Synthesis of acyclic, symmetrical 3,3'-allyl dithioethers, from the alkylation of 3-mercapto-2-mercaptomethylprop-1-ene in the presence of sodium hydride

Article abstract of DOI:10.1071/CH11117

A novel method where 3,3'-allyl dithioethers have been prepared from 3-mercapto-2-mercaptomethylprop-1-ene and two mol equivalent of alkyl halide in the presence of two mol equivalent of sodium hydride has been developed. Using this method, bisepoxide, 2,2'-(2-methylenepropane-1,3-diyl)bis(sulfanediyl) bis(methylene)dioxirane (8) has been synthesized from epichlorohydrin, whereas potassium carbonate was unable to deliver this product. These 3,3'-allyl dithioethers can be utilized either as monomers, or with further chemical reactions transformed into more complex monomers, for photoplastic polymer networks.

Full text of DOI:10.1071/CH11117

RESEARCH FRONT
Full Paper
CSIRO PUBLISHING
www.publish.csiro.au/journals/ajc
Aust. J. Chem. 2011, 64, 1083–1093
Synthesis of Acyclic, Symmetrical 3,39-Allyl Dithioethers,
from the Alkylation of 3-Mercapto-2-mercaptomethylprop-1-ene
in the Presence of Sodium Hydride
A
A
,
D
A
A
Cornelis M. Moorhoff, Wayne D. Cook,
Fei Chen, Dat Nghiem,
B
A
,
B
A
C
Carl Braybrook, San H. Thang,
and Christopher N. Bowman
Jiazeng Sun, Timothy F. Scott,
C
A
Department of Materials Engineering, Monash University, Clayton, Vic. 3800,
Australia.
B
Materials Science and Engineering, CSIRO, Clayton, Vic. 3168, Australia.
C
Department of Chemical and Biological Engineering, University of Colorado,
Boulder, CO 80309-0424, USA.
D
Corresponding author. Email: wayne.cook@monash.edu
0
A novel method where 3,3 -allyl dithioethers have been prepared from 3-mercapto-2-mercaptomethylprop-1-ene and two
mol equivalent of alkyl halide in the presence of two mol equivalent of sodium hydride has been developed. Using this
0
method, bisepoxide, 2,2 -(2-methylenepropane-1,3-diyl)bis(sulfanediyl)bis(methylene)dioxirane (8) has been synthe-
0
sized from epichlorohydrin, whereas potassium carbonate was unable to deliver this product. These 3,3 -allyl dithioethers
can be utilized either as monomers, or with further chemical reactions transformed into more complex monomers, for
photoplastic polymer networks.
Manuscript received: 22 March 2011.
Manuscript accepted: 21 July 2011.
Introduction
Our group has an interest in the field of stimuli responsive
any stress that had been imposed on the chains is relieved. It
might be considered that this process could continue without
end, but this does not occur because the process of radical
combination, and depletion of the photoinitiator concentration,
leads to a decrease in the number of radicals. This leads to the
cessation of the chain rearrangements thus limiting the extent of
shape change and/or stress relaxation.
[1]
polymers, and is active in the sub-area of photoplastic poly-
mers. Photoplasticity is the phenomenon where the stimulus of
radiation (usually UV or visible) can induce shape change, shape
creep, or stress relaxation in a crosslinked polymer and this has
the advantage in minimizing warpage or internal stresses that
can develop in crosslinked polymers as a result of polymeriza-
We were interested in extending the range of monomers
which are similar to 2 and we were particularly interested in the
[
2]
tion shrinkage. Such polymeric materials can be of significant
[
1]
importance for use in, for example, dental applications. The
first photoplastic system that we developed used the thiol-ene
0
bisepoxide monomer (2,2 -[2-methylenepropane-1,3-diyl]bis
[sulfanediyl]bis[methylene]dioxirane) (8), based on a thiol-
epichlorohydrin alkylation (Scheme 2, Table 1).
[
3]
reaction to form a crosslinked polymer. The thiol-ene reaction
employs a thiol, in this case pentaerythritol tetrakis(3-mercap-
topropionate) (PETMP) (1), to add to an unsaturated compound
such as 2-methylenepropane-1,3-di(thioethyl vinyl ether)
Reported syntheses of thioethers (sulfides) are numerous and
usually involve the alkylation of thiols (mercaptans) with alkyl
halides under basic conditions. A recent example is the use of
caesium carbonate as a base in DMF as a solvent and tetra-
(MDTVE) 2 (two mol equivalent to one), forming a 3D
network 3, schematically shown as 4 (Fig. 1).
[5]
butylammonium iodide (TBAI) as phase transfer catalyst.
It must be noted that the unique photoplastic property of such
a cured thiol-ene network 3, lies within the (2-methylenepropane-
It was found that potassium carbonate gave slightly lower
yields than caesium carbonate and that iodides gave better
yields than bromides although benzyl chloride gave a somewhat
1
have methylene groups which can be attacked by photogener-
,3-diyl)bis(sulfandiyl) moiety, 5 (Scheme 1). These sub-units
[
5]
higher yield than benzyl bromide. This shows that the type of
halide and alkali-carbonate base (K or Cs) does not have a
dramatic effect on product and yield; however, aprotic polar
solvents seem to have a more pronounced effect on yield. This
was highlighted when benzylmercaptan was alkylated with
ethyl iodide, ethyl bromide, and ethyl tosylate in DMF and
acetonitrile as solvents, in the presence of tetraethylammonium
ꢀ
ated carbon radicals, R , at the terminal alkene carbon of 5 to
form a bond and the simultaneous b-cleavage to regenerate
[
4]
another alkene-group and a sulfanyl radical (Scheme 1). This
radical then is able to attack another alkene in an adjacent
polymer chain, causing b-scission and the formation of a new
sulfanyl radical. As a result of these processes, the network
chains are broken and reformed in new configurations so that
[
6]
hydrogencarbonate as a base to obtain benzylethyl sulfide.
Ó CSIRO 2011 10.1071/CH11117 0004-9425/11/081083

RESEARCH FRONT
1
084
C. M. Moorhoff et al.
O
O
O
O
HS
HS
SH
SH
S
S
O
O
O
O
O
O
2
1
S
S
S
O
O
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
O
O
S
S
S
O
O
S
S
O
O
O
O
S
S
S
S
S
S
S
S
S
O
O
S
S
n
S
S
=
S
S
3
4
=
Fig. 1. Compounds 1–4.
R
S.
S
R
S
1
R
. S
.
S
S
S
S
S
RЉ
RЈ
2
RЉ
RЈ
RЈ
RЉ
3Ј
3
5؅
5
Scheme 1.
Mixture:
HS
Method A
Method B Mixture:
1
2
ϫ NaH
2 ϫ NaH
SH
S
S
Cl
Cl
R
2
R
THF
3Ј
3
THF
7
6
ϩ
X
R
ϩ
HS
R
3,3Ј-Allyl dithioether
Scheme 2.
Thus in DMF and acetonitrile all yields were around 90–93 %
but when diethyl ether was used the yield dropped to 72 % and
with dichloromethane the yield was even lower (41 %). An
alternative approach to thioether synthesis is the use of Lewis
acid catalysis. Thus, an alcohol and a mercaptan gave the
There are only a few examples of the synthesis of allyl
thioethers cited in the literature. One example for synthesizing
mono allylic thioethers is the iodine-catalyzed alkylation of
thiols with allylic alcohols in 1,4-dioxane at room tempera-
[
6]
[
12]
ture.
The disadvantage of this method is that a four-fold
corresponding thioether, using ZrCl on dry silica gel as cata-
4
excess of the thiol is required which is a major limitation in our
work because the synthesis of MDTVE 2, using this method,
would require 2-methylenepropane-1,3-diol, which is very
expensive, and 2-mercaptoethyl vinyl ether which is a difficult
compound to obtain, and will further undergo a thiol-ene
[
7]
lyst, with no solvent. However, this solvent free method did
not suit us, because of the restrictions of the amount we would be
able to convert into thioethers. Potassium fluoride on alumina in
refluxing acetonitrile was used to prepare thioethers, although
the substrates used to demonstrate this preparation were fairly
[
13]
reaction with itself. Another allylic thioether preparation is
the palladium(0)-catalyzed alkylation of allylic carbonates with
[
8]
simple. Certain aromatic heterocyclic mercaptans have been
[
alkylated with alkyl halides in the presence of zinc or
9]
[14]
aromatic thiols,
while ZrCl as an acid catalyst on silica can
4
[
10]
[7]
KOH,
but these reducing or strong basic conditions impose
also be used to condense thiols with allylic alcohols. Evans
and Rizzardo have been able to furnish cyclized compounds
having the 3,3 -allyl dithioether unit, but this method required
the presence of sodium methoxide as a base, highly dilute
reaction conditions, and long reaction times to enhance cycliza-
[15]
tion over generation of the acyclic compound. Thus we have
considerable limitations on the molecules that can be synthe-
sized. None of these synthetic methods investigated thiol-
alkylations with epichlorohydrin, which we were interested in.
Thus, for our work many of these thioether preparations were
0
0
not applicable to the synthesis of 3,3 -allyl dithioethers, particu-
larly because they are incompatible with the alkene moiety used
0
found that for a great number of our novel acyclic 3,3 -allyl
dithioether monomers that we wanted to prepare, we had to
[
11]
in the thiol-ene reaction.

RESEARCH FRONT
Synthesis of Allylic Dithioether Monomers
1085
Table 1. Synthesis of acyclic allyl thioethers, from the alkylation of 3-mercapto-2-mercaptomethylprop-1-ene (7) (Method A) or 3-chloro-
2
-chloromethylprop-1-ene (6) (Method B) in the presence of sodium hydride in THF
HS
SH
Cl
Cl
7
6
Yield using
NaH [%]
Yield using
CO [%]
Run
Reactant 1
Reactant 2
Product {by-product}
K
2
3
O
O
O
S
S
S
S
1
Cl
7
60
80
—
76
81
0
2
ϫ
8
9
OH
OH
OH
OH
OH
HO
OH
2
3
4
5
6
7
7
6
48
85
—
93
2
ϫ
HS
OH
O
Cl
Cl
S
S
S
S
Cl
Cl
2
ϫ
Cl
10
2 ꢁ 6
1
1
HO
OH
S
S
S
OH
2 ϫ HS
12
O
O
O
O
S
S
O
H
H
H
6
7
7
6
3
3
3
3
98
75
—
—
2
2
ϫ
ϫ
Cl
H
H
3
1
1
3
S
S
O
H
HS
3
3
HS
S
n
SH
8
9
2 ꢁ 7
6
trace
—
—
1
4, n ϭ 1, 5, ....
O
O
Cl
S
S
Cl
HS
SH
2 ꢁ 6
56
17
19
A
O
ϩ
Cl
S
S
{14}
20
2
(
Continued)

RESEARCH FRONT
1
086
C. M. Moorhoff et al.
Table 1. (Continued)
Yield using
NaH [%]
Yield using
CO [%]
Run
Reactant 1
Reactant 2
Product {by-product}
K
2
3
O
O
HS
SH
Cl
S
S
Cl
10
2 ꢁ 6
41
–
2
2
18
21
A
O
ϩ
Cl
S
S
{13}
2
2
22
HO
S
S
OH
B
7
11
2 mol equiv. (CH O)
2
n
99
—
23
A
B
By-product.
No NaH used.
adopt a different synthetic strategy. In this paper we have
developed a synthetic method (Scheme 2) for bisepoxide 8
and similar compounds that is fast and uses little solvent
(Table 1). We also describe the photoplastic properties of 8
cured with PETMP 1.
and disadvantages. For example, Method A uses the dimer-
captan 7, a compound having a severe, long-lasting stench.
However, the answer to which of Methods A or B should be used
also depends on the availability of either the alkyl mercaptans or
halides and which method gives the higher yield. In our first
attempt to make the bisepoxide 8, a mixture of 2 mol equivalents
of (ꢂ)-epichlorohydrin and 1 mol equivalent of allyl dithiol 7,
was added to a suspension 2 mol equivalents of sodium hydride
in THF at room temperature, and after an initial 5 min induction
time an extremely exothermic reaction occurred (.508C) con-
comitant with the strong evolution of a large volume of hydro-
gen gas which led to foaming in the reactor. However,
bisepoxide 8 was present among the polymeric material. We,
therefore, performed the reaction at ꢃ208C, but it was necessary
to perform the addition to the sodium hydride suspension as fast
as possible – it appears that a localized exotherm is necessary but
should be controlled. When the addition was performed too
slowly at ꢃ208C the yield of 8 was low. The preparation using
Method B was not investigated since the 2,3-epoxypropane-1-
Results and Discussion
Application of the method of Evans and Rizzardo was found to
[
15]
be unsuitable for the synthesis of bisepoxide 8.
The allylic
dithiol, 3-mercapto-2-mercaptomethylprop-1-ene (7) (Table 1),
with two mol of epichlorohydrin using the strong nucleophilic
sodium methoxide as base, produced only a trace amount of the
bisepoxide 8 in a glue-like product which was presumably a
polymer formed by chain growth anionic polymerization of the
epoxide rings. We then investigated other different methods to
react epichlorohydrin with the allylic dithiol 7. We found that a
[
16]
Protonsponge
[5.4.0]undec-7-ene (DBU),
produced no product, while 1,8-diazabicyclo
[
17]
gave very impure bisepoxide 8.
[
18]
Thus, we were aiming for conditions that would allow fast
deprotonation but have low nucleophilicity. This led us to
develop a new synthetic approach whereby 2 mol equivalents of
sodium hydride was used to abstract the protons of the thiol
groups of 7 but in the presence of two mol equivalents of alkyl
halide. The latter condition is important. We have found that in
the absence of alkyl halides, sodium hydride does not deproto-
nate the dimercaptan 7 in THF to the diionic disulfide species,
not even at an elevated temperature of 508C for an extended time
of 60 min. Depending on which alkyl halide was used with this
method, the liberation of hydrogen varied from being moderate
thiol is difficult to synthesize. The use of sodium hydride as a
base in thioether synthesis is not entirely new: Liu used sodium
hydride to alkylate simple alkyl mercaptans, R-SH (R ¼ Me, Et,
[
19]
Pr, Bu) with a 2-chloroethoxynucleoside compound.
It is noteworthy that when potassium carbonate was used as a
base, the reaction between epichlorohydrin and allylic dithiol 7
led to attack on the epoxide and ring-opening gave product 10
exclusively (Scheme 3). Surprisingly, 10 did not transform to 8.
The bis(chloropropyl sulfide) 10 may be hazardous, since it
resembles b-chloro sulfides, which are powerful vesicants and,
[
20]
therefore, dangerous.
compound, may also be toxic.
The bisepoxide 8, being a reactive
(over 30 min) to fast and exothermic (instantaneous). At this
stage we cannot explain this variation. We denote this method,
whereby a neat mixture of 7 and two mol of alkyl halide is added
to a stirred suspension of two mol of sodium hydride in
We also used a mixture of 2 mol of thioglycerol and allyl
dichloride 6 (Method B), and reacted it at room temperature to
obtain the allylic disulfide 9 in 80 % yield. Note that using
potassium carbonate as a base took over 12 h to react and gave a
lower yield (48 %) (Table 1). We were not able to transform
compound 9 satisfactorily into the bisepoxide 8 using the
Mitsunobu reaction conditions, also because of the poor solubil-
ity of the tetraol 9 in solvents.
0
anhydrous THF at room temperature to produce 3,3 -allyl
dithioether, as Method A (Scheme 2). In Method B, a neat
mixture of 3-chloro-2-chloromethylprop-1-ene (6) with two mol
equivalents of mercaptan (R-SH) is used under the same con-
ditions as for Method A. These two procedures have advantages

RESEARCH FRONT
Synthesis of Allylic Dithioether Monomers
1087
O
O
Mixture:
S
S
S
S
HS
SH
O
8, 0 %
7
OH
OH
Cl
K CO , CH Cl
2
3
2
2
2
ϫ
Cl
Cl
BTEAC
10, 85 %
Scheme 3.
δ 3.36, s
δ 3.36, d, J 8.1 Hz
HS
S
S
SH
HS
SH
n
δ 5.00, s
14, n 1, 5, ...
δ 5.00, s
7
Scheme 4.
O
O
solid NaOH
1
1
2
3
O
O
H O/CH Cl , 35ЊC
S
S
2
2
2
15
O
O
Љ
O
O
O
O
O
S
S
O
16
Scheme 5.
Likewise, following either Method A or B compounds 11, 12,
and 13 were synthesized (Table 1). Thus, using a four-fold
amount of dichloride 6 to 1 equivalent of dimercaptan 7 (Method
A), compound 11 was prepared in good yield and purity; in
addition, 60 % of the fairly expensive 6 used was recovered. It is
important to note that compound 11, in pure form, is prone to
decomposition and polymerization in air. Only a cold solution
use in Method A. As a comparison, potassium carbonate
produced a high yield using the dichloride 6 and 2-thioethanol.
Product 13 (Table 1) was successfully prepared using either
Method A or Method B. It is noteworthy that compounds 9, 12,
and 13 were chemoselectively produced. Compounds 12 and 13
were further transformed to their respective bisepoxides 15 and
16, using 2 mol of epichlorohydrin and excess solid sodium
hydroxide with 1 mol of water in the presence of benzyltriethyl-
ammonium chloride as a phase transfer catalyst in dichloro-
(preferably ,58C) of 11 in dichloromethane, under nitrogen, is
stable. Last mentioned reactants 6 and 7 were then also used in a
reaction with the opposite excess stoichiometry, by adding a
mixture of at least 2 mol of dimercaptan 7 and 1 mol of
dichloride 6 (Method B) to intentionally form the triple allylic
disulfide 14 (Scheme 4, Table 1). However this method gave an
impure, uncharacterizable mixture. Repeating the reaction with
a greater excess of 7 gave a strong sulfur-odorous mixture that
was difficult to purify and a low yield of a product was obtained.
This was analyzed as a mixture of oligomers, including 14 (n ¼ 1
and 5) (Table 1). The only characteristic NMR feature of this
[
21]
methane (Scheme 5). The photoplasticity of these monomers
are presently under investigation and the results will be pub-
lished elsewhere.
We then turned our attention to the synthesis of bis([allylic]
dithioether) systems for novel monomer synthesis that would
0
include two 3,3 -allyl dithioether groups for the preparation of
enhanced photoplastic polymers. The precursor dithiols 17 and
18 (Table 1) were prepared from their respective dichlorides
[
22]
using aqueous, in situ prepared, sodium trithiocarbonate.
product was the absence of the CH –S doublet of the dimercap-
2
Using Method B, the dithiols 17 and 18 were reacted with a
six-fold excess of allyl dichloride 6 to give the desired products
19 and 21 in modest yields of 56 and 41 %, respectively. In
addition, chalcogenated trienedichlorides 20 and 22 were also
obtained from the reaction mixture in low, yet distinctive
amounts, since no further products were isolated (Scheme 6).
In both cases, there appears to be a pattern. In addition to the
expected symmetric A-B-A pattern of 2 mol of 6 (A) alkylated to
1 mol of thiol (B), the thioglycols 17 and 18 also gave the
symmetric A-B-A-B-A pattern of alkylation as a by-product and
tan 7 (d at 3.35) and instead a singlet was present (d at 3.35)
H
H
(Scheme 4). We, therefore, found that when reacting the
difunctional compounds of dihalides and dithiols, to use the
following approach of employing an approximately six-fold
excess of dihalide with one equivalent of dithiol 7 rather than the
other way around.
Compound 12 (Table 1) was prepared from the dichloride 6
and 2-thioethanol as described in Method B, since 2-chloroethanol
could not easily be purchased, because of its high toxicity, for

RESEARCH FRONT
1
088
C. M. Moorhoff et al.
O
1. 2 ϫ NaH, THF, (r.t, o/n)
. 2 mol MeOH, 20ЊC, 48h
HS
SH
ϩ
2 ϫ Cl
Cl
2
17
6
O
Cl
Cl
S
S
S
S
Cl
ϩ
19 56 %
O
O
S
S
Cl
20, 14 %
O
SH
2 ϫ NaH, THF, (r.t, o/n)
HS
O
ϩ
2 ϫ Cl
Cl
18
6
O
O
S
Cl
Cl
Cl
S
O
2
1, 41 %
S
S
O
S
O
O
S
Cl
22, 13 %
Scheme 6.
2
ϫ paraformaldehyde
30ЊC
HS
SH
HO
S
S
S
OH
1
7
23, 99 %
6
ϫ solid NaOH, 1 ϫ H O
2
O
23
O
O
S
O
O
6
ϫ Cl
40 min at 40ЊC
24
O
O
O
S
S
O
S
S
S
S
8
, 61 %, impure
Scheme 7.
the combined yield was ,70 %. We were not able to isolate any
longer oligomeric compounds or by-products like the symmetric
B-A-B and B-A-B-A-B or asymmetric compounds like B-A-B-A.
Few examples of dithioether formation by alkylation of a
dihalide were found in the literature. For example, the study
of the alkylation of thiols with dihaloalkanes X-R-X in the
presence of hydrazine and KOH produced overwhelmingly the
23 with epichlorohydrin under the same basic conditions as
applied for 12 and 13 was unsuccessful. Instead of the desired
bis-epoxide 24, only a crude mixture of impure bisepoxide 8 was
found. This suggests that compound 23 had undergone base-
promoted release of formaldehyde, followed by subsequent
alkylation with epichlorohydrin to form 8 (Scheme 7). Likewise,
in our hands, we were unable to alkylate product 12 (Table 1)
with 2-chloroethyl vinyl ether in the presence of two mol of
NaH. In the last mentioned reaction, an uncharacterizable black
tar was produced.
As an example of the importance of monomers containing
the bisallylic dithio moiety in the phenomenon of photoplasti-
city, Fig. 2 shows the stress relaxation behaviour of two
specimens during irradiation of bisepoxide 8. The specimen
without benzoin ethyl ether (PhC[¼O]CH[OEt]Ph) does not
0
mono-thioether, R S-R-X, and only a little of the dithioether,
[23]
0
0
R S-R-SR , was isolated.
Compounds 19 and 21 are being
further investigated for bis([allylic] dithioether) synthesis and
the occurrence of trienedichlorides 20 and 22 will be further
studied and this research will be reported elsewhere.
Paraformaldehyde and dimercapto compound 7 reacted,
without solvent or base, at 1308C within an hour to form the
diol 23 as a viscous colourless oil. However, the reaction of diol

RESEARCH FRONT
Synthesis of Allylic Dithioether Monomers
1089
0
1
% BEE
% BEE
5
4
3
2
1
ϫ 105
HO
S
S
HO
ϫ 105
O
O
S
S
S
S
S
O
O
O
O
UV on
ϫ 105
O
O
S
OH
S
S
ϫ 105
OH
2
5
n
ϫ 105
0
0
500
1000
Time [s]
1500
Fig. 2. Photoinduced stress relaxation of two specimens of the crosslinked network 25 formed from the crosslinking reaction of bisepoxide 8
and a stoichiometric quantity of pentaerythritol tetra(3-mercaptopropionate) (1) using 0.5 wt-% N,N-dimethylbenzylamine as an anionic catalyst
during cure at 808C for 6 h. One of these specimens also contained 1 wt-% benzoin ethyl ether as a radical source when irradiated with 350 nm UV
radiation.
show any significant change in stress during the irradiation
period because the crosslinked network structure does not
significantly absorb radiation and so no b-scission occurs. In
contrast, the sample containing 1 wt-% benzoin ethyl ether
shows a sudden loss of stress when the UV lamp is switched
on and this stress loss is not significantly recovered when the
irradiation is terminated. This behaviour is initiated by the
production of carbon radicals from the photolysis of the benzoin
ethyl ether. These carbon radicals and the subsequently pro-
duced sulfur radicals add to the allylic dithioether group of
bisepoxide 8 and cause strand rearrangement as shown in
Scheme 1.
III 400 (9.4 Tesla magnet) with a 5 mm broadband inverse probe,
1
H at 400.13 MHz, or a Bruker DPX300 (7.05 Tesla magnet)
1
with a 5 mm quad H/ Cswitchable probe, H at 300.13 MHz,
13
1
1
or a Bruker AV200 (4.7 Tesla magnet) with 5 mm H/ C probe
13
with Z-gradients at 30 8C in CDCl using the residual chloroform
3
peaks at 7.26 ppm as a reference in proton and 77.16 ppm in
carbon spectra.
For the photoplasticity experiments, a specimen 30 mm long,
6 mm wide, and 0.6 mm thick was held between the specimen
grips of a dynamic mechanical spectrometer DMTA IV
(Rheometrics, USA) and then stretched to 4.5 % elongation at
808C. The stress (force applied by the DMTA to keep the sample
stretched, divided by the sample cross-sectional area) was
measured as a function of time. After 300 s, the 350 nm UV
radiation from a Polilight 400 light source (Rofin, Australia) was
used to irradiate the sample for 1200 s with an intensity of
Conclusions
0
A method has been developed whereby novel 3,3 -allyl dithio-
ethers have been prepared from 7 and 2 mol equivalents of alkyl
ꢃ2
9 mW cm at room temperature and then the UV source was
switched off.
halide in the presence of 2 mol equivalents of sodium hydride.
0
Thus, the sensitive bisepoxide, 2,2 -(2-methylenepropane-1,3-
diyl)bis(sulfanediyl)bis(methylene)dioxirane 8, has been syn-
thesized and cured with PETMP 1, to form a photoplastic
polymer network 25.
2
-(2-(2-Mercaptoethoxy)ethoxy)ethanol
Carbon disulfide (5.00 g, 65.67 mmol) was added to a solution of
sodium sulfide nonahydrate (15.00 g, 62.62 mmol) in water
(
8 mL) at 408C, and this mixture was stirred for 4 h. 2-(2-(2-
Experimental
Chloroethoxy)ethoxy)ethanol (10.00 g, 59.30 mmol) was then
added to this deep orange solution of aqueous sodium trithio-
carbonate and was stirred overnight at 608C. The reaction
mixture was cooled to room temperature and diluted with water
(40 mL) and extracted with EtOAc (30 mL) to remove unreacted
chloroalcohol impurities. The aqueous solution was then slowly
acidified with ,6 M H SO until pH ,3. The mixture was then
All reactions were performed under nitrogen. THF was dried
over sodium hydride. All purchased chemicals were used as
received. Compound 6 (Secant Chemicals Inc., MI, USA) was
used for the preparation of 7, according to the method of Evans
[
15]
and Rizzardo.
glycol, and triethylene glycol were purchased from Aldrich,
-thioglycerol from Fluka, and 2-(2-(2-chloroethoxy)ethoxy)
Epichlorohydrin, 2-thioethanol, diethylene
2
4
1
extracted with EtOAc (2 ꢁ 50 mL) and the organic extract was
ethanol from Wako Chemicals.
Mass spectrometry experiments were carried out on a
Waters Q-TOF II instrument, employing electrospray ionization
then treated with 1 g of NaHCO in water (10 mL) and after
3
vigorous extraction resulted in neutralization of the organic
extract. The aqueous layer contained orange, unwanted, water-
soluble byproducts and was discarded. The organic extract was
dried (Na SO ) and filtered and after rotary evaporation gave the
mercaptoalcohol (4.35 g, 44 %). dH (300 MHz, CDCl ) 3.68–
3
3.61 (m, 2H, CH OH), 3.62 (m, 2H, CH O), 3.61 (s, 4H,
2
(ESI) with a 35 eV cone voltage unless otherwise stated and
employing lock spray and sodium iodide as a reference sample.
Other mass spectra experiments were carried out on a
ThermoQuest MAT95XP instrument, employing electron
impact (EI) at 70 eV and employing perfluorokerosene (PFK)
as a reference sample. NMR spectra were run on Bruker Avance
2
4
2
OCH CH O), 3.60 (m, 2H, CH O), 2.70 (dt, J 8.2, 6.4, 2H,
2
2
2
CH S), 2.5 (br s, 1H, OH), 1.58 (t, J 8.2, 1H, SH).
2

RESEARCH FRONT
1
090
C. M. Moorhoff et al.
0
0
2
,2 -(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)bis
3,3 -(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)
(
methylene)dioxirane (8)
dipropane-1,2-diol (9): using K CO
2
3
A 2 mL aliquot of a mixture of 7 (7.00 g, 58.21 mmol, 1 equiv.)
and epichlorohydrin (12.60 g, 136.2 mmol, 2.3 equiv.) was
added to a stirred, oil-free suspension of sodium hydride (3.00 g,
1-Thioglycerol (2.50 g, 23.10 mmol, 2.3 equiv.) and benzyl-
triethylammonium chloride (BTEAC) (0.08 g) was added to a
stirred suspension of potassium carbonate (4.00 g, 28.94 mmol,
2.9 equiv.) and butanone (3 mL), followed by the addition of 6
(1.25 g, 10.0 mmol, 1 equiv.). Within minutes the mixture
became hot and was stirred for 18 h at 758C. The reaction
mixture was then diluted with THF (50 mL) and filtered over a
3 cm thick bed of silica gel. The residue was further washed with
1:1 dichloromethane:petroleum ether (100 mL) and the com-
bined filtrate rotary evaporated dry on a hot waterbath (908C) to
give 9 (1.28 g, 48 %).
1
25.0 mmol, 2.2 equiv.) in THF (75 mL) at ꢃ208C. After a 5 min
induction time, a slow evolution of hydrogen gas occurred. The
remainder of the mixture was then added cautiously and
continuously over 60 min while maintaining the temperature
between ꢃ10 and ꢃ58C. The pale yellow-white mixture was
then allowed to come to room temperature over 20 min. The
reaction mixture was diluted with THF (25 mL) and petroleum
spirits (100 mL) and filtered over a 5 cm bed of silica gel on a
sintered glass funnel to remove polar impurities and NaCl salt.
A further mixture of 50 % THF/50 % petroleum spirits (50 mL)
was then used to remove most of the product from the filter. The
combined clear solution was then rotary evaporated and gave the
crude bisepoxide 8 (8.15 g, 60 %). Removal of excess epichloro-
hydrin and other volatile residues was done at 708C at
0
3,3 -(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)bis(1-
chloropropan-2-ol) (10)
A mixture of 7 (0.70 g, 5.82 mmol, 1 equiv.) and epichloro-
hydrin (1.20 g, 12.97 mmol, 2.2 equiv.) was added to a suspen-
sion of potassium carbonate (1.50 g, 10.85 mmol) and BTEAC
0
.5 mmHg. The product was stirred with hexane (10 mL) at
(
3
0.03 g) in dichloromethane (2 mL) and stirred overnight at
58C. The reaction mixture was cooled to 208C, and then diluted
room temperature to dissolve residual paraffin oil from the
heavier product. The latter was collected and passed though a
small Hirsch funnel having a 3 mm layer of silica gel and a 3 mm
layer of Celite. The hexane was removed from the filtrate under
with EtOAc (5 mL) before filtering the suspension over silica
gel. The clear solution was then rotary evaporated dry to give a
crude, colourless, viscous oil of 10 (1.51 g, 85 %). d (200 MHz,
H
vacuum to give colourless 8 (5.6 g, 41 %). R 0.41 EtOAc 50 %/
f
CDCl ) 5.07 (s, 2H, H C¼), 3.94 (ddd, 2H, J 7.1, 5.1, 4.8,
3
2
petroleum spirits 50 %. dH (300 MHz, CDCl ) 5.07 (s, 2H,
3
2
ꢁ CH CH[OH]CH ), 3.67 (ddd, 2H, J 12.4, 4.6, 0.6, 2 ꢁ
2 2
2
2
H C¼), 3.39 (s, 4H, 2 ꢁ SCH -allyl), 3.12 (dddd, 2H, J 5.7, 5.4,
2
2
ClCH CH[OH]), 3.66 (dd, 2H, J 12.4, 5.2, 2 ꢁ ClCH CH[OH]),
–
O–
4
.3, 2.6, 2 ꢁ CH CH ), 2.80 (dd, 2H, J 4.7, 4.3, 2 ꢁ
2 2 2
2
3
.33 (s, 4H, 2 ꢁ SCH -allyl), 2.77 (dd, 2H, J 4.8, 1.5 Hz, 2 ꢁ
2
–
O–
–O–
2
CH CH ), 2.64 (dd, 2H, J 14.1, 5.7, 2 ꢁ SCH CH CH ),
OH), 2.70 (ddd, 2H, J 13.8, 5.1, 1.5, 2 ꢁ SCH CH[OH]), 2.59
–
O–
2
.59 (m 2H, 2 ꢁ CH CH ), 2.55 (dd, 2H, J 14.1, 5.4, 2 ꢁ
2
(
ddd, 2H, J 13.8, 7.1, 1.3, 2 ꢁ SCH CH[OH]). d (50 MHz,
–
O–
2
C
SCH CH CH ). d (50 MHz, CDCl ) 140.4 (C¼), 116.5
2 2 C 3
CDCl ) 140.1 (1 ꢁ C¼), 117.1 (1 ꢁ H C¼), 70.0 (2 ꢁ CHOH),
3 2
–
O–
–O–
(
H C¼), 51.5 (2 ꢁ CH CH ), 46.7 (2 ꢁ CH CH ), 35.6
2
2
2
4
M ); 211 (51); 179 (100), 161 (10), 129 (13), 117 (17), 109 (18).
8.2 (2 ꢁ CH Cl), 35.8 and 35.2 (4 ꢁ CH S). m/z (EI) 304 (5 %,
þ
–
O–
2
2
(
(
2 ꢁ SCH CH CH ), 33.0 (2 ꢁ SCH -allyl). m/z (EI) 232
3
76), 55 (30). m/z HRMS Anal. Calc. for C H O S :
10 16 2 2
2 2 2
þ
3 %, M ), 175 (37), 143 (49), 117 (53); 101 (17), 85 (100), 73
35 32
2
m/z HRMS Calc. for C H O Cl S : 304.0120. Found:
2
2
10 18
2
(
3
04.0121.
2
32.0586. Found: 232.0582.
(2-Methylenepropane-1,3-diyl)bis((2-(chloromethyl)allyl)
sulfane) (11)
0
3
,3 -(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)
A mixture of 6 (21.32 g, 170.6 mmol, 4.2 equiv.) and 7 (4.85 g,
4
dipropane-1,2-diol (9)
A mixture of 6 (1.83 g, 14.64 mmol, 1 equiv.) and 1-thioglycerol
3.60 g, 33.28 mmol, 2.3 equiv.) in THF (1 mL) was added
within 10 min to a stirred suspension of sodium hydride (0.78 g,
2.50 mmol, 2.14 equiv.) in THF (30 mL) at 208C. A slow
evolution of hydrogen gas occurred for 30 min. This mixture
was then further stirred for 15 h at 208C. The grey suspension
turned white. This mixture was diluted with THF (50 mL) and
filtered over a 3 cm bed of silica gel (3 cm diameter). The filter
was further eluted with 1:1 dichloromethane:petroleum spirits
0.34 mmol, 1 equiv.) was added to a suspension sodium
hydride (2.40 g, 100.0 mmol, 2.5 equiv.) in THF (60 mL) at
208C, resulting in a moderate evolution of hydrogen gas. The
reaction mixture was stirred for 72 h at 208C and then diluted
with THF (60 mL) and filtered over a 5 cm bed of silica gel. The
residue was further eluted with THF (100 mL) and the combined
filtrate rotary evaporated dry on a hot waterbath (708C) to give
the crude, colourless oil 11 (11.15 g, 93 %) which solidified as a
waxy white material. The waxy solid product was dissolved in
ethyl acetate (15 mL) at 508C. This solution was quickly cooled
to room temperature and then put immediately (before crystal-
lizing) on a 100 g silica gel column and chromatographed using
5 % EtOAc/95 % petroleum spirits, increasing to 10 % EtOAc/
90 % petroleum spirits as eluent. After rotary evaporation and
high-vacuum removal of solvents, 11 (9.15 g, 76 %) was
isolated. d (400 MHz, CDCl ) 5.25 (d, 2H, J 0.8, H C¼), 5.09
(
3
(
100 mL) and the combined filtrate rotary evaporated dry on a
hot waterbath (908C) to give a clear, viscous oil of 9 (3.14 g,
0 %) that solidified at room temperature as a waxy solid.
8
d (300 MHz, [D ]DMSO) 4.99 (s, 2H, H C¼), 4.72 (d, 2H, J
H
6
2
5
2
.0, 2 ꢁ OH), 4.52 (t, 2H, J 5.6, 2 ꢁ OH), 3.53 (h, 2H, J 5.3,
ꢁ CH CH[OH]CH ), 3.35 (d, 2H, J 4.4, 2 ꢁ CH), 3.30 (d, 2H,
2
2
H
3
2
J 5.6, 2 ꢁ CH), 3.24 (s, 4H, 2 ꢁ SCH ), 2.51 (dd, 2H, J 13.2, 5.3,
(d, 2H, J 1.2, H C¼), 5.02 (s, 2H, H C¼), 4.20 (d, 4H, J 0.8,
2 2 C
2
2
2
2
ꢁ CH), 2.33 (dd, 2H, J 13.2, 6.6, 2 ꢁ CH). d (75 MHz, [D ]
2 ꢁ ClCH ), 3.21 (d, 8H, J 1.2, 4 ꢁ SCH -allyl). d (100 MHz,
3 2
C
6
DMSO) 142.0 (C¼), 116.2 (H C¼), 71.2 (2 ꢁ OCH), 65.4
CDCl ) 141.0 (2 ꢁ C¼), 140.2 (1 ꢁ C¼), 117.6 (2 ꢁ H C¼),
2 2 2
2
(
2
2 ꢁ OCH ), 36.9 (2 ꢁ SCH ), 35.3 (2 ꢁ SCH -allyl). m/z (EI)
116.5 (1 ꢁ H C¼), 46.1 (2 ꢁ CH Cl), 34.8 (2 ꢁ CH -allyl),
2 3
2
2
2
þ
68 (M , 5 %), 193 (41), 161 (65), 99 (22), 91 (100), 87 (29), 85
33.8 (2 ꢁ CH -allyl). Mp 54–58 8C. m/z (ESI, in CHCl /MeOH)
3
4
2
67), 55 (40). m/z HRMS Calc. for C H O S : 268.0798.
þ
(
Found: 268.0797.
319 (100 %, [M þ Na] ). m/z HRMS (ESI) Calc. for
12 18 2 2
1
0
20
2
3
C H Cl S Na: 319.0125. Found: 319.0113. Note: the product
2

RESEARCH FRONT
Synthesis of Allylic Dithioether Monomers
1091
was diluted as a 1:1 compound:dichloromethane solution and
stored at 108C to inhibit 11 going off.
11-Methylene-3,6,16,19-tetraoxa-9,13-dithiahenicosane-
1,21-diol (13) using Compound 7
A mixture of 7 (1.20 g, 10.0 mmol, 1 equiv.) and 2-(2-(2-
chloroethoxy)ethoxy)ethanol (3.50 g, 20.76 mmol, 2.1 equiv.)
was added neat within 2 min to a suspension of sodium hydride
0
2
,2 -(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)
diethanol (12)
(0.51 g, 21.25 mmol, 2.1 equiv.) in THF (20 mL) at 208C. An
A mixture of 6 (7.50 g, 60.00 mmol) and 2-mercaptanethanol
(9.60 g, 122.9 mmol) was added neat within 30 min to a sus-
pension of sodium hydride (3.0 g, 125 mmol) in THF (120 mL)
at 208C. After an induction time of 5 to 10 min a slow evolution
of hydrogen gas resulted with an increase in reaction tempera-
ture to 458C. This mixture was then further stirred for 24 h at
immediate evolution of hydrogen gas occurred and the reaction
was exothermic (508C) and was cooled in a waterbath. This now
yellowish-white reaction mixture was stirred for 24 h and was
diluted with THF (30 mL) and filtered over a 3 cm bed of silica
gel (3 cm diameter). The filter was further eluted with THF
(
(
30 mL) and the filtrate rotary evaporated dry on a hot waterbath
708C) to give the crude product 13 (2.71 g, 71 %).
2
08C. This mixture was diluted with THF (50 mL) and filtered
over a 4 cm bed of silica gel (5 cm diameter). The filter was
further eluted with THF (200 mL) and the combined filtrate
rotary evaporated dry to give, after high-vacuum drying at 908C,
a viscous oil of 12 (10.10 g, 81 %). d (300 MHz, CDCl ) 5.01
0
2
1
,2 -(7-Methylene-2,12-dioxa-5,9-dithiatridecane-1,
3-diyl)dioxirane (15)
H
3
Crude 12 (2.90 g, 13.94 mmol, 1 equiv.) was added within 5 min
to a mixture of NaOH (7.00 g, 175 mmol, 12 equiv.), BTEAC
0.60 g, 3.00 mmol), water (0.60 g, 16.7 mmol, 1.2 equiv.), and
epichlorohydrin (16.00 g, 173.9 mmol, 13 equiv.) and stirred for
40 min at 408C. The reaction mixture was then cooled to 208C
and the solid paste was washed twice with CH Cl (50 mL) to
(
2
d, 2H, J 0.6, H C¼) 3.69 (t, 4H, J 6.0, 2 ꢁ OCH ), 3.29 (s, 4H,
2
2
ꢁ SCH -allyl), 2.62 (t, 4H, J 6.0, 2 ꢁ SCH ), 2.5 (br s, 2 ꢁ
C 3 2
2
2
(
OH). d (75 MHz, CDCl ) 140.6 (C¼), 116.3 (H C¼), 60.4
(
2
2 ꢁ OCH ), 35.1 (2 ꢁ SCH -allyl), 34.1 (2 ꢁ SCH ). m/z (EI)
2
2
2
þ
08 (6 %, M ); 163 (24), 131 (93), 130 (32), 99 (61), 86 (39),
3
2
2
2
85 (100), 55 (44). m/z HRMS Calc. for C H O S : 208.0586.
8 16 2 2
Found: 208.0581.
dissolve all organic material. The combined CH Cl layer was
2
2
washed with water (50 mL) and the organic layer dried over
sodium sulfate. This solution was then treated with petroleum
spirits (50 mL) and filtered over silica gel and the silica gel was
eluted with 50 % ethyl acetate/50 % petroleum spirits. Rotary
evaporation of the filtrate on a hot waterbath (908C) gave a crude
0
2
,2 -(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)
diethanol (12): K CO method
2
3
2-Mercaptoethanol (2.00 g, 25.60 mmol) in butanone (3 mL)
was added to potassium carbonate (4.45 g, 32.20 mmol) and
BTEAC (0.06 g) as a phase transfer catalyst. Compound 6
(1.27 g, 10.16 mmol) was then added to the stirred reaction
mixture upon which the reaction mixture became warm. This
mixture was further stirred for 18 h at 758C. The reaction mix-
ture was then diluted with EtOAc (12 mL) and filtered over a
oil of 15 (2.15 g, 48 %). dH (300 MHz, CDCl ) 4.96 (s, 2H,
3
–
O–
H C¼), 3.71 (dd, 2H, J 11.6, 3.0, 2 ꢁ OCH CH CH ), 3.63
2
2
2
(
dd, 2H, J 9.6, 6.6, 2 ꢁ OCH CH S), 3.56 (dd, 2H, J 9.6, 6.6,
2
2
–
O–
2
ꢁ OCH CH S), 3.33 (dd, 2H, J 11.6, 5.7, 2 ꢁ OCH CH
2 2
2
2
2
–
O–
CH ), 3.27 (s, 4H, 2 ꢁ SCH -allyl), 3.08 (m, 2H, 2 ꢁ CH
–
O–
CH ), 2.73 (dd, 2H, J 5.1, 4.8, 2 ꢁ CH CH ), 2.55 (dd, 4H,
C
2
2
–
O–
J 6.9, 6.9, 2 ꢁ SCH ), 2.54 (m, 2H, 2 ꢁ CH CH ). d
2
2
2
cm bed of silica gel (3 cm diameter). The filter was further
(
7
3
75 MHz, CDCl ) 140.8 (C¼), 115.9 (H C¼), 71.5 (2 ꢁ OCH ),
3
2
2
eluted with EtOAc (100 mL) and the clear combined filtrate
rotary evaporated dry on a hot waterbath (908C) to give a clear,
viscous oil of 12 (1.97 g, 93 %).
–
O–
–O–
0.6 (2 ꢁ OCH ), 50.7 (2 ꢁ CH CH ), 44.0 (2 ꢁ CH CH ),
2
2
2
5.6 (2 ꢁ SCH -allyl), 30.4 (2 ꢁ SCH CH O). m/z (EI) 320
2 2 2
þ
(
4 %, M ), 219 (29), 187 (100), 117 (20), 113 (22), 99 (17),
7 (20), 86 (38), 85 (43), 61 (20), 57 (49), 55 (14). m/z HRMS
8
3
2
1
1
1-Methylene-3,6,16,19-tetraoxa-9,13-dithiahenicosane-
,21-diol (13) using Compound 6
Calc. for C14H O S : 320.1111. Found: 320.1103.
24 4 2
0
2
,2 -(13-Methylene-2,5,8,18,21,24-hexaoxa-11,15-
A mixture of 6 (1.50 g, 12.0 mmol, 1 equiv.) and crude 2-(2-(2-
mercaptoethoxy)ethoxy)ethanol (4.10 g, 24.66 mmol, 2.1
equiv.) was added neat in 5 min to a suspension of sodium
hydride (0.60 g, 25.00 mmol, 2.1 equiv.) in THF (20 mL). An
immediate, very rapid evolution of hydrogen gas occurred,
foaming up into the overflow bulb and the reaction was exo-
thermic (.508C). The now yellowish-white reaction mixture
was stirred overnight at 208C and then diluted with THF (30 mL)
and filtered over a 3 cm bed of silica gel (3 cm diameter). The
filter was further eluted with THF (30 mL) and the filtrate rotary
evaporated dry on a hot waterbath (708C) to give a viscous oil of
dithiapentacosane-1,25-diyl)dioxirane (16)
Crude 13 (5.40 g, 14.04mmol, 1 equiv.) was rapidly added within
5 min to a mixture of NaOH (7.00 g, 175 mmol, 12 equiv.),
BTEAC (0.60 g, 3.00 mmol), water (0.60 g, 16.70 mmol,
1.2 equiv.), epichlorohydrin (16.00 g, 173.9 mmol, 13 equiv.),
and stirred for 40 min at 408C. The reaction mixture was then
cooled to 208C and the solid paste was washed twice with
CH Cl (50 mL) to dissolve all organic material. The combined
2
2
CH Cl layer was washed with water (50 mL) and the organic
2
2
layer dried over sodium sulfate. This solution was then treated
with 50 mL of petroleum spirits and filtered over silica gel and
the silica gel was eluted with 50 % ethyl acetate/50 % petroleum
spirits. Rotary evaporation of the filtrate on a hot waterbath
(908C) gave a crude oil of 16 (3.85 g, 55 %). dH (400 MHz,
CDCl ) 5.00 (s, 2H, H C¼), 3.72 (dd, 2H, J 11.7, 3.2, 2 ꢁ
1
3
3 (4.52 g, 98 %). d (200 MHz, CDCl ) 5.00 (s, 2H, H C¼),
H
3
2
.7–3.55 (2 ꢁ m, 12H, 6 ꢁ OCH ), 3.60 (s, 8H, 2 ꢁ
2 2 2
2
OCH CH O), 3.30 (s, 4H, 2 ꢁ SCH -allyl), 2.60 (t, J 6.8, 4H,
2
ꢁ CH S), 2.6 (br s, 2H, 2 ꢁ OH). d (100 MHz, CDCl ) 140.9
2 2
2
C
3
(
(
(
C¼), 116.0 (H C¼), 72.5, 70.6, 70.4, 70.3 (8 ꢁ CH O), 61.7
2 2 2
3
2
–
O–
2 ꢁ CH OH), 35.7 (2 ꢁ SCH -allyl), 30.4 (2 ꢁ CH S). m/z
OCH CH CH ), 3.7–3.6 (m, 12H, 6 ꢁ OCH ), 3.60 (s, 8H,
2
2
2
þ
–O–
ESI, in MeOH, 100 eV cone voltage) 407 (100 %, [M þ Na] ).
2 ꢁ OCH CH O), 3.43 (dd, 2H, J 11.7, 5.6, 2 ꢁ OCH CH
2 2
2
2
2
3
6
2
–O–
m/z HRMS (ESI) Calc. for C H O S Na: 407.1538. Found:
1
CH ), 3.31 (s, 4H, 2 ꢁ SCH -allyl), 3.14 (m, 2H, 2 ꢁ CH
2 2
6
32
2
–O–
4
07.1534.
CH ), 2.78 (dd, 2H, J 4.8, 4.8, 2 ꢁ CH CH ), 2.61 (t, J 6.4, 4H,

RESEARCH FRONT
1
092
C. M. Moorhoff et al.
–
O–
2
ꢁ SCH ), 2.60 (m, 2H, 2 ꢁ OCH CH CH ). d (100MHz,
exothermic (508C). This now yellowish-white reaction mixture
was then stirred overnight at 208C and then diluted with THF
(30 mL) and filtered over a 3 cm bed of silica gel (3 cm dia-
meter). The filter was further eluted with THF (30 mL) and the
combined filtrate rotary evaporated dry on a hot waterbath
(708C) to give 4.9 g of crude product as an opaque oil. Chro-
matography of the crude product on 90 g of silica gel (30 cm
column) started with slow elution with 5 % EtOAc/95 %
hexanes and after 100 mL of eluent increased to 10 % EtOAc/
90 % hexanes and then to 15 % EtOAc/85 % hexanes to give 21
2
2
2
C
CDCl ) 140.9 (C¼), 116.0 (H C¼), 72.0 (2 ꢁ OCH ), 70.8
3
2
2
–O–
(
2ꢁ OCH ), 70.7 (6 ꢁ OCH ), 70.4 (2 ꢁ OCH ), 50.8 (2 ꢁ CH
2
2
2
–
O–
CH ), 44.3 (2 ꢁ CH CH ), 35.7 (2 ꢁ SCH -allyl), 30.4 (2 ꢁ
2 2 2
þ
SCH CH O). m/z (EI) 496 (4 %, M ): 307 (76); 275 (100), 144
2
2
(
(
25), 117 (72), 115 (97), 113 (28), 101 (43), 87 (43), 86 (32), 85
3
2
29), 57 (57). m/z (HRMS) Anal. Calc. for C H O S :
2
2
40
8
2
4
96.2159. Found: 496.2166.
0
2
,2 -Oxybis(ethane-2,1-diyl)bis((2-(chloromethyl)allyl)
sulfane) (19) and 2,22-Bis(chloromethyl)-12-methylene-
,17-dioxa-4,10,14,20-tetrathiatricosa-1,22-diene (20)
(
5
3
1.33 g, 41 %). d (300 MHz, CDCl ) 5.24 (d, 2H, J 1.0, H C¼),
H
3
2
.11 (dt, 2H, J 1.0, 1.0, H C¼), 4.20 (d, 4H, J 1.0, 2 ꢁ CH Cl),
2 2
7
2
2
.63 (t, 4H, J 6.6, 2 ꢁ CH O), 3.60 (s, 4H, 2 ꢁ CH O), 3.34
0
A mixture of 6 (7.50 g, 60.0 mmol, 6 equiv.) and 2,2 -
oxydiethanethiol (17) (1.37 g, 9.91 mmol, 1 equiv.) was added
neat in one addition to a suspension of sodium hydride (0.60 g,
(
d, 4H, J 1.0, 2 ꢁ SCH -allyl), 2.62 (t, 4H, J 6.6, 2 ꢁ CH S).
2
2
d (75 MHz, CDCl ) 141.3 (2 ꢁ C¼), 117.5 (2 ꢁ H C¼), 70.9
C 3 2
(
(
[
3
8
5
2 ꢁ OCH ), 70.5 (2 ꢁ OCH ), 45.9 (2 ꢁ ClCH -allyl), 35.2
2
2
2
2
5.00 mmol, 2.5 equiv.) in THF (30 mL) under nitrogen. After
2 ꢁ SCH -allyl), 30.6 (2 ꢁ CH S). m/z (ESI) 381 (100 %,
2
2
the addition, the reaction mixture reacted very slowly, evolving
hydrogen gas, and was stirred overnight. NMR analysis showed
that only about half of the reaction mixture had reacted. The grey
suspension mixture was then treated with anhydrous methanol
þ
35 32
M þ Na] ); m/z HRMS (ESI) Calc. for C H O Cl S Na:
1
4
24
2
2
2
81.0492. Found: 381.0500. Further elution with 20 % EtOAc/
0 % hexanes gave 22 (0.35 g, 13 %). dH (300 MHz, CDCl3)
.24 (d, 2H, J 0.9, H C¼), 5.11 (d, 2H, J 0.9, H C¼), 5.01 (s, 2H,
2
2
(
0.5 mL) which resulted in an immediate evolution of hydrogen
H C¼), 4.20 (d, 4H, J 0.9, 2 ꢁ CH Cl), 3.63 (t, 4H, J 6.9, 2 ꢁ
2
2
gas and the grey mixture become light-yellow. The reaction
mixture was stirred at 208C for 48 h. This mixture was then
diluted with THF (30 mL) and filtered over a 3 cm bed of silica
gel (3 cm diameter). The filter was further eluted with THF
20 mL) and the filtrate rotary evaporated dry on a hot waterbath
708C) to give the crude product as a slightly pale-yellow oil
2.95 g). Excess 6 (1.69 g, 33.7 %) was also recovered. This
crude product was then chromatographed on 50 g of silica gel
30 cm column) and eluted with 5 % EtOAc/95 % petroleum
spirits to give 19 (1.65 g, 56 %) dH (400 MHz, CDCl ) 5.24
CH O), 3.62 (t, 4H, J 6.9, 2 ꢁ CH O), 3.61 (s, 8H, 4 ꢁ CH O);
2
2
2
3
2
(
(
.34 (d, 4H, J 0.9, 2 ꢁ SCH -allyl), 3.32 (s, 4H, 2 ꢁ SCH -allyl),
2 C 3
2
2
.62 (t, 8H, J 6.9 Hz, 4 ꢁ CH S). d (75 MHz, CDCl ) 141.2
2 ꢁ C¼), 141.0 (C¼), 117.5 (2 ꢁ H C¼), 116.1 (H C¼), 70.9
2 2 2
2
2
(
(
(
2 ꢁ OCH ), 70.8 (2 ꢁ OCH ), 70.5 (2 ꢁ OCH ), 70.4 (2 ꢁ
OCH ), 45.9 (2 ꢁ ClCH -allyl), 35.8 (2 ꢁ SCH -allyl), 35.2
2
2
2
(
2 ꢁ SCH -allyl), 30.6 (2 ꢁ CH S), 30.5 (2 ꢁ CH S). m/z (ESI)
2
2
2
þ
6
m/z HRMS (ESI) Calc. for C H O Cl S Na: 615.1241.
15 (79 %, [M þ Na] ), 529 (26), 419 (29), 437 (28), 319 (100).
24 42 4 2 4
(
35 32
3
Found: 615.1240.
(
(
(
(
(
(
dt, 2H, J 0.8, 0.8, H C¼), 5.11 (dt, 2H, J 0.8, 0.8, H C¼), 4.20
2
2
d, 4H, J 0.8, 2 ꢁ ClCH ), 3.60 (t, 4H, J 6.8, 2 ꢁ OCH ), 3.34
2 2
(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)
dimethanol (23)
d, 4H, J 0.8, 2 ꢁ SCH -allyl), 2.61 (t, 4H, J 6.8, 2 ꢁ SCH ). d
2
2
C
100 MHz, CDCl ) 141.3 (2 ꢁ C¼), 117.5 (2 ꢁ H C¼), 70.6
3
2
Paraformaldehyde (1.20 g, 39.96 mmol) and
7 (2.40 g,
2 ꢁ OCH ), 45.9 (2 ꢁ ClCH ), 35.3 (2 ꢁ SCH -allyl), 30.8
2
2
2
þ
19.96 mmol) were mixed to a paste and stirred and heated at
308C. After 1 h the paste had become a translucent gel and was
2 ꢁ CH S). m/z (EI) 314 (2 %, M ), 227 (42), 225 (100),
2
1
1
6
51 (36), 149 (97), 121 (71), 120 (33), 113 (85), 89 (56), 85 (41),
3
1 (25). m/z HRMS Calc. for C H O Cl S : 314.0327.
5
32
2
cooled to 208C. This mixture was dissolved in acetone, the
opaque solution filtered over Celite, and evaporated to give a
clear oil of 23 (3.60 g, 99 %). d (200 MHz, CDCl ) 5.13 (s, 2H,
1
2
20
2
Found: 314.0317. Further elution with 90 % hexanes/10 %
EtOAc gave 20 (0.35 g, 14 %). dH (300 MHz, CDCl ) 5.22
H
3
3
H C¼), 4.68 (s, 4H, 2 ꢁ SCH OH), 3.45 (s, 4H, 2 ꢁ SCH -
2
2
2
(
d, 2H, J 0.9, H C¼), 5.09 (dt, 2H, J 0.9, 0.9, H C¼), 4.99 (s, 2H,
2
2
allyl), 2.6 (br s, 2H, 2 ꢁ OH). d (200 MHz, [D ]DMSO) 5.56
H
6
H C¼), 4.18 (d, 4H, J 0.9, 2 ꢁ ClCH ), 3.58 (t, 4H, J 6.6, 2 ꢁ
2 2
(
2
t, 2H, J 7.0, 2 ꢁ OH), 5.04 (s, 2H, H C¼), 4.54 (d, 4H, J 7.0,
2
OCH ), 3.57 (t, 4H, J 6.6, 2 ꢁ OCH ), 3.32 (d, 4H, J 0.9, 2 ꢁ
2
2
ꢁ SCH OH), 3.33 (s, 4H, 2 ꢁ SCH -allyl). d (50 MHz,
2 2 C
SCH -allyl), 3.30 (s, 4H, 2 ꢁ SCH -allyl), 2.59 (t, 4H, J 6.6,
2
2
CDCl ) 141.2 (C¼), 116.6 (H C¼), 65.2 (2 ꢁ OCH ), 34.0
3
2
2
2
1
7
(
(
ꢁ SCH ), 2.58 (t, 4H, J 6.6, 2 ꢁ SCH ). d (75 MHz, CDCl )
2 2
2
2
C
3
(2 ꢁ SCH -allyl).
2
41.2 (2 ꢁ C¼), 140.9 (C¼), 117.5 (2 ꢁ H C¼), 116.0 (H C¼),
0.5 (2 ꢁ OCH ), 70.4 (2 ꢁ OCH ), 45.8 (2 ꢁ ClCH ), 35.8
2
2
2
Attempted Reaction of 23 with Epichlorohydrin
Under Strong Basic Conditions
2 ꢁ SCH -allyl), 35.2 (2 ꢁ SCH -allyl), 30.6 (4 ꢁ CH S). m/z
þ
2
2
2
ESI, in MeOH) 527 (91 %, [M þ Na] ), 403 (100), 337 (67).
3
5
m/z HRMS (ESI) Calc. for C H O Cl S Na: 527.0697.
32
2
Crude 23 (2.60 g, 14.42 mmol, 1 equiv.) was rapidly added
within 5 min to a mixture of NaOH (3.50 g, 87.5 mmol,
2
0
34
2
4
Found: 527.0716.
6
1
6
.1 equiv.), BTEAC (0.30 g, 1.50 mmol), water (0.30 g,
6.67 mmol, 1.2 equiv.), epichlorohydrin (8.00 g, 88.35 mmol,
.1 equiv.), and stirred for 40 min at 408C. The reaction mixture
2
1
7
1
,15-Bis(chloromethyl)-7,10-dioxa-4,13-dithiahexadeca-
,15-diene (21) and 2,28-Bis(chloromethyl)-15-methylene-
,10,20,23-tetraoxa-4,13,17,26-tetrathianonacosa-
,28-diene (22)
was then cooled to 208C and the solid paste was washed twice
with CH Cl (30 mL) to dissolve all organic material. The
2
2
combined CH Cl layer was washed with water (20 mL) and
2
2
A mixture of 6 (7.00 g, 56.00 mmol, 6 equiv.) and distilled 18
1.65 g, 9.05 mmol, 1 equiv.) was added neat in one addition to a
stirring grey suspension of sodium hydride (0.45 g, 18.75 mmol,
.04 equiv.) in THF (30 mL) at 208C. An immediate, very rapid
evolution of hydrogen gas occurred and the reaction was
the organic layer dried over sodium sulfate. This solution was
then treated with petroleum spirits (10 mL) and filtered over
silica gel and the silica gel was eluted with 50 % ethyl acetate/
50 % petroleum spirits. Rotary evaporation of the filtrate on a
hot waterbath (908C) gave a crude oil of 8 (2.05 g, 61 %).
(
2

RESEARCH FRONT
Synthesis of Allylic Dithioether Monomers
1093
Acknowledgements
[12] X. Zhang, W. Rao, P. W. H. Chan, Synlett 2008, 2204. doi:10.1055/
S-2008-1078254
13] (a) B. A. Trofimov, A. S. Atavin, A. V. Gusarov, S. V. Amosova, S. E.
The authors acknowledge the support of ARC DP0877382 in this work and
thank Dr Tara Schiller for her advice.
[
Korostova, Zhurnal Organicheskoi Khimii 1969, 5, 816.
(b) B. A. Trofimov, A. S. Atavin, A. V. Gusarov, M. F. Shostakovskii,
N. I. Golovanova, IzvestiyaAkademiiNaukSSSR. SeriyaKhimicheskaya
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