 6.5 Hz, OCH CH ), 3.70 (s, 4H, –OSO CH C). C NMR ␦:
196.0 °C, it melted. R 0.55 (butanol−water−methanol 10:5:2).
2
2
3
2
F
1
1
3.8 (CH ), 18.4 (CH CH ), 31.3 (CH CH CH ), 43.4 (q C), 65.1
H NMR (DMSO-d ) ␦: 0.85 (t, 6H, J = 6.5 Hz, CH ), 1.21–1.33 (complex
3
3
2
3
2
2
6
3
(
–OSO CH ), 69.4 (CCH ), 70.5 (OCH CH ). LR ESI MS m/z calcd. for
m, 28H, 2 × (CH ) ), 1.46 (quintet, 4H, J = 6.5 Hz, OCH CH ), 3.28 (s,
3
2
2
2
2
2 7 2 2
C H O S : 407.10; found: 406.9; calcd. for C H O S Na:
4H, CCH ), 3.31 (t, 4H, J = 6.5 Hz, OCH CH ), 3.70 (s, 4H, −OSO CH C).
2 2 2 3 2
1
3
27 10
2
13 26 10
2
1
3
4
29.09; found: 429.3; calcd. for (C H O S )/2: 203.05; found:
C NMR ␦: 14.0 (CH ), 22.1 (CH CH ), 25.7 (OCH CH CH ), 28.7,
13
26 10
2
3 3 2 2 2 2
2
03.1. Anal. calcd. for C H O S Na .H O: C 33.19, H 6.00; found:
28.9, 29.0, 29.1 (4 alkyl C), 29.2 (OCH CH ), 31.3 (CH CH CH ), 43.4
2 2 3 2 2
13
26 10
2
2
2
C 32.97, H 5.77.
(q C), 65.3 (–OSO CH ), 69.4 (CCH O), 70.8 (OCH CH ). ESI MS m/z
3 2 2 2 2
calcd. for C25H O S : 575.29; found: 575.1; for C25H50O S Na:
51
10
2
10 2
Disodium 2,2-bis(hexyloxymethyl)-1,3-propadiyl disulfate (3)
Reaction of a hexanes-washed 60% oil dispersion of NaH (5.20 g,
5
97.27; found: 597.5; for (C H O S )/2: 287.14; found: 287.3. Anal.
25 50 10 2
calcd. for C H O S Na : C 48.38, H 8.12; found: C 48.37, H 8.15.
25
50 10
2
2
0.13 mol, 2.8 equiv.) and 1-hexanol (4.68 g, 0.046 mol, 2.1 equiv.) in
DMF (200 mL) with a DMF (25 mL) solution of the spirobicyclic
sulfate 1 (5.60 g, 0.022 mol) as for compound 2 using an additional
aliquot of hexanes-washed NaH (4.40 g, 0.11 mol, 2.4 equiv.) and a
longer reaction time, 48 h, gave a yellow solid that was recrystal-
lized from 1:19 water−MeOH to give the title compound (6.63 g,
Disodium 2,2-bis(dodecyloxymethyl)-1,3-propadiyl disulfate (6)
The reaction was performed as for 2 with hexanes-washed 60%
oil dispersion of sodium hydride (2.20 g, 10.5 equiv., 0.093 mol),
1-dodecanol (3.49 g, 2.1 equiv., 0.0186 mol) in DMF (50 mL), and
spirobicyclic sulfate (1, 2.35 g, 0.0209 mol) in DMF (10 mL) for 5 h
when additional NaH oil dispersion (1.90 g) was added. After 48 h,
workup as for 2 and concentration gave a yellow viscous liquid
that was extracted with boiling MeOH (ϳ1.5 L). The solid residue
obtained after removal of the MeOH was dissolved in water
(100 mL) and extracted with CH Cl (50 mL). The water layer was
0
.0215 mol, 61%). The analytical sample was recrystallized from
1
methanol: mp 185–187 °C. H NMR (DMSO-d ) ␦: 0.86 (t, 6H,
6
J = 6.9 Hz, CH ), 1.23–1.32 (complex m, 12H, 2 × (CH ) ), 1.46 (p, 4H,
3
2 3
J = 6.7 Hz, OCH CH ), 3.29 (s, 4H, CCH ), 3.32 (t, 4H, J = 6.5 Hz,
2
2
2
13
OCH CH ), 3.70 (s, 4H, –OSO CH C). C NMR ␦ 13.9 (CH ), 22.1
2
2
3
2
3
2
2
(
CH CH ), 25.3 (OCH CH CH ), 29.1 (OCH CH ), 31.1 (CH CH CH ),
concentrated to give a white solid that was crystallized from 10%
3
2
2
2
2
2
2
3
2
2
4
3.4 (q C), 65.1 (−OSO CH ), 69.4 (CCH ), 70.8 (OCH CH ). HR ESI MS
H O in MeOH. The title compound (2.10 g, 14%) was collected as a
3
2
2
2
2
2
m/z calcd. for C H O S Na: 485.1497; found: 485.1503. Anal.
colorless powder: complex melting behavior was observed: at
52.0 °C, it softened, at 102.6 °C, it became a slightly transparent
solid, at 116.2 °C, it became a colourless opaque fluid, at 141.3 °C, it
became an increasingly transparent semisolid, and at 181.3 °C, it
1
7 34 10 2
.
calcd. for C H O S Na H O: C 38.78, H 6.89; found: C 38.29,
1
7
34 10
2
2
2
H 6.92.
Disodium 2,2-bis(octyloxymethyl)-1,3-propadiyl disulfate (4)
A 60% oil dispersion of sodium hydride (6.08 g, 6.6 equiv.,
1
melted. R 0.58 (butanol−water−methanol 10:5:2). H NMR (DMSO-
F
d ) ␦: 0.85 (t, 6H, J = 7.0 Hz, CH ), 1.21–1.32 (complex m, 36H, 2 ×
6
3
0
.152 mol) was washed exhaustively with dried hexanes and then
added to an ice-cold DMF (200 mL) solution of 1-octanol (6.60 g,
.2 equiv., 0.0506 mol). The solution was left to stir under N and
(
4
CH ) ), 1.46 (p, 4H, J = 6.5 Hz, OCH CH ), 3.28 (s, 4H, CCH ), 3.31 (t,
H, J = 6.5 Hz, OCH CH ), 3.69 (s, 4H, –OSO CH ). C NMR ␦: 14.0
2 9 2 2 2
13
2 2 3 2
2
2
(CH ), 22.2 (CH CH ), 25.7 (OCH CH CH ), 28.8, 29.0, 29.1, 29.2 (×2),
3 3 2 2 2 2
in an ice bath for 20 min. A DMF solution (50 mL) of the spi-
robicyclic sulfate 1 (6.00 g, 0.0230 mol) was added slowly dropwise
to the ice-cold mixture over a 15 min period. The mixture was then
allowed to slowly reach room temperature and left to stir for 24 h.
MeOH was added dropwise to an ice-cold reaction mixture until
no more gas was formed. This was followed by dropwise addition
of 20% H SO until a neutral (pH paper) solution was obtained.
Concentration gave a yellow viscous liquid that was extracted
with boiling MeOH (ϳ1.5 L). A concentrated extract was allowed to
undergo water-promoted crystallization. The title compound
2
9.9, 30.7 (alkyl CH ), 31.4 (CH CH CH ), 43.4 (q C), 65.3
2 3 2 2
(
–OSO CH ), 69.4 (CCH ), 70.8 (OCH CH ). ESI MS m/z calcd. for
3 2 2 2 2
C29H59O S : 631.35; found: 631.2; for C29H58O S Na: 653.34;
found: 553.5; for (C29H58O S )/2: 315.17; found: 315.3. Anal. calcd.
for C29H58O S Na : C 51.46, H 8.54; found: C 51.40, H 8.76.
10
2
10 2
10
2
10
2
2
Disodium 2,2-bis(tetradecyloxymethyl)-1,3-propadiyl
disulfate (7)
2
4
The sodium salt of 1-tetradecanol (8.40 g, 2.2 equiv., 0.0392 mol)
in DMF (200 mL) was formed by reaction with NaH (4.70 g, 60% oil
dispersion, 6.6 equiv., 0.1175 mol) as for 2 and reacted with a DMF
solution (50 mL) of the spirobicyclic sulfate (1, 4.63 g, 0.0178 mol)
as for 4. The reaction was monitored by recording NMR spectra of
aliquots using singlets at ϳ5.00 and ϳ4.70 ppm to monitor bicy-
clic sulfate and monoproduct, respectively. If reaction was still
incomplete after 72 h, the reaction mixture was warmed to 45 °C
for 2 h. Workup and concentration as for 2 gave a colorless viscous
liquid that was extracted with boiling MeOH (1.5 L). The extract
was concentrated. On trituration with water, the residue solidi-
fied to a white powder (9.7 g, 75%): mp 195 °C. R 0.30 (butanol−
water−methanol 10:5:2). H NMR (DMSO-d ) ␦: 0.85 (t, 6H, J = 7.0 Hz,
2
2
3
(9.40 g, 72%) was a white powder with complex melting behavior:
at 37.3 °C, softening occurs and the sample became slightly trans-
parent, at 108.0 °C, it solidified and became more opaque, at
159.8 °C, it became increasingly opaque, at 167.1 °C, it softened
and becomes transparent, at 184.9 °C, it melted. R 0.53 (butanol−
F
1
water−methanol 10:5:2). H NMR (DMSO-d ) ␦: 0.85 (t, 6H, J = 7.0 Hz,
6
CH ), 1.22–1.31 (complex m, 20H, 2 × (CH ) ), OCH CH ), 1.46 (p, 4H,
3
2 5
2
2
J = 7.0 Hz, OCH CH ), 3.29 (s, 4H, CCH ), 3.31 (t, 4H, J = 6.5 Hz,
2
2
2
13
3
.71 (s, 4H, –OSO CH ). C NMR ␦: 14.0 (CH ), 22.1 (CH CH ),
3 2 3 3 2
2
5.7 (OCH CH CH ), 28.7, 28.9 (2 alkyl C), 29.2 (OCH CH ), 31.3
F
2
2
2
2
2
1
(
(
CH CH CH ), 43.4 (q C), 65.3 (–OSO CH ), 69.3 (CCH ), 70.8
6
3
2
2
3
2
2
CH ), 1.21–1.32 (complex m, 44H, 2 × 11 CH ), 1.47 (p, 4H, J = 6.5 Hz,
OCH CH ). HR ESI MS m/z calcd. for C H O S Na: 541.2123;
3
2
2
2
21 42 10 2
OCH CH ), 3.29 (s, 4H, CCH O), 3.31 (t, 4H, J = 6.5 Hz, OCH CH ),
found: 541.2140. Anal. calcd. for C H O S Na : C 44.67, H 7.50;
2
2
2
2
2
2
1
42 10
2
2
1
3
.71 (s, 4H, –OSO CH ). C NMR ␦: 13.9 (CH ), 22.1 (CH CH ), 25.7
found: C, 44.18, H 7.84.
3
2
3
3
2
(
OCH CH CH ), 28.7, 28.9, 29.01, 29.06 (×3), 29.09, 29.11, 29.14 (al-
2 2 2
Disodium 2,2-bis(decyloxymethyl)-1,3-propadiyl disulfate (5)
Reaction of a hexanes-washed 60% oil dispersion of sodium
hydride (5.53 g, 6.6 equiv., 0.138 mol) and 1-decanol (6.60 g, 2.2 equiv.,
kyl C), 31.3 (CH CH CH ), 43.3 (q C), 65.2 (–OSO CH ), 69.3 (CCH O),
3 2 2 3 2 2
70.7 (OCH CH ). ESI MS m/z calcd. for C33H66O S Na: 709.40;
2
2
10 2
found: 709.6. Anal. calcd. for C33H66O S Na : C 54.08, H 9.08;
10
2
2
0.0461 mol) in DMF (200 mL) with compound 1 (5.45 g, 0.0209 mol)
found: C, 53.72, H 9.00.
Published by NRC Research Press

Tran et al.
1089
Disodium 2,2-bis(hexadecyloxymethyl)-1,3-propadiyl
disulfate (8)
to give a product with physical constants that matched those of 11
prepared previously: yield 5.50 g, 39%.
2
7
The sodium salt of 1-hexadecanol (1.03 g, 2.2 equiv., 0.0043 mol)
in DMF (150 mL) was formed by reaction with hexanes-washed
NaH (1.13 g, 63% oil dispersion, 7.3 equiv., 0.0311 mol) as for 2 and
then reacted with a DMF solution (50 mL) of the spirobicyclic
sulfate (1, 0.504 g, 0.00194 mol) for 72 h at 40 °C. Workup as for 2
followed by concentration gave a colorless solid that was ex-
tracted with diethyl ether and then with dichloromethane. Crys-
tallization from ethyl acetate containing a few drops of methanol
2
,2-Bis(tetradecyloxymethyl)-1,3-propanediol (12)
Compound 8 (31.4 g, 0.043 mol) was dissolved in a mixture of
THF and water (2:1, 750 mL) and then concentrated HCl (250 mL)
was added slowly in portions to avoid boiling. The clear solution
was allowed to stir for 1 h and then the resulting cloudy suspen-
sion was refluxed for 0.5 h, at which point TLC indicated that all
starting material had been consumed. When the reaction mixture
was allowed to cool to room temperature, two layers formed. The
mixture was extracted with ether (3 × 500 mL) and the combined
organic layers were washed with a BaCl solution (5.0 g in 500 mL
of water, 0.25 equiv.), dried (MgSO ), and concentrated to give a
white solid. The title compound (12) was crystallized from meth-
anol, yield 16.5 g, 74.3%. The NMR spectra and melting point
gave colorless granules: yield 0.86 g, 26%; mp 110 °C. R 0.60
F
1
(
butanol−water−methanol 10:5:2). H NMR (CDCl ) ␦: 0.88 (t, 6H, J =
3
2
6
.9 Hz, 2 CH ), 1.26–1.29 (brs, 52H, 2 × 26 CH ), 1.49 (p, 4H, J =
3
2
4
6
.4 Hz, 2 OCH CH ), 3.35 (t, 4H, J = 6.6 Hz, OCH CH ), 3.43 (s, 4H,
2
2
2
2
13
CCH O), 4.04 (s, 4H, –OSO CH ). C NMR ␦: 14.2 (CH ), 22.0
2
3
2
3
(
CH CH ), 26.3 (OCH CH CH ), 29.87 (×4), 29.82 (×5), 29.7, 29.5 (al-
3 2 2 2 2
27
matched values for compound 12 made previously.
kyl C), 32.1 (CH CH CH ), 44.2 (q C), 67.4 (–OSO CH ), 69.1 (CCH O),
3
2
2
3
2
2
7
3
1.9 (OCH CH ). HR MS m/z calcd. for C H74O S : 371.2356; found:
2 2 37 10 2
Disodium 5,5-bis(octyloxymethyl)-3,7-dioxa-1,9-nonadiyl
disulfate (13)
To a stirred ice-bath-cooled solution of 2,2-bis(octyloxymethyl)-
71.2360.
,2-Bis(octyloxymethyl)-1,3-propanediol (9)
2
1,3-propanediol (2) (5.40 g, 0.015 mol) in THF (100 mL) was added a
Compound 4 (12.6 g, 0.0223 mol) was dissolved in a mixture of
hexanes-washed 60% oil dispersion of sodium hydride (2.60 g,
THF and water (1:1, 300 mL) and then concentrated HCl (100 mL)
was added slowly in portions to avoid boiling. The clear solution
was allowed to stir for 1 h and then the resulting cloudy suspen-
sion was refluxed for 0.5 h, at which point TLC indicated that all
starting material had been consumed. When the reaction mixture
was allowed to cool to room temperature, two layers formed. The
mixture was extracted with ether (3 × 200 mL) and the combined
organic layers were washed with a BaCl solution (1.2 g in 200 mL
of water, 0.25 equiv.), dried (MgSO ), and concentrated to give a
white solid. The title compound (9) was crystallized from meth-
anol, yield 6.42 g, 79.8%. The NMR spectra and melting point
0
3
0
.065 mol, 4.3 equiv.). The cooled reaction mixture was stirred for
48,49
0 min and then a solution of ethylene sulfate
(4.0 g,
.032 mol, 2.2 equiv.) in THF (50 mL) was added dropwise to the
reaction mixture over a 20 min period. The reaction mixture was
stirred for 19 h at room temperature and then MeOH was added
carefully dropwise until foaming ceased. Ten percent HCl was
added to neutralize the reaction (pH paper). Concentration gave a
white paste that was purified using column chromatography with
a solvent gradient changing from pure EtOAc to MeOH−EtOAc 2:3.
The product was obtained as a white solid (6.87 g, 70%): mp 143.0–
2
4
1
1
45.5 °C. H NMR (500.13 MHz, MeOD−CDCl 50:50) ␦: 0.89 (t, J =
3
2
7
matched values for compound 9 made previously.
6
.8 Hz, 6H, 2 × CH ), 1.31 (br m, 20H, alkyl protons), 1.54 (quintet,
3
J = 7.0 Hz, 4H, 2 × OCH CH ), 3.38 (s, 4H, CH CH CH OCH C), 3.39
2
2
2
2
2
2
2
,2-Bis(decyloxymethyl)-1,3-propanediol (10)
Compound 5 (18.7 g, 0.0301 mol) was dissolved in a mixture of
(
t, J = 6.5 Hz, 4H, 2 × OCH CH ), 3.49 (s, 4H, O SOCH CH OCH C),
2 2 3 2 2 2
3
.68 (XX= part of AA=XX= pattern, J + J
= 10.0 Hz, 4H, 2 ×
A=X
AX
THF and water (1:1, 400 mL) and then concentrated HCl (150 mL)
was added slowly in portions to avoid boiling. The clear solution
was allowed to stir for 1 h and then the resulting cloudy suspen-
sion was refluxed for 0.5 h, at which point TLC indicated that all
starting material had been consumed. When the reaction mixture
was allowed to cool to room temperature, two layers formed. The
mixture was extracted with ether (3 × 300 mL) and the combined
organic layers were washed with a BaCl solution (1.6 g in 200 mL
of water, 0.25 equiv.), dried (MgSO ), and concentrated to give a
white solid. The title compound (10) was crystallized from meth-
anol, yield 9.26 g, 73.8%. The NMR spectra and melting point
−
O SOCH CH ), 4.14 (AA= part of AA=XX= pattern, J
+ J
=
3
2
2
AX
A=X
−
13
1
0.0 Hz, 4H, 2 × O SOCH CH ). C NMR (125.77 MHz, MeOD) ␦: 14.3
3 2 2
(
2 × CH ), 23.2 (2 × CH CH ), 26.8 (2 × OCH CH CH ), 30.0, 30.1, 30.2
3 2 3 2 2 2
(
2 × OCH CH and 2 × 2 alkyl chain carbons), 32.5 (2 × CH CH CH ),
2 2 2 2 3
4
6.3 (q C), 67.6 (2 × OSO CH ), 70.1 (2 × CH OCH CH CH ), 70.7
3 2 2 2 2 2
(
2 × OSO CH CH ), 71.1 (2 × O SOCH CH OCH ), 72.4 (2 ×
3 2 2 3 2 2 2
OCH CH CH ). ESI MS (neg. ion mode): calcd. for C25H50O S Na
2
2
2
12 2
2
(M-Na): 629.26; found: 629.3; calcd. for (M-2Na)/2: 303.14; found:
303.3; calcd. for M-2Na+H: 607.28; found: 607.1; calcd. for 2M-Na:
4
1
281.52; found: 1281.1. Anal. calcd. for C25H50O S Na : C 46.00, H
12 2 2
7.72; found: C 46.11, H 7.47.
2
7
matched values for compound 10 made previously.
Disodium 5,5-bis(decyloxymethyl)-3,7-dioxa-1,9-nonadiyl
disulfate (14)
Reaction of 2,2-bis(decyloxymethyl)-1,3-propanediol (3) (2.60 g,
2
,2-Bis(dodecyloxymethyl)-1,3-propanediol (11) via the
corresponding disulfate
To an ice-bath-cooled solution of 1-dodecanol (12.31 g, 0.066 mol)
in DMF (150 mL) was added hexanes-washed sodium hydride (60%
oil dispersion, 8.8 g, 0.22 mol, 3.3 equiv.). After the reaction mix-
ture had been stirred for 30 min, a DMF (20 mL) solution of pen-
taerythritol spirobicyclic sulfate30 (1, 8.0 g, 0.031 mol, 0.47 equiv.)
was added dropwise and the reaction mixture was stirred for 36 h
and then quenched by adding MeOH dropwise until foaming
ceased. The reaction mixture was neutralized (pH paper) with
0
.0063 mol) in THF (50 mL) with hexane-washed sodium hydride
(
(
60% oil dispersion, 1.25 g, 0.0313 mol, 5.0 equiv.) with a THF
25 mL) solution of ethylene sulfate (1.72 g, 0.0138 mol, 2.2 equiv.)
was done for 26 h as for 13. Workup as for 13 followed by
concentration gave a colorless solid. The product was extracted
with hot methanol and the concentrated extract was allowed to
undergo water-promoted crystallization. The title compound
was a powder that was crystallized from EtOAc−MeOH to give a
colorless crystalline product: yield (3.79 g, 86%); mp 165–172 °C.
10% HCl and then concentrated to a white solid. The solid was
1
dissolved in 20% H SO (360 mL) and then diethyl ether (100 mL)
H NMR (500.13 MHz, DMSO) ␦: 0.84 (t, J = 6.5 Hz, 6H, 2 × CH3),
2
4
was added and the reaction was allowed to stir for 12 h. The
reaction was then refluxed for 48 h and then cooled to room
temperature and extracted with diethyl ether (250 mL). The or-
1.24 (br m, 28H, alkyl protons), 1.46 (quintet, J = 7.2 Hz, 4H, 2 ×
OCH CH ), 3.26 (s, 4H, 2 × CH CH CH OCH C), 3.38 (s, 4H, 2 ×
2
2
2
2
2
2
O SOCH CH OCH C), 3.39 (t, J = 6.6 Hz, 4H, 2 × OCH CH ), 3.47
3
2
2
2
2
2
ganic layer was dried (MgSO ) and concentrated to give the prod-
uct as a white powder. The product was recrystallized from MeOH
(XX= part of AA=XX= pattern, J
+ J
= 10.0 Hz, 4H, 2 ×
4
AX
A=X
−
O SOCH CH ), 3.77 (AA= part of AA=XX= pattern, J + J
=
A=X
3
2
2
AX
Published by NRC Research Press

1090
Can. J. Chem. Vol. 91, 2013
−
1
1
2
0.0 Hz, 4H, 2 × O SOCH CH ). 13C NMR (125.77 MHz, MeOD) ␦:
71.3 (2 × OSO CH CH OCH ), 72.5 (2 × OCH CH CH ). HR MS calcd.
for (M-Na) C37H74O S Na: 797.4525; found: 797.4517.
12 2
3
2
2
3
2
2
2
2
2
2
3.9 (2 × CH ), 22.1 (2 × CH CH3), 25.6 (2 × OCH CH CH ), 28.7,
8.8, 29.0, 29.0, 29.1 (2 × OCH CH and 2 × 4 other alkyl chain
carbons), 31.3 (2 × CH CH CH ), 45.1 (q C), 64.8 (2 × OSO CH ),
3
2
2
2
2
2
2
Disodium 6,6-bis(octyloxymethyl)-4,8-dioxa-1,11-
undecanedisulfonate (17)
2
2
3
3
2
6
8.9 (2 × CH OCH CH CH ), 69.6 (2 × OSO CH CH ), 70.0 (2 ×
2 2 2 2 3 2 2
1
,3-Propanesultone (4.1 mL, 10 eq.) in THF (5 mL) was added to a
stirred solution of 2,2-bis(octyloxymethyl)-1,3-propanediol (2)
1.7 g, 4.7 mmol) in THF (5 mL) under an argon atmosphere and
OSO CH CH OCH ), 70.7 (2 × OCH CH CH ). ESI MS: calcd. for
C29H58O S Na: 685.325; found: 685.325. Anal. calcd. for
C29H58O S Na : C 49.14, H 8.25; found: C 49.36, H 8.38.
3
2
2
2
2
2
2
12
2
(
12
2
2
then a suspension of hexanes-washed sodium hydride (60% oil
dispersion, 0.43 g, 10.6 mmol, 2.25 equiv.) in THF (3 mL) was added
dropwise over a 20–30 min period. The resulting mixture was
stirred for 18 h at 40 °C. Another addition of a suspension of
sodium hydride (60% oil dispersion, 0.21 g, 5.34 mmol, 1.13 equiv.)
in THF (3 mL) was made and the reaction mixture was stirred for
an additional 6 h at 40 °C and then for 24 h at room temperature.
Methanol was added dropwise to the ice-bath-cooled reaction mix-
ture until foaming ceased. Ten percent HCl was added until the
reaction mixture was neutral (pH paper). Concentration gave a
white solid that was purified using flash column chromatography
initially eluting with an ethyl acetate ethanol mixture (80:20 v/v)
and then eluting with ethanol − ethyl acetate (80:20 v/v) to afford
the title compound as a white solid that was precipitated out from
ethanol water and then recrystallized from ethyl acetate − methanol
to yield colorless granules: yield 2.31 g, 76%; mp 185 °C, became
Disodium 5,5-bis(dodecyloxymethyl)-3,7-dioxa-1,9-nonadiyl
disulfate (15)
Reaction of 2,2-bis(dodecyloxymethyl)-1,3-propanediol (4) (7.08 g,
0.015 mol) in THF (100 mL) with hexanes-washed 60% oil disper-
sion of NaH (2.20 g, 0.055 mol, 3.6 equiv.) and then a solution of
ethylene sulfate (4.0 g, 0.032 mol, 2.2 equiv.) in THF (50 mL) was
performed as for 13 for 21 h at room temperature. When TLC
showed that not all starting material had been consumed, more
ethylene sulfate (0.1 g, 0.8 mmol) was added and the reaction
mixture was stirred for another 3 h. Workup as for 13 followed by
concentration yielded a white paste that was taken up in a 1:1
CH Cl −MeOH. The mixture was heated to a boil and then filtered.
2
2
The filtrate was then heated until the mixture became clear. The
solution was allowed to cool to room temperature before being
refrigerated. The product was collected by filtration (9.53 g,
1
0
.0125 mol, 83%): mp 144.5–146.0 °C. H NMR (500.13 MHz, MeOD)
transparent, 220–235 °C, decomposed. R 0.34 (butanol−water−
F
1
␦
: 0.90 (t, J = 7.1 Hz, 6H, 2 × CH ), 1.29 (br m, 36H, alkyl protons),
methanol 10:2.5:1.5). H NMR (500.13 MHz, methanol-d ) ␦: 0.90 (t,
3
4
1
.54 (quintet, J = 7.2 Hz, 4H, 2 × OCH CH ), 3.38 (s, 4H, 2 ×
J = 6.9 Hz, 6H, 2 × CH ), 1.31 (br m, 20H, alkyl protons), 1.52 (pentet,
2
2
3
−
CH CH CH OCH C), 3.39 (t, J = 6.6 Hz, 4H, 2 × OCH CH CH ), 3.47
J = 6.7 Hz, 4H, 2 × OCH CH CH CH ), 2.02 (m, 4H, 2 × O SCH CH ),
2
2
2
2
2
2
2
2
2
2
2
3
2
2
−
(
J
s, 4H, O SOCH CH OCH C), 3.64 (AA= part of AA=XX= pattern, J
+
2.87 (m, 4H, 2 × O SCH ), 3.36 (s, 4H, 2 × CH CH CH CH OCH C),
3
2
2
2
−
AX
3 2 2 2 2 2 2
= 10.0 Hz, 4H, 2 × O SOCH CH ), 4.09 (XX= part of AA=XX=
3.377 (t, 4H, J = 6.3 Hz, 2 × OCH CH CH ), 3.383 (s, 4H, 2 ×
2 2 2
A=X
3
2
2
−
13
−
−
3 2 2 2 2 3
pattern, J + J
= 10.0 Hz, 4H, 2 × O SOCH CH ). C NMR
O SCH CH CH OCH C), 3.48 (t, 4H, J = 6.1 Hz, 2 × O SCH2
AX
A=X
3
2
2
1
3
(125.77 MHz, MeOD) ␦: 14.6 (2 × CH ), 23.9 (2 × CH CH ), 27.6 (2 ×
CH CH ). C NMR (125.77 MHz, methanol-d ) ␦: 14.4 (2 × CH ), 23.7
2 2 4 3
(2 × CH CH ), 26.7 (2 × O SCH CH ), 27.4 (2 × OCH CH CH ), 30.47,
3
2
3
−
2 3 3 2 2 2 2 2
OCH CH CH ), 30.6, 30.8, 30.9 (×3), 31.0 (×2) (2 × OCH CH and 2 ×
2
2
2
2
2
6
other alkyl chain carbons), 33.2 (2 × CH CH CH ), 47.0 (q C), 68.3
30.54, 30.7 (2 × OCH CH and 2 × 2 other alkyl chain carbons),
2 2
2
2
3
−
2 2 3 3 2
(2 × OSO CH ), 70.7 (CH OCH CH CH ), 71.3 (2 × OSO CH CH ), 71.4
33.0 (2 × CH CH CH ), 46.7 (q C), 50.0 (2 × O SCH ), 70.7 (2 ×
3
2
2
2
2
2
3
2
2
−
(2 × OSO CH CH OCH ), 72.7 (2 × OCH CH CH ). ESI MS (neg. ion
CH OCH CH CH CH ), 70.9 (2 × O SCH CH CH OCH ), 71.2 (2 ×
2 2 2 2 2 3 2 2 2 2
3
2
2
2
2
2
2
−
mode): calcd. for (M-Na) C33H66O S Na: 741.39; found: 741.5; calcd.
O SCH CH CH O), 72.5 (OCH CH CH CH ). HR ESI MS m/z calcd.
12
2
3 2 2 2 2 2 2 2
for (M-2Na)/2: 350.20; found: 359.3; calcd. for M-2Na + H: 719.40;
found: 719.2; calcd. for 2M-Na: 1505.77; found: 1506.3. Anal. calcd.
for C33H66O S Na : C 51.82, H 8.70; found: C 52.04, H 8.86.
for C27H54O S Na (M-Na): 625.3051; found: 625.3082.
10 2
Disodium 6,6-bis(decyloxymethyl)-4,8-dioxa-1,11-
undecanedisulfonate (18)
12
2
2
Disodium 3,7-dioxa-5,5-bis(tetradecyloxymethyl)-1,9-nonadiyl
disulfate (16)
Reaction of 2,2-bis(tetradecyloxymethyl)-1,3-propanediol (5)
Compound 18 was made as for 17 except that workup of the
neutralized reaction mixture was changed. 2,2-Bis(decyloxymethyl)-
1,3-propanediol (3) (1.72 g, 4.13 mmol) in THF (5 mL) was reacted
with 1,3 propanesultone (4.0 mL, 10 equiv.) under argon using two
additions of suspensions of hexanes-washed 60% oil dispersions of
sodium hydride (0.37 g, 9.3 mmol, 2.25 equiv.) in THF (3 mL) and
(0.186 g, 5.17 mmol, 1.13 equiv.) in THF (3 mL). The colorless solid
resulting from concentration of the neutralized reaction mixture
was washed repeatedly with ethyl acetate until NMR indicated
that all sultone had been removed. The product was then ex-
tracted with hot ethanol. The hot ethanol extract was concen-
trated and then the residue was taken up in boiling ethanol
containing a few drops of water. Cooling resulted in a precipitate
that was crystallized from ethyl acetate − methanol to give color-
less granules of the title compound: yield 2.4 g, 83%; mp 187 °C,
(2.5 g, 0.0047 mol) in THF (75 mL) with a hexanes-washed 60% oil
dispersion of NaH (1.0 g, 0.0236 mol, 5.0 equiv.) followed by solution
of ethylene sulfate (1.29 g, 0.0104 mol, 2.2 equiv.) in THF (20 mL) was
performed as for 13 at 40 °C for 24 h. After 24 h, more NaH
(
1
0.19 g 1.0 equiv.) and ethylene sulfate (0.645 g, 0.005 mol,
.1 equiv.) was added at 0 °C and then the reaction mixture was
heated to 40 °C and then stirred for another 24 h. Workup as for
3 followed by concentration yielded a light yellow solid that
1
was purified using flash column chromatography eluting with
ethyl acetate − methanol mixtures changing from 95:05 to
8
0:20 to afford the title compound (16) as a colorless powder.
Recrystallization from ethyl acetate − methanol yielded a color-
less crystalline product: yield 2.34 g, 60%; mp 145 °C, became
became transparent, 215–230 °C, decomposed. R 0.38 (butanol−
F
1
1
transparent, 160 °C, melted. H NMR (500.13 MHz, MeOD) ␦: 0.90 (t,
water−methanol 10:2.5:1.5). H NMR (500.13 MHz, methanol-d ) ␦:
4
J = 7.5 Hz, 6H, 2 × CH ), 1.29 (br m, 40H, alkyl protons), 1.54
0.89 (t, J = 6.9 Hz, 6H, 2 × CH ), 1.34 (br m, 28H, alkyl protons),
3
3
(
quintet, J = 6.5 Hz, 4H, 2 × OCH CH ), 3.35 (s, 4H, 2 ×
1.54 (pentet, J = 6.5 Hz, 4H, 2 × OCH CH CH CH ); 2.02 (m, 4H,
2
2
2
2
2
2
−
−
3 2 2 3 2
CH CH CH OCH C), 3.39 (t, J = 6.5 Hz, 4H, 2 × OCH CH CH ), 3.46
2 × O SCH CH ), 2.89 (m, 4H, 2 × O SCH ), 3.36 (s, 4H, 2 ×
2
2
2
2
2
2
2
(
s, 4H, O SOCH CH OCH C), 3.64 (AA= part of AA=XX= pattern, J
+
CH CH CH CH OCH C), 3.377 (t, 4H, J = 6.3 Hz, 2 × OCH CH CH ),
2 2 2 2 2 2 2 2
3
2
2
2
−
AX
−
J
= 10.0 Hz, 4H, 2 × O SOCH CH ), 4.09 (XX= part of AA=XX=
3.382 (s, 4H, 2 × O SCH CH CH OCH C), 3.48 (t, 4H, J = 6.1 Hz, 2 ×
A=X
3
2
2
3 2 2 2 2
O SCH CH CH ). H NMR (500.13 MHz, DMSO-d ) ␦: 0.86 (t, J =
3 2 2 2 6
−
13
−
1
pattern, J + J
= 10.0 Hz, 4H, 2 × O SOCH CH ). C NMR
AX
A=X
3
2
2
(125.77 MHz, MeOD) ␦: 14.4 (2 × CH ), 23.7 (2 × CH CH ), 27.4 (2 ×
6.8 Hz, 6H, 2 × CH ), 1.24 (br m, 28H, alkyl protons), 1.46 (pentet, J =
3
2
3
3
−
OCH CH CH ), 30.5, 30.6, 30.76 (×4), 30.84 (×3) (2 × OCH CH and
2
6
6.6 Hz, 4H, 2 × OCH CH CH CH ), 1.77 (m, 4H, 2 × O SCH CH ),
2
2
2
2
2
2
×
2
2
2
3
2
2
−
× 8 other alkyl chain carbons), 33.1 (2 × CH CH CH ), 46.8 (q C),
2.44 (m, 4H,
2
O SCH ), 3.255, 3.257 (2s, 8H, 2 ×
2
2
3
3 2
−
2 2 2 2 2 3 2 2 2 2
8.1 (2 × OSO CH ), 70.5 (CH OCH CH CH ), 71.2 (2 × OSO CH CH ),
CH CH CH CH OCH C, 2 × O SCH CH CH OCH C), 3.31 (t, 4H, J =
3
2
2
2
2
2
3
2
2
Published by NRC Research Press

Tran et al.
1091
6
.4 Hz, 2 × −O SCH CH CH ), 3.36 (t, 4H, J = 6.3 Hz, 2 ×
3,3-Bis(octyloxymethyl)oxetane (21)
3
2
2
2
−
13
O SCH CH CH ). C NMR (125.77 MHz, methanol-d ) ␦: 14.4
A stirred solution of 2,2-bis(octyloxymethyl)-1,3-propanediol (2)
(2.06 g, 5.72 mmol) in THF (50 mL) was cooled in an ice bath under
a nitrogen atmosphere and then hexanes-washed sodium hydride
(60% oil dispersion, 0.92 g, 22.9 mmol, 4.0 equiv.) was added. After
1 h, a solution of 1,3-propane sultone (1.57 g, 12.8 mmol,
2.25 equiv.) in THF (20 mL) was added dropwise over 1 h while the
reaction mixture was maintained at 0 °C. The reaction mixture
was stirred for 24 h at 50 °C. Another addition of sodium hydride
3
2
2
2
4
−
3 2 3 3 2 2
(2 × CH ), 23.7 (2 × CH CH ), 26.7 (2 × O S-CH CH ), 27.4 (2 ×
OCH CH CH ), 30.5, 30.6, 30.7 (×2), 30.8 (2 × OCH CH and 2 ×
4
2
2
2
2
2
other alkyl chain carbons), 33.1 (2 × CH CH CH ), 46.7 (q C),
2 2 3
−
−
3 2 2 2 9 3 2 2
50.0 (2 × O SCH ), 70.7 (2 × CH O(CH ) ), 70.9 (2 × O SCH CH
−
CH OCH ), 71.2 (2
HR ESI MS m/z calcd. for C H NaO S (M-Na): 681.3677; found:
×
O SCH CH CH O), 72.5 (OCH (CH ) ).
3 2 2 2 2 2 8
2
2
31
62
10 2
6
81:3706.
(
0.46 g 11.4 mmol, 2.0 equiv.) and 1,3-propane sultone (0.79 g,
Disodium 6,6-bis(dodecyloxymethyl)-4,8-dioxa-1,11-
undecanedisulfonate (19)
Compound 19 was made as for 18. 2,2-Bis(dodecyloxymethyl)-
6.44 mmol, 1.13 equiv.) in THF (10 mL) was made and stirring was
continued at 50 °C for 4 h and then the reaction mixture was
stirred for 12 h at room temperature. Methanol was added drop-
wise to the ice-bath-cooled reaction mixture until foaming ceased.
Ten percent HCl was added until the reaction mixture was neutral
(pH paper). The colorless solid resulting from concentration of the
neutralized reaction mixture was washed with ethyl acetate to
1,3-propanediol (4) (1.32 g, 2.79 mmol) in THF (5 mL) was reacted
with 1,3-propanesultone (2.5 mL, 28 mmol, 10 equiv.) in THF (5 mL)
under argon using two additions of suspensions of hexanes-
washed 60% oil dispersion of sodium hydride (0.25 g, 6.3 mmol,
2
.25 equiv.) in THF (3 mL) and 1.13 equiv. in THF (3 mL). The color-
afford the title compound as a colorless syrup: yield 0.41 g, 40%. R
0.29(hexanes − ethyl acetate 90:10). H NMR ␦: 0.88 ppm (t, 6H, J =
6.9 Hz, 2 × Me), 1.27–1.34 (br s, 20H, alkyl protons), 1.54 (pentet, 4H,
F
1
less solid resulting from concentration of the neutralized reaction
mixture was washed repeatedly with ethyl acetate until NMR in-
dicated that all sultone had been removed. The product was then
extracted with hot ethanol. The hot ethanol extract was concen-
trated and then the residue was taken up in boiling ethanol con-
taining a few drops of water. Cooling resulted in a precipitate that
was crystallized from ethylacetate − methanol to give colorless
granules of the title compound: yield 1.80 g, 85%; mp 180 °C,
J = 6.6 Hz, 2 OCH
4H, OCH C), 4.46 (s, 4H, oxetane CCH
22.8 (2 × CH CH ), 26.3 (2 × CH CH
3 other octyl CH ), 32.0 (2 × CH CH
CCH OCH CH ), 72.1 (2 × CH CH OC), 76.8 (2 × oxetane CCH
ESI MS m/z calcd. for (C21 + Na): 365.3026; found: 365.3007.
CH ), 3.44 (t, 4H, J = 6.5 Hz, octyl OCH
), 3.61 (s,
O). C NMR ␦: 14.2 (2 × Me),
CH O), 29.4, 29.6, 29.7 (2 ×
CH ), 44.1 (q C), 71.8 (2 ×
O). HR
2
2
2
1
3
2
2
2
3
2
2
2
2
2
2
3
2
2
2
2
2
2
H O
42 3
became transparent, 215–240 °C, decomposed. R 0.41 (butanol−
F
1
3,3-Bis(decyloxymethyl)oxetane (22)
water−methanol 10:2.5:1.5). H NMR (500.13 MHz, methanol-d ) ␦:
4
1
Colorless syrup, R 0.33 (hexanes − ethyl acetate 90:10). H NMR
F
0
.89 (t, J = 6.9 Hz, 6H, 2 × CH ), 1.29–1.35 (br s, 36H, 18 × CH ), 1.56
3
2
␦
: 0.88 ppm (t, 6H, J = 6.9 Hz, 2 × Me), 1.26–1.30 (br s, 28 H, 14 × CH2),
(
pentet, J = 6.6 Hz, 4H, 2 × OCH CH CH CH ), 2.02 (m, 4H, 2 ×
2 2 2 2
−
1
.56 (pentet, 4H, J = 7.1 Hz, 2 OCH CH ), 3.45 (t, 4H, J = 6.6 Hz, decyl
−
2 2
O SCH CH ), 2.87 (m, 4H, 2 × O SCH ), 3.36 (s, 4H, 2 ×
3
2
2
3
2
1
3
OCH ), 3.61 (s, 4H, OCH C), 4.46 (s, 4H, CCH O). C NMR ␦: 14.2 (2 ×
2
2
2
(
CH ) OCH C), 3.377 (t, 4H, J = 6.3 Hz, 2 × OCH (CH ) ), 3.382 (s,
2 11 2 2 2 10
−
Me), 22.8 (2 × CH CH ), 26.2 (2 × CH CH CH O), 29.5, 29.6, 29.70,
2
3
2
2
2
4
H, 2 × O SCH CH CH OCH C), 3.48 (t, 4H, J = 6.1 Hz, 2 ×
3 2 2 2 2
2
9.74, 29.79 (2 × 5 other decyl CH ), 32.1 (2 × CH CH CH ), 44.1 (q C),
−
13
2 2 2 3
O SCH CH CH ). C NMR (125.77 MHz, MeOD) ␦: 14.5 (2 × CH ),
3
2
2
2
3
7
1.8 (2 × CCH OCH ), 72.1 (2 × CH CH OC), 76.8 (2 × oxetane
−
2 3 3 2 2 2 2 2
2
2
2
2
2
3
6
5
3.7 (2 × CH CH ), 26.7 (2 × O SCH CH ), 27.4 (2 × OCH CH CH ),
CCH O). HR ESI MS m/z calcd. for (C25H50O Na): 421.3652; found:
2
3
0.5, 30.59, 30.65, 30.78 (×2), 30.82 (×2) (2 × OCH CH and 2 ×
2
2
421.3648.
other alkyl chain carbons), 33.1 (2 × CH CH CH ), 46.7 (q C),
2
2
3
−
−
0.0 (2 × O SCH ), 70.7 (2 × CH O(CH ) ), 70.9 (2 × O SCH
3
2
2
2 11
3
2
3,3-Bis(tetradecyloxymethyl)oxetane (24)
−
CH CH OCH ), 71.2 (2 × O S(CH ) CH O), 72.5 (OCH (CH ) ). HR ESI
2
2
2
3
2 2
2
2
2 10
Colorless crystalline solid: mp 32–34 °C, R 0.38 (hexanes − ethyl
F
MS m/z calcd. for C H NaO S (M-Na): 737.4303; found: 737.4256.
1
35
70
10
2
acetate 90:10). H NMR ␦: 0.88 ppm (t, 6H, J = 6.7 Hz, 2 × Me), 1.26 (br
s, 44H, 18 × CH ), 1.56 (pentet, 4H, J = 6.5 Hz, 2 OCH CH ), 3.45 (t,
2
2
2
Disodium 4,8-dioxa-6,6-bis(tetradecyloxymethyl)-1,11-
undecanedisulfonate (20)
Compound 20 was made as for 18 from 1,3-propanesultone
4
H, J = 6.5 Hz, decyl OCH ), 3.61 (s, 4H, OCH C), 4.47 (s, 4H, CCH O).
2 2 2
13
C NMR ␦: 14.2 (2 × Me), 22.8 (2 × CH CH ), 26.3 (2 × CH CH CH O),
2
3
2
2
2
29.5, 29.6, 29.7, 29.80 (×3), 29.84 (×3) (2 × 9 other tetradecyl CH2),
(
2 mL, 21 mmol, 10 equiv.) in THF (5 mL) and compound 5 (1.13 g,
.14 mmol) in dry THF (5 mL) using two identical additions of
suspensions of 60% oil dispersions of sodium hydride (0.2 g,
.3 mmol, 2.25 equiv.), each followed by stirring for 12 h at 40 °C,
3
2.1 (CH CH CH ), 44.2 (q C), 71.8 (CCH OCH ), 72.2 (CH CH OC),
2
2
3
2
2
2
2
2
7
6.8 (oxetane CCH O). HR MS m/z calcd. for (C33H66O Na):
2
3
533.4904; found: 533.4876.
4
and then a third addition (0.1 g, 2.4 mmol, 1.13 equiv.) followed by
stirring at 35 °C for 24 h and then for 12 h at room temperature.
Normal work up gave a white solid that was purified by column
chromatography as for compound 17 followed by crystallization
from ethyl acetate − methanol to give an amorphous colorless
solid: yield 1.43 g, 82%; mp 175–180 °C, became transparent, 210–
Supplementary material
Supporting information: H NMR and 13C NMR spectra of all
new compounds. Supplementary material is available with the
article through the journal Web site at http://nrcresearchpress.
com/doi/suppl/10.1139/cjc-2013-0256.
1
2
45 °C, decomposed. R 0.44 (butanol−water−methanol 10:2.5:1.5).
F
Acknowledgements
1
H NMR (500.13 MHz, methanol-d ) ␦: 0.89 (t, J = 6.8 Hz, 6H, 2 ×
CH ), 1.28–1.31 (br s, 44H, 22 × CH ), 1.54 (pentet, J = 6.5 Hz, 4H,
4
We thank the Atlantic Innovation Fund and the Natural Sci-
ences and Engineering Research Council of Canada for support.
NMR spectra were recorded at the NMR-3. We thank Dr. Eugen A.
Karpichev and Tyler Mercer for measurement of surface tensions
and Dr. Hiroshi Furue for translation of reference 18.
3
2
−
2 2 2 11 3 2 2
2
× OCH CH (CH ) ), 2.05 (m, 4H, 2 × O SCH CH ), 2.91 (m, 4H, 2 ×
−
O SCH ), 3.36 (s, 4H, 2 × (CH ) OCH C), 3.377 (t, 4H, J = 6.3 Hz,
3
2
2 13
2
−
2 2 13 3 2 3 2
2
× OCH (CH ) ), 3.382 (s, 4H, 2 × O S(CH ) OCH C), 3.48 (t, 4H,
−
13
J = 6.1 Hz, 2 × O S(CH ) CH O). C NMR (125.77 MHz, D O) ␦: 13.9
3
2 2
2
2
−
(2 × CH ), 22.8 (2 × CH CH ), 24.7 (2 × O SCH CH ), 26.4 (2 ×
References
3
2
3
3
2
2
OCH CH CH ), 29.7–30.1 (2 × OCH CH and 2 × 8 other alkyl chain
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