Reactions and products revealed by NMR spectra of deuterated dimethylsulfoxide with iodomethane in neutral and basic media

Article abstract of DOI:10.1080/17415993.2015.1066376

Reactions occurring within each one of two mixtures, a mixture of deuterated dimethylsulfoxide, DMSO-d₆, with CH₃I (system I) and another mixture of DMSO-d₆ with CH₃I, NaOH and water (system II), were monitored by 1D and 2D nuclear magnetic resonance (¹H, ¹³C, heteronuclear multiple quantum correlation, heteronuclear multiple bond correlation and diffusion-ordered NMR spectroscopy). The analysis of the spectra as a function of reaction time revealed the formation of methoxy-bis(trideuteromethyl)sulfonium iodide, 3; the precipitation of hexadeuterated trimethyloxosulfonium, 2a; a methyl exchange between DMSO-d₆ and 2a to produce trideuterated dimethylsulfoxide, DMSO-d3, 4, and nona-deuterated trimethyloxosulfonium iodide, 2b; and the production of small quantities of methanol, 5, trideuterated dimethylsulfide, 6, and dimethyl ether, 7, in both systems. Only system II precipitated deuterated [Na4(DMSO-dx)15][(I3)3I], 1a, a green solid with metallic shine that corresponds to an isotopomer of 1, which is produced by the self-assembly of DMSO and CH₃I in the presence of NaOH and water.

Full text of DOI:10.1080/17415993.2015.1066376

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Reactions and products revealed
by NMR spectra of deuterated
dimethylsulfoxide with iodomethane in
neutral and basic media
E. Avella-Morenoa, N. Nuñez-Dallosa, L. Garzón-Tovara & A.
Duarte-Ruiza
a Departamento de Química, Facultad de Ciencias, Universidad
Nacional de Colombia, Sede Bogotá, Carrera 30 No. 45-03,
Bogotá, Colombia
Published online: 12 Aug 2015.
Click for updates
To cite this article: E. Avella-Moreno, N. Nuñez-Dallos, L. Garzón-Tovar & A. Duarte-Ruiz (2015):
Reactions and products revealed by NMR spectra of deuterated dimethylsulfoxide with iodomethane
in neutral and basic media, Journal of Sulfur Chemistry, DOI: 10.1080/17415993.2015.1066376
To link to this article: http://dx.doi.org/10.1080/17415993.2015.1066376
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Journal of Sulfur Chemistry, 2015
http://dx.doi.org/10.1080/17415993.2015.1066376
Reactions and products revealed by NMR spectra of deuterated
dimethylsulfoxide with iodomethane in neutral and basic media
E. Avella-Moreno, N. Nuñez-Dallos, L. Garzón-Tovar and A. Duarte-Ruiz∗
Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Sede Bogotá,
Carrera 30 No. 45-03, Bogotá, Colombia
(Received 22 June 2015; accepted 23 June 2015)
Reactions occurring within each one of two mixtures, a mixture of deuterated dimethylsulfoxide, DMSO-
d6, with CH3I (system I) and another mixture of DMSO-d6 with CH3I, NaOH and water (system II),
were monitored by 1D and 2D nuclear magnetic resonance (1H, 13C, heteronuclear multiple quan-
tum correlation, heteronuclear multiple bond correlation and diffusion-ordered NMR spectroscopy).
The analysis of the spectra as a function of reaction time revealed the formation of methoxy-
bis(trideuteromethyl)sulfonium iodide, 3; the precipitation of hexadeuterated trimethyloxosulfonium, 2a;
a methyl exchange between DMSO-d6 and 2a to produce trideuterated dimethylsulfoxide, DMSO-d3,
4, and nona-deuterated trimethyloxosulfonium iodide, 2b; and the production of small quantities of
methanol, 5, trideuterated dimethylsulfide, 6, and dimethyl ether, 7, in both systems. Only system II pre-
cipitated deuterated [Na4(DMSO-dx)15][(I3)3I], 1a, a green solid with metallic shine that corresponds to
an isotopomer of 1, which is produced by the self-assembly of DMSO and CH3I in the presence of NaOH
and water.
Keywords: iodomethane; deuterated dimethylsulfoxide; NMR analysis of reaction mixtures; isotopomer
of [Na4(DMSO)15][(I3)3I]; methyl exchange
1. Introduction
=
Dimethyl sulfoxide (DMSO), CH3(S O)CH3, was obtained for the first time in 1867 by Alexan-
der Mikhaylovich Zaytsev through the oxidation of dimethyl sulfide, CH3SCH3. It is widely
known as a polar aprotic solvent and for its usefulness in medicine.[1,2] DMSO is nucleophilic
through oxygen (hard donor) or sulfur (soft donor), electrophilic in virtue of the weak acid-
ity of its hydrogens, and it acts as an oxidizing or reducing agent with some compounds.[3,4]
These qualities allow it to solvate hydrophilic and hydrophobic substances, to form complexes
*Corresponding author. Email: aduarter@unal.edu.co
© 2015 Taylor & Francis

2
E. Avella-Moreno et al.
with metals and with organic substances, and to generate cations such as alkoxy dimethyl-
+
+
=
sulfonium, (CH3)2( S–OR), alkyl dimethyloxosulfonium, (CH3)2R( S O), and ylide anions
CH3R(+S = O)CH−2 , among other products.[3–11]
In nuclear magnetic resonance (NMR) spectroscopy, hexadeuterated dimethyl sulfoxide
=
(DMSO-d6), CD3(S O)CD3 is a common solvent, and is not expected to react with solutes.
It is used for its capacity to dissolve heterocyclic compounds and salts that are insoluble in
other solvents, but its low volatility, its viscosity, its high affinity for water, and eventually some
reactivity make it an inconvenient solvent.[11]
Recently the synthesis of [Na4(DMSO)15][(I3)3I], 1, was published. Compound 1 is a hexaco-
ordinated sodium complex that is formed through a self-assembly process driven by ion–dipole
interactions, where DMSO molecules are connected with Na+ ions t−o form a one-dimensional
(1D) oligomeric structure stabilized by linear chains of triiodide (I3 ) and iodide (I−) anions
along the crystal.[12]
In that earlier work, 1 was synthesized at room temperature in a reaction medium containing
DMSO, iodomethane (CH3I), sodium hydroxide (NaOH) and water in which trimethyloxosulfo-
nium iodide was also obtained, [(CH3)3SO]I, 2, [12] (some details of the structures of 1 and 2
are given in supplementary information). Since information published about the chemical reac-
tions that occur in this reaction medium was scarce,[12,13–15] this work proposes to study two
reaction systems (I and II) by NMR as a function of time in analogous conditions to those in
the synthesis of 1 and 2, with the objective of better understanding what happens during the
process and determining the possible species and reactions that contribute to the formation and
stabilizing of the oligomeric structure of 1. System I is a mixture of DMSO-d6 with CH3I and
system II is a mixture of DMSO-d6 with CH3I, NaOH and water. An analysis is presented for the
evolution of the signals in a series of 1H NMR and 13C NMR spectra of both systems which were
maintained for more than 300 days in sealed tubes at 295 2 K, through which the reactivity of
DMSO-d6 with CH3I is observed.
2. Results and discussion
Prior to and during the monitoring of systems I and II containing CH3I in DMSO-d6, the NMR
spectra showed signals in addition to those expected if no reaction had occurred within the media.
Those signals include a quintet at δ 2.50 (DMSO-d5) and singlets at δ 2.18 (CH3I), δ 3.33 or 3.30
(H2O) and δ 3.53–3.57 (1,4-dioxane) in 1H NMR spectra, and a septet at δ 39.5 (DMSO-d6) and
singlets at δ −21.0 (CH3I) and at δ 66.3 (1,4-dioxane) in 13C NMR spectra.[16–18]
Signals in the spectra of both systems provide evidence of a reaction occurring by showing
consumption of CH3I and production of other chemical species (Figures 1 and 2). 1,4-Dioxane
was used as an internal standard for quantification. The water signals correspond to a residual
signal in system I and the water added in system II.
1
The assignment of signals in H NMR and 13C NMR spectra in systems I and II (Table 1)
was confirmed through acquisition of two-dimensional NMR spectra (heteronuclear multiple
quantum correlation (HMQC), heteronuclear multiple bond correlation (HMBC) and diffusion-
ordered NMR spectroscopy (DOSY)) and compared using the shape and chemical shifts (δ) of
signals with information in published spectra [12,16,17,19] or simulated ones using specialized
software.[18]
In 1H NMR spectra from both systems, there was a widening and decreasing of the intensity
of the water signal and a persistence of the intensity of the 1,4-dioxane signal. A slight varia-
tion in the chemical shift, δ, was observed in some of the signals and was attributed to changes
in composition of the environment in terms of nature and solute concentration due to reactions
that slowly diversified the interactions between the species and modified the electromagnetic

Journal of Sulfur Chemistry
3
Figure 1. 1H NMR spectra of system
I showing the variation of the signals intensities vs. time (d:
days, h: hours after mixture of CH3I with DMSO-d6). 2a, hexadeuterated trimethyloxosulfonium iodide; 3,
methoxy-bis(trideuteromethyl)sulfonium iodide; 4, DMSO-d3; 5, methanol and 6, CH3SCD3. Extension: δ 4.08–3.75
(left) and δ 2.60–2.45 (right).
environment of the nucleus to those that correspond to the signals.[11] The most notable δ varia-
tions in the signals of the system I spectra (Figure 1) were those of water (δ 3.29 → 3.54), 2a (δ
3.83 → 3.91 → 3.89), 1,4-dioxane (δ 3.57 → 3.54) and CH3I (δ 2.18 → 2.13). In the system
II spectra (Figure 2), there were small δ changes in water signals (δ 3.37 → 3.39 → 3.41 →
3.53), 2a (δ 3.82 → 3.91 → 3.90), 1,4-dioxane (δ 3.55 → 3.53) and CH3I (δ 2.16 → 2.13).
The concentration of species evolved during the reaction was determined by the integration
1
of signals in the H NMR spectra series of systems I and II and was normalized with respect
to maximum concentration, as shown in Figures 3 and 4. The changes in intensity of the sig-
1
nals in the H NMR spectra (Figures 1 and 2) and those in the concentration of the respective
species were evidence of the consumption of CH3I from the beginning of reaction and until
its depletion in both systems. Initially, a signal with very low intensity in δ 3.99 (1H) and in δ
62.11 (13C), attributable to methoxy-bis(trideuteromethyl)sulfonium iodide 3, appeared, and was
rapidly extinguished, while another signal that was attributed to 2a, appeared in δ 3.89 (1H) and
δ 39.2 (13C), as illustrated in Scheme 1. These results agree with those published by Smith and
Winstein about isomerization in solution, promoted by the nucleophilic character of the nonbond-
ing pairs of electrons in the sulfur atom of the alkoxy dimethylsulfonium cation to produce an
alkyl dimethyloxosulfonium cation.[15] However, it does not exclude that 3 could be an isomeric
contact ion pair of 2. 2a is detected by NMR, without isolating it from the medium and by pro-
ducing it in a closed recipient, without inert atmosphere, refluxing or anhydrous DMSO, under
different experimental conditions and having reagents in different proportions to those used by
Kuhn and Trischmann [13,14] or other authors, to obtain 2 or some isotopomer of 2.[20–24]
After the concentration of 2a reached a maximum point, it diminished while the trideuterated
dimethylsulfoxide, DMSO-d3 (4) signal appeared (1H NMR: δ 2.54 and 13C NMR: δ 40.3). This
behavior is attributed to the exchange of CH3 for CD3 between 2a and DMSO-d6 described
in Scheme 2, to produce DMSO-d3 and nona-deuterated trimethyloxosulfonium iodide, 2b,

4
E. Avella-Moreno et al.
Figure 2. 1H NMR spectra of system II showing the variation of the signals intensities vs. time (d: days, h:
hours after mixture of CH3I, DMSO-d6, NaOH and water). 2a, hexadeuterated trimethyloxosulfonium iodide; 3,
methoxy-bis(trideuteromethyl)sulfonium iodide; 4, DMSO-d3; 5, methanol; 6, CH3SCD3 and 7, dimethyl ether.
Extension: δ 4.04–3.78 (left) and δ 2.58–2.46 (right).
(13C NMR: δ 38.4). In both systems, there was an increase in the concentration of 4 while 2a
and CH3I diminished. It was determined that the exchange of CH3 for CD3 happened between
2a and DMSO-d6 because the concentration of 4 increased during the rest of the monitoring,
even after CH3I was depleted, and from the remaining species in the medium, 2a was the only
one whose concentration continued diminishing (Figures 3 and 4). As an antecedent of obtain-
ing products from this exchange, Ripmeester published that by decomposition at 190°C and in a
vacuum, a solution of 4 in DMSO-d6 was produced from 2a.[20]
As time went on in systems I and II, the red color of the medium was intensified due to the
generation of iodine, I2, and, at the same time, precipitation of a white solid that we attribute to
the isotopomers from 2, 2a and 2b, given the similarity of the appearance of the solid and the
chemical shift of the signals observed in the spectra with those from 2, as recorded in a previous
study.[12] The start of the precipitation of the white solid coincided with reaching the maximum
recorded concentration of 2a (at 11.9 days, in system I, and at seven days in system II). Only
in system II was a compound which was solid green with metallic shine precipitated, which is
attributed to deuterated Na4(DMSO-dx)15][(I3)3I], 1a, an isotopomer of 1 whose physical appear-
ance and the chemical shift of the signals in the spectra are very similar to those of product 1 that
was obtained in similar conditions by self-assembly between DMSO and CH3I.[12] The start of
precipitation of 1a also coincided with the maximum recorded concentration of 2a. These results
show that precipitation of 2a and 1a is preceded by a saturation of the solution of the medium
with 2a.
In both systems, the formation of methanol, CH3OH, 5, (1H, δ 3.13 and 13C, δ 48.5),
CH3SCD3, 6, (1H, δ 2.92 and 13C, δ 25.9) and dimethyl ether, 7, CH3OCH3 (1H, δ 3.16 and

Journal of Sulfur Chemistry
5
Table 1. The assignment of the signals of 1H NMR and 13C NMR spectra in systems I (DMSO-d6 and CH3I) and II
(DMSO-d6, CH3I, NaOH and H2O).
1H NMR
13C NMR
Multiplicity
δ:
Multiplicity
δ:
Assignment
2.18a
2.5
2.52
s
− 21.44a
39.51
39.77
S
CH3 (CH3I)
Quintet
m
Septet
CHD2 (DMSO-d5) and CD3 (DMSO-d6)
CHD2 and CD3 ([Na4(DMSO-dx)15][(I3)3I], 1a)
CH3 (DMSO-d3, 4)
CH3 (dimethylsulfide, 6)
CH3 (CH3OH, 5)
CH3 (dimethyl ether, 7)
H (H2O)
CH2 (1,4-dioxane)
CH3S (hexadeuterated trimethyloxosulfonium iodide, 2a)
CH3O (methoxy-bis(trideuteromethyl)sulfonium iodide, 3)
M
S
S
S
s
2.54
s
s
s
s
40.29
2.92a
3.13a
3.16a
3.29a
3.57a
3.89a
3.99a
25.87a
48.53a
59.77a
s (broad)
s
s
s
66.29a
39.18a
s
s
s
62.11 a,b
Note: m, multiplet, s, singlet.
aChemical shift of these signals changed slightly during the process. That was attributed to effects of changes in concentration and
interactions between substances in the reaction mixture.
bIt is a low-intensity signal attributable to CH3 in 3. The small septet expected for the CD3 in 3, apparently is overlapped with the big
signal of DMSO-d6 ( ≈ 39.51 ppm).
Scheme 1. Formation of 3 and 2a from CH3I and DMSO-d6.
Scheme 2. Exchange of CH3 for CD3 between 2a and DMSO-d6.
13C, δ 59.8) was detected. For comparable times measured from the beginning of the process
and in relation to the amount of CH3I initially allowed, system II produced less quantity of 2a
and DMSO-d3, but generated a little more of 5, 6 and 7 than in system I. These differences were
attributed to the addition of NaOH and water in system II, which compete with DMSO-d6 for
the CH3I in the substitution in which 2a is formed to produce methanol, 5, and dimethyl ether, 7.
For that reason, the maximum concentration of 2a in system II was less that in system I and
1
was reached 4 days before (Figures 3 and 4). On the other hand, in the H NMR spectra of
system II, signals with very low intensity were observed, corresponding to hydrogen bonded to
carbon sp3, characteristic of aliphatic compounds, attributable to ethane (δ 0.90–0.95) and to
other hydrocarbons present in such scarce concentration that they could not be quantified with
certainty.
The results of NMR monitoring allowed for proposing the sequence of reactions shown in
Scheme 3 to explain the formation of 1a in system II as an oligomeric structure stabilized by
triiodide anions (I3−) and iodide (I−) obtained by self-assembly in solution between DMSO-d6
and CH3I, in which production of trideuterated dimethyl sulfide 6, is evidenced, by the reduction

6
E. Avella-Moreno et al.
Figure 3. Evolution of the concentration of four major components of system I.
Figure 4. Evolution of the concentration of six major components of system II.
of DMSO-d3, 4, with HI,[25] together with ethane, and iodine, generated probably by photolysis
of CH3I,[26] among other detected products (2a, 5, 7). In order to complement our work we are
considering to study the reaction between DMSO and CH3I with small additions of aqueous HI.
The 1H NMR and 13C NMR DOSY spectra of system II, acquired toward the end of the mon-
itoring period, evidenced that signals assigned to different chemical species in the NMR spectra
effectively correspond to different discreet entities present in the mixture. Up to six different
diffusion coefficients were found that correlate to the chemical shift of DMSO-d3, 4, methanol,

Journal of Sulfur Chemistry
7
Scheme 3. Sequence of chemical reactions in system II that explains the formation of 1a.
5, trideuterated dimethyl sulfide, 6, dimethyl ether, 7, hexadeuterated trimethyloxosulfonium, 2a,
water, 1,4-dioxane, DMSO-d5 and DMSO-d6.
In 13C NMR spectra of systems I and II, acquired at the end of monitoring period, signals were
observed that confirm the predominance of DMSO-d3, 4, and the existence of small quantities
of 2a, and additional low-intensity signals were detected that gave indication of the formation of
deuterated species corresponding to deuterated methanol, 5b, at δ 47.6, hexadeuterated dimethyl
sulfide, 6b, at δ 25.5, and hexadeuterated dimethyl ether, 7b, at δ 59.6, as products of the chem-
ical exchange of hydrogen or methyl between species present in the medium. However, this
information is not enough to establish with certainty the mechanism by which this exchange
occurs.
3. Conclusions
Monitoring of a mixture of DMSO-d6 with CH3I (system I) and of another mixture of DMSO-
d6 with CH3I, NaOH and water (system II) by means of NMR analysis, at 295 1 K for more
than 300 days allowed detection of chemical species that are formed, and the propounding of
concurrent chemical reactions for the production of [Na4(DMSO)15][(I3)3I], 1. In both systems,
there was a consumption of CH3I and DMSO-d6 to produce 3 (methoxy-bis(trideuteromethyl)
sulfonium iodide) and indications of the fast isomerization of the cation of 3 to produce 2a
(hexadeuterated trimethyloxosulfonium iodide) was seen. An exchange of CH3 by CD3 was
detected between 2a and DMSO-d6 to produce 4 (DMSO-d3) and 2b (nona-deuterated trimethy-
loxosulfonium iodide) that occurred later, at room temperature (295 2 K) and local pressure
∼
(
563 mm Hg). 2a, the white solid that precipitated from the reaction medium, and 2b were
=
attributed to isotopomers of 2 (trimethyloxosulfonium iodide). Additionally, in both systems
small quantities of methanol, 5, trideuterated dimethyl sulfide, 6, and dimethyl ether, 7, were
detected. Only in system II, 1a ([Na4(DMSO-dx)15][(I3)3I] deuterated) was obtained as a green
precipitate very similar to 1, and a greater quantity of 5, 6, and 7 was detected than in system
I. This is attributed to the presence of NaOH and water from the beginning in the mixture of
system II.
The results obtained during this monitoring enabled the proposal of a sequence of reactions
to explain the formation of 1a in system II and prove that there is considerable reactivity of
DMSO-d6 with CH3I when acquiring and analyzing NMR spectra, obtained in this solvent.

8
E. Avella-Moreno et al.
4. Experimental
4.1. General
The reagents, DMSO (Carlo Erba, 99.9%), DMSO-d6 (Sigma-Aldrich, 99.9%-D), CH3I (Merck,
98%, stabilized with Ag), NaOH (Merck, ≥ 97%, pellets), distilled water and 1,4-dioxane
(Sigma-Aldrich, 99.8%) were used without additional purification. 1,4-dioxane was used as an
internal standard for quantification.
4.2. Preparation of Systems I and II
The solutions for Systems I and II were prepared by weighing the components on an analytic
scale, directly within the NMR tube (Norell® , Item No. 507-HP-8; 5 mm OD and 8 inch).
System I: 1.0552 g of DMSO-d6 (in excess), 0.2121 g of CH3I and 0.0102 g of 1,4-dioxane.
System II: 1.0398 g of DMSO-d6 (in excess), 0.2135 g of CH3I, 0.0105 g of NaOH, 0.0081 g
of distilled H2O and 0.0124 g of 1,4-dioxane.
The solutions in the tubes were frozen with liquid nitrogen, and the tubes were sealed at
once with an oxyacetylene flame at atmospheric pressure (563 mmHg). Later they were kept at
295 2 K (laboratory temperature). In that way, they were undisturbed most of the time; they
were only agitated mechanically (DAIGGER Vortex Genie 2, Cat. No. 222204) for 3 min before
each NMR spectra acquisition.
4.3. NMR
The NMR spectra of each system were acquired at 295 1 K in a Bruker Avance 400 spectrom-
1
eter outfitted with a broadband observe probe, operating at 400.13 MHz for H and at 100.62
MHz for 13C. The residual DMSO signal was used as a scale reference in the 1H NMR (δ: 2.50,
quintet, 2JHD
1.9 Hz) and 13C NMR (δ: 39.5, 1JCD
21.0 Hz) spectra. The integration of the
∼
=
∼
=
1,4-dioxane (δ: 3.53–3.57) in 1H NMR [13,14] signal was used as an internal pattern for quantifi-
cation, following prescriptions given in the literature.[27–29] Each FID was processed 10 times
until obtaining integral averages with variation coefficients (CV) ≤ 5%, in intervals with 95%
confidence limits (according to test t from Student) for signals with signal to noise at ≥ 150:1
(MestReC® ).[30]
The 1H NMR and 13C NMR spectra were acquired for system I from 0.3 h to 343 days (d) 0.4
h after the mixture of reagents, and for system II from 1.8 h to 307 d 0.3 h. The assignment of the
signals, as seen in Table 1, and the composition of the reagent mixtures was verified by means
of the acquisition of 2D NMR spectra (HMQC, HMBC and DOSY). The acquisition parameters
of all the NMR experiments, other NMR (13C, HMQC, HMBC and DOSY) spectra, and some
useful enlargements of these are available in the supplementary information.
Disclosure statement
No potential conflict of interest was reported by the authors.
Supplemental data
Supplemental data for this article can be accessed at http://dx/doi.org/10.1080/17415993.2015.1066376.
Note
1. It is a low-intensity signal attributable to CH3 in 3. The small septet expected for the CD3 in 3, apparently is
overlapped with the big signal of DMSO-d6 ( ≈ 39.51 ppm).

Journal of Sulfur Chemistry
9
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