Synthesis of 3,4-dialkylsulfanyl-and 3,4,5-trialkylsulfanyl derivatives of bromobenzene and benzaldehyde

Article abstract of DOI:10.1080/17415993.2011.644554

3,4-Dialkylsulfanyl-(1a[n], n = 8, 9, 11) and 3,4,5- trialkylsulfanylbromobenzenes (1b[n], n = 6, 8, 10, 12) were prepared from 3,4-difluoro-and 3,4,5-trifluorobromobenzene, respectively, in 50-60% yields. The bromobenzenes 1[n] were converted to benzalde

Full text of DOI:10.1080/17415993.2011.644554

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Synthesis of 3,4-dialkylsulfanyl- and
3,4,5-trialkylsulfanyl derivatives of
bromobenzene and benzaldehyde
Aleksandra Jankowiak a , Żaneta Debska b , Jarosław Romański b
& Piotr Kaszyński a b
a Organic Materials Research Group, Department of Chemistry ,
Vanderbilt University , Nashville , TN , 37235 , USA
b Faculty of Chemistry , University of Łódź , Tamka 12, 91403 ,
Łódź , Poland
Published online: 31 Jan 2012.
To cite this article: Aleksandra Jankowiak , Żaneta Debska , Jarosław Romański & Piotr Kaszyński
(2012) Synthesis of 3,4-dialkylsulfanyl- and 3,4,5-trialkylsulfanyl derivatives of bromobenzene and
benzaldehyde, Journal of Sulfur Chemistry, 33:1, 1-7, DOI: 10.1080/17415993.2011.644554
To link to this article: http://dx.doi.org/10.1080/17415993.2011.644554
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Journal of Sulfur Chemistry
Vol. 33, No. 1, February 2012, 1–7
Synthesis of 3,4-dialkylsulfanyl- and 3,4,5-trialkylsulfanyl
derivatives of bromobenzene and benzaldehyde
a
b
b
a,b
˙
Aleksandra Jankowiak , Zaneta De¸bska , Jarosław Roman´ski , and Piotr Kaszyn´ski
*
aOrganic Materials Research Group, Department of Chemistry, Vanderbilt University, Nashville, TN 37235,
USA; bFaculty of Chemistry, University of Łódz´, Tamka 12, 91403 Łódz´, Poland
(Received 22 September 2011; final version received 23 November 2011)
3,4-Dialkylsulfanyl- (1a[n], n = 8, 9, 11) and 3,4,5-trialkylsulfanylbromobenzenes (1b[n], n = 6, 8, 10,
12) were prepared from 3,4-difluoro- and 3,4,5-trifluorobromobenzene, respectively, in 50–60% yields.
The bromobenzenes 1[n] were converted to benzaldehydes 2[n] by lithium–halogen exchange followed
by reaction with DMF.
Br
Br
CHO
F
Y
CnH2n+1
S
X
X
CnH2n+1
S
F
CnH2n+1
S
CnH2n+1
S
X = H, SCnH2n+1
Y = H, F
Keywords: synthesis; nucleophilic aromatic substitution; alkyl aryl sulfides; substituted bromobenzenes;
substituted benzaldehydes
1. Introduction
Alkylsulfanyl groups are used to modify molecular and bulk properties of organic materials
that are based primarily on aromatic compounds. These substituents lower the ionization poten-
tial of the aromatic compounds, and sufficiently long chains increase solubility, lower melting
points, or even induce liquid crystalline behavior. Good examples are derivatives of triphenylene
(1) and phenanthrene (2), in which six hexylsulfanyl groups induce discotic columnar behavior
and modify their electronic properties, so the materials exhibit relatively high hole mobility of
photo-generated charges (3). Short alkylsulfanyl substituents are used in designing aromatics for
charge-transfer salts (4), and C6H13S substituents modify electronic properties of a ligand for Ru2+
complex developed for solar cells (5). Six hexylsulfanyl groups have been used as substituents
in highly fluorescent oligophenylenevinylenes designed for detection of Ag+ ions (6). When the
*Corresponding author. Email: piotr.kaszynski@vanderbilt.edu
ISSN 1741-5993 print/ISSN 1741-6000 online
© 2012 Taylor & Francis
http://dx.doi.org/10.1080/17415993.2011.644554
http://www.tandfonline.com

2
A. Jankowiak et al.
sulfur center is oxidized, the moderately electron-donating alkylsulfanyl group is transformed to
a powerful electron-withdrawing alkylsulfonyl substituent that is particularly useful in designing
of non-linear optical materials (7–9). We have envisioned di- and trialkylsulfanylphenyl groups
as components of liquid crystalline 6-oxoverdazyls (10).
Polyalkylsulfanylphenyl groups are often introduced to more complexed molecular archi-
tectures by taking advantage of the bromo substituent that readily undergoes Pd-catalyzed
coupling reactions (11) and lithium–halogen exchange (12). Reactions of the resulting aryllithum
derivatives (4, 6, 9) give access to a variety of functional groups.
The preparation of the monoalkylsulfanyl bromobenzenes involves a straightforward alky-
lation of the readily available bromothiophenols (8, 9, 11). Alternatively, 1-alkylsulfanyl-
4-bromobenzenes can be obtained by an Ullmann-type S-arylation of alkylmercaptans
(13, 14), which exhibits high chemoselectivity for iodine (13, 15). Among polymercap-
tobromobenzenes, only 4-bromo-1,2-dimercaptobenzene is known (16), but its cumber-
some preparation makes this route to 1-bromo-3,4-dialkylsulfanylbenzenes (1a[n]) imprac-
tical. Consequently, such compounds are scarce. Recently, a report (6) of 1-bromo-3,4,5-
trihexylsulfanylbenzene (1b[6]), prepared from 1-bromo-3,4,5-trifluorobenzene, demonstrated
a new route to poly(alkylsulfanyl)bromobenzenes. Although no experimental or analytical details
were given, the reaction occurs in DMSO, and the net aromatic nucleophilic substitution process
involves the SRN1 mechanism (17, 18). We have examined this reaction in detail and expanded
it to other 1-bromo-3,4,5-trialkylsulfanylbenzenes (1b[n]) and also to 3,4-dialkylsulfanyl deriva-
tives (1a[n]). Subsequently, these bromobenzenes were converted to the corresponding di- and
trialkylsulfanylbenzaldehydes (2a[n] and 2b[n]), which belong to a class of practically unknown
compounds (6, 19). Here we report general methods for preparation of a series of these compounds
and their characterization.
CnH2n+1
S
CnH2n+1
S
CnH2n+1
S
Br
CnH2n+1
S
CHO
n = 6, 8-12
X
X
1a[n], X = H
1b[n], X = SCnH2n+1
2a[n], X = H
2b[n], X = SCnH2n+1
2. Results and discussion
3,4-Dialkylsulfanyl- and 3,4,5-trialkylsulfanylbromobenzes (1[n]) were prepared by reacting 1-
bromo-3,4-difluorobenzene and 1-bromo-3,4,5-trifluorobenzene, respectively, with appropriate
sodium alkanethiolate in dry DMSO (Scheme 1). However, the efficient preparation of higher
homologs, especially trisubstituted bromobenzenes (1b[n]), requires THF as a co-solvent (up
to 30%) for a better dissolution of the highly aliphatic thiolates and the products. The initial
reaction of the fluorobenzenes with the thiolate is exothermic, and for better control of the product
formation, fluorobenzene was added at ambient temperature. Under these conditions, a 1:1 mixture
of the desired product 1b[8] and a partially substituted intermediate (7.22 ppm, d, J = 6.1 Hz)
1
was observed after 30 min by H NMR in a reaction of 1-bromo-3,4,5-trifluorobenzene and
octanethiolate.
Subsequent heating of the reaction mixture led to the formation of bromides (1[n]) and products
of bromine substitution (3[n]) as the sole products in proportions ranging from 10:1 to 10:5 for
the longer members of the homologous series. The formation of the latter was demonstrated
1
for two derivatives 3b[8] and 3b[12]. The by-products were easily identified in the H NMR
spectra by the upfield-shifted aromatic signals. For instance, in 3b[n], the aromatic singlet is

Journal of Sulfur Chemistry
3
Scheme 1. Reaction of polyfluorobromobenzenes with alkanethiolates.
moved by about 0.17 ppm relative to that in bromide 1b[n] (6.96 ppm). The observed exhaustive
alkylsulfanylation of the bromofluorobenzenes cannot be avoided, but it can be minimized at lower
temperatures. For instance, the ratio of 1b[8] to 3b[8] was 20:14, when the reaction mixture was
heated at 100–105 ◦C, and 20:9 at 60 ◦C. The by-products 3[n] were separated from bromides 1[n]
by chromatography as the more polar fraction. However, complete purification of bromobenzene
1[n] is often not necessary, since by-products 3[n] are inert in the lithiation process and are readily
separated from aldehydes 2[n].
CnH2n+1
S
X
CnH2n+1
S
1. n-BuLi, THF
2. DMF
CnH2n+1
S
Br
CnH2n+1
S
CHO
-78οC
X
1a[n], X = H
1b[n], X = SCnH2n+1
2a[n], X = H
2b[n], X = SCnH2n+1
Scheme 2. Synthesis of benzaldehydes 2[n].
Benzaldehydes 2[n] were prepared in a routine way via lithium–halogen exchange of alkyl-
sulfanylbromobenzenes 1[n] with n-BuLi and subsequent reaction of the generated aryllithium
with dry DMF at −78 ◦C (Scheme 2) (20). The resulting aldehydes were isolated by column
chromatography as yellow oils or low melting solids in purities sufficient for subsequent trans-
formations (10). Aldehyde 2b[6] was also obtained by formylation of aryllithium derived from
1b[6] with N-forylmorpholine (6).
Another protocol for the preparation of such benzaldehydes by nucleophilic substitution of the
bromo and nitro groups in ethyl 3,5-dibromo-4-nitrobenzoate followed by reduction of the ester
group was demonstrated for 2b[1] (19).
3. Conclusions
Polyfluorobromobenzenes are convenient starting materials for the preparation of polyalkylsul-
fanylbromobenzenes in DMSO or DMSO/THF mixtures by the SRN1 mechanism. Although
substitution of fluorine is faster than that of bromine in the starting material, the selectivity is
low, and typically 3:1 mixtures of the desired bromide 1[n] and the exhaustively sulfanylated by-
product 3[n] are formed, which requires chromatographic separation. The bromo derivatives 1[n]
are convenient starting materials for other functional derivatives as demonstrated for aldehydes
2[n] and serve as key building blocks for advanced materials.

4
A. Jankowiak et al.
4. Experimental
Melting points are not corrected. NMR spectra were obtained at 400 or 600 MHz (1H) and
151 MHz (13C) in CDCl3 and referenced to the solvent, unless otherwise specified. IR spectra
were recorded using neat samples or KBr pellets.
4.1. 4,5-Dialkylsulfanyl- and 3,4,5-trialkylsulfanyl-1-bromobenzenes 1a[n] and 1b[n]:
general procedure
To a suspension of NaH (1.1 equiv. per mercaptane, 60% in oil) in dry DMSO (200 mL/25 mmol
of 1-bromo-3,4-difluorobenzene, for the preparation of 1a[n], or 1-bromo-3,4,5-trifluorobenzene,
for the preparation of 1b[n]), stoichiometric amounts of alkanethiol (2.0 or 3.0 equiv., respec-
tively) were added slowly under Ar. For the preparation of tridecylsulfanyl and tridodecylsulfanyl
derivatives 1b[10] and 1b[12], a mixture of DMSO and THF in a 5:2 ratio (280 mL/25 mmol of
the substrate) was used to increase the solubility of the reactants and products.
The mixture was kept at ambient temperature by using a water bath, while adding the thiol.
After 30 min, 1 equiv. of 1-bromo-3,4-difluorobenzene or 1-bromo-3,4,5-trifluorobenzene was
added slowly at ambient temperature and the mixture was stirred at 60 ◦C overnight. The mixture
was cooled, poured into water, organic products were extracted (hexanes), combined extracts
dried (Na2SO4), and solvents evaporated. The oily viscous residue was passed through a sil-
ica gel plug (hexane) and then separated on a silica gel column. Initially, hexane was used to
remove non-polar impurities (presumably partially substituted products), while a more polar
eluent (hexanes/CH2Cl2, 8:1) gave the expected bromides 1a[n] or 1b[n] followed by tri- or
tetrasulfanyl by-products 3a[n] or 3b[n]. The bromides were obtained in typical yields of 50–
60% and purity >96%. Analytically pure samples were obtained by additional chromatography
and/or recrystallization (hexane).
4.1.1. 1-Bromo-3,4-dioctylsulfanylbenzene (1a[8])
1H NMR (600 MHz, CDCl3) δ 0.884 (t, J = 7.0 Hz, 3H), 0.879 (t, J = 7.0 Hz, 3H), 1.27–1.34
(m, 16H), 1.40–1.49 (m, 4H), 1.64 (quin., J = 7.1 Hz, 2H), 1.69 (quin., J = 7.1 Hz, 2H), 2.87
(t, J = 7.4 Hz, 2H), 2.90 (t, J = 7.4 Hz, 2H), 7.11 (d, J = 8.3 Hz, 1H), 7.21 (dd, J1 = 8.3 Hz,
J2 = 2.0 Hz, 1H), 7.31 (d, J = 2.1 Hz, 1H); 13C NMR (151 MHz, CDCl3) δ 14.1, 22.6, 28.6,
28.86, 28.91, 29.00, 29.12, 29.13, 31.8, 33.2, 33.6, 119.9, 128.5, 130.0, 130.4, 135.5, 140.5. Anal.
Calcd for C22H37BrS2: C, 59.30; H, 8.37; S, 14.39. Found: C, 59.50; H, 8.43; S, 14.08.
4.1.2. 1-Bromo-3,4-dinonylsulfanylbenzene (1a[9])
1H NMR (600 MHz, CDCl3) δ 0.876 (t, J = 7.1 Hz, 3H), 0.880 (t, J = 7.0 Hz, 3H), 1.24–1.34
(m, 20H), 1.40–1.48 (m, 4H), 1.64 (quin., J = 7.4 Hz, 2H), 1.69 (quin., J = 7.2 Hz, 2H), 2.87
(t, J = 7.2 Hz, 2H), 2.90 (t, J = 7.2 Hz, 2H), 7.11 (d, J = 8.3 Hz, 1H), 7.21 (dd, J1 = 8.3 Hz,
J2 = 2.1 Hz, 1H), 7.31 (d, J = 2.1 Hz, 1H); 13C NMR (151 MHz, CDCl3) δ 14.1, 22.7, 28.5,
28.85, 28.90, 28.95, 29.17, 29.24, 29.4, 31.9, 33.2, 33.6, 119.9, 128.5, 129.9, 130.4, 135.5, 140.5.
Anal. Calcd for C24H41BrS2: C, 60.86; H, 8.73; S, 13.54. Found: C, 61.01; H, 9.01; S, 13.27.
4.1.3. 1-Bromo-3,4-diundecylsulfanylbenzene (1a[11])
m.p. 37–38 ◦C; 1H NMR (600 MHz, CDCl3) δ 0.88 (t, J = 7.0 Hz, 6H), 1.22–1.34 (m, 28H), 1.40–
1.48 (m, 4H), 1.64 (quin., J = 7.1 Hz, 2H), 1.69 (quin., J = 7.1 Hz, 2H), 2.87 (t, J = 7.5 Hz, 2H),

Journal of Sulfur Chemistry
5
2.90 (t, J = 7.5 Hz, 2H), 7.11 (d, J = 8.3 Hz, 1H), 7.21 (dd, J1 = 8.3 Hz, J2 = 2.0 Hz, 1H), 7.32
(d, J = 2.0 Hz, 1H); 13C NMR (151 MHz, CDCl3) δ 14.1, 22.7, 28.55, 28.86, 28.89, 28.94, 29.2,
29.3, 29.5, 29.58, 29.62, 29.64, 31.9, 33.2, 33.6, 119.9, 128.5, 130.0, 130.5, 135.5, 140.5. Anal.
Calcd for C28H49BrS2: C, 63.49; H, 9.32; S, 12.11. Found: C, 63.65; H, 9.46; S, 12.03.
4.1.4. 1-Bromo-3,4,5-trihexylsulfanylbenzene (1b[6]) (6)
m.p. 44–45 ◦C; 1H NMR (400 MHz, CDCl3) δ 0.87 (t, J = 6.9 Hz, 3H), 0.90 (t, J = 6.9 Hz, 6H),
1.24–1.37 (m, 12H), 1.38–1.43 (m, 2H), 1.45–1.52 (m, 4H), 1.59 (quin., J = 7.4 Hz, 2H), 1.72
(quin., J = 7.5 Hz, 4H), 2.81 (t, J = 7.2 Hz, 2H), 2.84 (t, J = 7.2 Hz, 4H), 6.96 (s, 2H); 13C
NMR (100 MHz, CDCl3) δ 14.01(2C), 14.04, 22.5(2C), 22.6, 28.0(2C), 28.6, 28.8(2C), 29.6,
31.36(2C), 31.43, 32.35(2C), 34.9, 122.5(CH), 123.9, 126.6, 148.5. Anal. Calcd for C24H41BrS3:
C, 57.00; H, 8.17. Found: C, 56.83; H, 8.16.
4.1.5. 1-Bromo-3,4,5-trioctylsulfanylbenzene (1b[8])
m.p. 32–35 ◦C; 1H NMR (400 MHz, CDCl3) δ 0.87 (t, J = 6.9 Hz, 3H), 0.89 (t, J = 6.7 Hz, 6H),
1.22–1.37 (m, 24H), 1.38–1.43 (m, 2H), 1.44–1.52 (m, 4H), 1.59 (quin., J = 7.5 Hz, 2H), 1.72
(quin., J = 7.4 Hz, 4H), 2.81 (t, J = 7.2 Hz, 2H), 2.84 (t, J = 7.3 Hz, 4H), 6.96 (s, 2H); 13C
NMR (100 MHz, CDCl3) δ 14.1, 22.6, 28.0, 28.9, 29.11, 29.14, 29.19, 29.6, 31.79, 31.82, 32.35,
34.9, 122.5(CH), 123.9, 126.6, 148.5. Anal. Calcd for C30H53BrS3: C, 61.09; H, 9.06. Found: C,
61.33; H, 9.00.
4.1.6. 1-Bromo-3,4,5-tridecylsulfanylbenzene (1b[10])
m.p. 52–53 ◦C; 1H NMR (400 MHz, CDCl3) δ 0.86 (t, J = 6.9 Hz, 3H), 0.88 (t, J = 6.8 Hz, 6H),
1.22–1.36 (m, 36H), 1.37–1.42 (m, 2H), 1.43–1.52 (m, 4H), 1.59 (quin., J = 7.4 Hz, 2H), 1.72
(quin., J = 7.4 Hz, 4H), 2.81 (t, J = 7.4 Hz, 2H), 2.84 (t, J = 7.3 Hz, 4H), 6.96 (s, 2H); 13C NMR
(100 MHz, CDCl3) δ 14.1, 22.7, 28.0, 28.9, 29.10, 29.18, 29.22, 29.29, 29.33, 29.47, 29.54, 29.57,
31.88, 31.90, 32.35, 34.9, 122.5(CH), 123.9, 126.6, 148.5. Anal. Calcd for C36H65BrS3: C, 64.15;
H, 9.72. Found: C, 64.12; H, 9.77.
4.1.7. 1-Bromo-3,4,5-tridodecylsulfanylbenzene (1b[12])
m.p. 63–64 ◦C; 1H NMR (400 MHz, CDCl3) δ 0.88 (t, J = 6.7 Hz, 9H), 1.22–1.37 (m, 48H), 1.38–
1.43 (m, 2H), 1.44–1.52 (m, 4H), 1.59 (quin., J = 7.7 Hz, 2H), 1.72 (quin., J = 7.4 Hz, 4H), 2.81
(t, J = 7.4 Hz, 2H), 2.84 (t, J = 7.4 Hz, 4H), 6.96 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 14.1,
22.7, 28.0, 28.9, 29.10, 29.18, 29.21, 29.33, 29.47, 29.54, 29.58, 29.62, 29.64, 29.67, 31.9, 32.3,
34.9, 122.5(CH), 123.9, 126.6, 148.5. Anal. Calcd for C42H77BrS3: C, 66.54; H, 10.24. Found:
C, 66.52; H, 10.38.
4.2. 3,4-Dialkylsulfanyl- and 3,4,5-trialkylsulfanylbenzaldehydes (2a[n] and 2b[n]):
general procedure
A solution of 1-bromo-3,4-dialkylsulfanylbenzene (1a[n]) or 1-bromo-3,4,5-trialkylsulfanylben-
zene (1b[n]) (1.0 mmol) in dry THF (20 mL) was quickly cooled to −78 ◦C and, before the starting
material began to precipitate, n-BuLi (1.1 mmol) was added under Ar. The mixture was stirred
at −78 ◦C for 1 h and then warmed up to 0 ◦C. After 1 h, the mixture was cooled to −78 ◦C, and

6
A. Jankowiak et al.
rigorously dried DMF (1.5 mmol) was added. The mixture was stirred for 1 h, quenched with 5%
HCl, organic products were extracted (Et2O), extracts dried (Na2SO4), and solvents evaporated.
The residue was passed through a silica gel plug (hexane/CH2Cl2, 2:1) and the resulting crude
aldehyde was purified by column chromatography (hexane/CH2Cl2, 2:1) giving the expected
product 2a[n] or 2b[n] as a yellowish oil or low melting solid in a typical yield of 60–80%.
4.2.1. 3,4-Dioctylsulfanylbenzaldehyde (2a[8])
1H NMR (600 MHz, CDCl3) δ 0.875 (t, J = 6.9 Hz, 3H), 0.881 (t, J = 6.9 Hz, 3H), 1.22–1.37
(m, 16H), 1.42–1.51 (m, 4H), 1.68 (quin., J = 7.5 Hz, 2H), 1.75 (quin., J = 7.5 Hz, 2H), 2.98
(t, J = 7.3 Hz, 2H), 2.99 (t, J = 7.3 Hz, 2H), 7.28 (d, J = 8.2 Hz, 1H), 7.60 (dd, J1 = 8.1 Hz,
J2 = 1.6 Hz, 1H), 7.74 (d, J = 1.6 Hz, 1H), 9.90 (s, 1H); 13C NMR (151 MHz, CDCl3) δ 14.1,
22.6, 28.4, 28.8, 28.9, 29.05, 29.12, 29.13, 31.8, 31.9, 32.4, 33.5, 33.6, 125.1, 127.7, 129.0, 133.2,
136.3, 147.5, 191.0; IR (film, cm−1) 1694 (C O). Anal. Calcd for C23H38OS2: C, 69.99; H, 9.70;
S, 16.25. Found: C, 70.11; H, 9.85; S, 16.31.
=
4.2.2. 3,4,5-Trihexylsulfanylbenzaldehyde (2b[6]) (6)
1H NMR (400 MHz, CDCl3) δ 0.87 (t, J = 7.0 Hz, 3H), 0.90 (t, J = 7.1 Hz, 6H), 1.20–1.35 (m,
10H), 1.36–1.44(m, 2H), 1.46–1.56(m, 6H), 1.61(quin., J = 7.4 Hz, 2H), 1.75(quin., J = 7.5 Hz,
4H), 2.90 (t, J = 7.4 Hz, 2H), 2.94 (t, J = 7.4 Hz, 4H), 7.34 (s, 2H), 9.95 (s, 1H); IR (film, cm−1
)
+
=
1702 (C O). HRMS Calcd for C25H43OS3 (MH ): m/z 455.2471, found m/z 455.2476.
4.2.3. 3,4,5-Trioctylsulfanylbenzaldehyde (2b[8])
1H NMR (400 MHz, CDCl3) δ 0.87 (t, J = 7.0 Hz, 3H), 0.88 (t, J = 7.0 Hz, 6H), 1.20–1.35 (m,
24H), 1.36–1.44(m, 2H), 1.46–1.53(m, 4H), 1.61(quin., J = 7.4 Hz, 2H), 1.75(quin., J = 7.4 Hz,
4H), 2.90 (t, J = 7.4 Hz, 2H), 2.94 (t, J = 7.4 Hz, 4H), 7.34 (s, 2H), 9.95 (s, 1H). HRMS Calcd
for C31H55OS3 (MH+): m/z 539.3410, found m/z 539.3435.
4.2.4. 3,4,5-Tridecylsulfanylbenzaldehyde (2b[10])
1H NMR (400 MHz, CDCl3) δ 0.87 (t, J = 6.9 Hz, 3H), 0.91 (t, J = 6.9 Hz, 6H), 1.22–1.37 (m,
36H), 1.38–1.44(m, 2H), 1.45–1.54(m, 4H), 1.60(quin., J = 7.4 Hz, 2H), 1.75(quin., J = 7.5 Hz,
4H), 2.90 (t, J = 7.4 Hz, 2H), 2.94 (t, J = 7.4 Hz, 4H), 7.34 (s, 2H), 9.95 (s, 1H). HRMS Calcd
for C37H67OS3 (MH+): m/z 623.4349, found m/z623.4353.
4.2.5. 3,4,5-Tridodecylsulfanylbenzaldehyde (2b[12])
1
m.p. 46–48 ◦C; H NMR (500 MHz, CDCl3) δ 0.88 (t, J = 6.8 Hz, 9H), 1.21–1.37 (m, 48H),
1.38–1.45 (m, 2H), 1.46–1.53 (m, 4H), 1.60 (quin., J = 7.5 Hz, 2H), 1.75 (quin., J = 7.5 Hz,
4H), 2.90 (t, J = 7.4 Hz, 2H), 2.94 (t, J = 7.4 Hz, 4H), 7.34 (s, 2H), 9.95 (s, 1H). HRMS Calcd
for C43H79OS3 (MH+): m/z 707.5288, found m/z 707.5305.
4.3. 1,3,4,5-Tetraoctylsulfanylbenzene (3b[8])
Isolated as a white solid by column chromatography as a more polar fraction during purification
of 1b[8]: m.p. 37–38 ◦C; 1H NMR (400 MHz, CDCl3) δ 0.84–0.92 (m, 12H), 1.20–1.35 (m, 32H),

Journal of Sulfur Chemistry
7
1.36–1.52 (m, 8H), 1.61 (quin., J = 7.4 Hz, 2H), 1.64–1.76 (m, 6H), 2.81 (t, J = 7.4 Hz, 2H), 2.85
(t, J = 7.4 Hz, 4H), 2.92 (t, J = 7.4 Hz, 2H), 6.79 (s, 2H). HRMS Calcd for C38H71S4 (MH+):
m/z 655.4433, found m/z 655.4428.
4.4. 1,3,4,5-Tetradodecylsulfanylbenzene (3b[12])
Isolated as a white solid by column chromatography as a more polar fraction during purification of
1b[12]: m.p. 59–60 ◦C; 1H NMR (400 MHz, CDCl3) δ 0.88 (t, J = 6.7 Hz, 12H), 1.22–1.34 (m,
64H), 1.35–1.51 (m, 8H), 1.61 (quin., J = 7.4 Hz, 2H), 1.64–1.75 (m, 6H), 2.81 (t, J = 7.4 Hz,
2H), 2.85 (t, J = 7.5 Hz, 4H), 2.91 (t, J = 7.4 Hz, 2H), 6.78 (s, 2H). HRMS Calcd for C54H103S4
(MH+): m/z 879.6937, found m/z 879.6907.
Acknowledgements
This project was supported by Vanderbilt University Discovery grant.
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