A Transition-Metal-Free and Base-Mediated Carbene Insertion into Sulfur-Sulfur and Selenium-Selenium Bonds: An Easy Access to Thio- and Selenoacetals

Article abstract of DOI:10.1002/adsc.201600855

A transition-metal-free and base-mediated carbene insertion across sulfur-sulfur and selenium-selenium bonds has been developed by employing N-tosylhydrazone as a stable and safe carbene precursor. The ylide formation from carbene followed by Stevens rearrangement are considered to be the key steps. This thiol and selenol-free protocol delivers thioacetals and selenoacetals in good to excellent yields in short reaction time with good functional group tolerance. A one-pot synthesis involving in situ generation of tosylhydrazone has also been demonstrated. (Figure presented.).

Full text of DOI:10.1002/adsc.201600855

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DOI: 10.1002/adsc.201600855
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A Transition-Metal-Free and Base-Mediated Carbene Insertion
into Sulfur-Sulfur and Selenium-Selenium Bonds: An Easy Access
to Thio- and Selenoacetals
Dhanarajan Arunprasatha and Govindasamy Sekara,*
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a
Department of Chemistry, Indian Institute of Technology Madras, Chennai-600 036, Tamil Nadu, India
Fax: (+91)-44-2257-4202; e-mail: gsekar@iitm.ac.in
Received: August 2, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600855
free reductive coupling of N-tosylhydrazones have
Abstract: A transition-metal-free and base-medi-
ated carbene insertion across sulfur-sulfur and
selenium-selenium bonds has been developed by
employing N-tosylhydrazone as a stable and safe
been developed by Barlunga et al. and others.[7]
On the other hand, the remarkable stability of
thioacetals under acidic or basic conditions makes
them as a versatile protecting group and as a key
carbene precursor. The ylide formation from car-
intermediate in various natural product synthesis.[8]
bene followed by Stevens rearrangement are con-
Noteworthy examples are dehydrogliotoxin[8a] and
sidered to be the key steps. This thiol and selenol-
lignans.[8b] However, traditional methods for the syn-
free protocol delivers thioacetals and selenoacetals
thesis of thioacetals were associated with the draw-
in good to excellent yields in short reaction time
back of handling of thiol or dithiol which are known
with good functional group tolerance. A one-pot
for their foul odour.[9] Some progress has been made
synthesis involving in situ generation of tosylhydra-
for the thiol-free synthesis of thioacetals using tribu-
zone has also been demonstrated.
tylphosphine,[10a] methylthiotrimethylsilane[10b] and In-
TMSCl[10c] independently. Nevertheless, these attempts
Keywords: Carbene insertion; N-tosylhydrazones;
Transition-metal-free; Thioacetals; Selenoacetals
are often suffer from the generation of phosphine
oxide as inevitable byproduct, removal of this material
is experimentally tedious and silane reagents are
highly moisture sensitive as well as expensive.
37 Carbene insertion reactions have proven to be a highly
Conversely, the reaction between carbene and
38 versatile and powerful strategy for the formation of disulfides has received less attention.[11] Fu et al.
39 CÀC and C-hetero bonds.[1] During the past decades, applied rhodium catalyzed carbene insertion approach
40 catalytic, thermal and photochemical assisted carbene into SÀS bond to obtain thioacetals by employing N-
41 insertions on CÀH bond have been well studied and sulfonyl-1,2,3-triazoles and diaryldisulfides.[12] In re-
42 have become carbene’s representative reactions.[2] cent years, insertion using N-tosylhydrazones into
43 Quite apart from many CÀH insertion reactions, homonuclear bonds, have gained great interest as
44 carbenes undergo insertion into an array of XÀH these tactic enable the synthesis of gem-metallated
45 bonds where X is N, Si, O, S, Se, P or halogen.[3] Diazo and non-metallated compounds.
46 compounds are widely employed as precursors for the
In 2012, Wang and co-workers reported the first
47 generation of carbene species. However, diazo com- example of carbon insertion utilizing N-tosylhydra-
48 pounds which are not bearing any electron-withdraw- zones across the BÀB bond under metal-free con-
49 ing groups often present a challenge with respect to ditions (Scheme 1, eq 1).[13] Most recently, the same
50 their uncertain explosive and instability nature.[4] In group has developed an attractive protocol to access
51 this context, N-tosylhydrazones have emerged as geminal bis(silane) and geminal bis(stannane) deriva-
52 alternative and safe carbene precursors where non- tives through carbene insertion into SiÀSi and SnÀSn
53 stabilized transient diazo compounds could be gener- bonds using palladium catalyst (Scheme 1, eq 2).[14] In
54 ated in situ by base-mediated thermolysis.[5] N-tosylhy- continuing our study of employing N-tosylhydrazone
55 drazones have been extensively utilized in metal as a carbene precursor,[15] herein we report a metal-
56 catalyzed cross-coupling reactions.[6] Subsequently, free, base mediated carbene insertion into SÀS and
57 some unprecedented transformation involving metal- SeÀSe bonds using N-tosylhydrazones to synthesize
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thio- and selenoacetals under thiol and selenol-free
conditions (Scheme 1, eq 3).
The addition of phase transfer catalyst which is
typically used to accelerate the decomposition of N-
tosylhydrazone to diazo species has no effect on the
reaction as the addition of 3 equiv. of TBAC (n-tetra-
butylammoniumchloride) led to a similar yield (en-
try 3). Further screening of bases to improve the
efficacy of the reaction was not beneficial (entries 4–
6). Then, we observed that solvent significantly
influenced the yield of the insertion reaction. Solvents
such as THF, toluene and acetonitrile were inves-
tigated but they were less effective than 1,4-dioxane
(entries 7–9). Interestingly, a dramatic change in the
reaction rate was observed when the reaction was
carried out in DMF, thus the product was isolated in
81% yield within 30 min (entry 10). Pleasingly,
DMSO stood out to be a better choice as it gave the
desired product in 89% yield within 10 min (entry 11).
Further attempts to decrease the reaction temperature
Scheme 1. Insertion into homonuclear bonds using N-tosyl-
hydrazones.
We began the exploration of this insertion process were not beneficial as it provided the product with
20 by using benzaldehyde derived N-tosylhydrazone 1a reduced yield and took longer reaction time (en-
21 as model substrate with diphenyldisulfide 2a. The try 12). The reaction proceeded faster at higher
22 reaction was carried out with 1 equiv. of 2a in the temperature but yield was not improved (entry 13). A
23 presence of 2 equiv. of KOtBu as a base in 1,4-dioxane blank reaction was performed without adding base. As
24 at 1008C. To our delight, the expected product bis expected, there was no reaction and both the reactants
25 (phenylthio)acetal 3a was isolated in 45% yield were remained as such (entry 14).[16]
26 (Table 1, entry 1). The use of 1.5 equiv. of Ph2S2
27 provided 73% yield of the product. (entry 2).
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With this optimized reaction conditions, we then
proceeded to explore the scope of the reaction and
results are summarized in Table 2. Initially, a series of
N-tosylhydrazones were employed as substrates in this
insertion reaction. Reaction conditions were found to
be general regardless of the steric and electronic
nature of substrates as the wide range of N-tosylhy-
drazones underwent reaction smoothly to provide the
corresponding bis(arylthio)acetals in good to excellent
yields. Electron-donating group containing substrates
furnished the insertion product in good yield irrespec-
tive of the relative position (3b–k). Halogen-substi-
tuted N-tosylhydrazones found to be suitable sub-
strates and corresponding isolated products can
undergo further derivatizations (3l–s). Phenylethynyl
substituted tosylhydrazone also proceeded well and
afforded the product in 92% yield (3t). As with the
electron withdrawing substituents like nitro, cyano
and CF3 groups, the outcome were fruitful (3u–y).
Notably, sensitive functional group like ester was also
well tolerated under the reaction conditions (3z). N-
tosylhydrazones containing heterocycle units such as
2-furyl, 3-pyridyl and 2-thiophene were also under-
went conversion and provided satisfactory yields
(3aa–ac). However, aliphatic aldehyde and ketone
derived N-tosylhydrazones failed to afford desired
product under the optimized reaction conditions.
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Table 1. Optimization of reaction conditions.[a]
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Entry
Base
Solvent
Temp
(oC)
Time
(h)
Yield[b]
(%)
1
2
3
4
5
6
7
8
KOtBu
KOtBu
KOtBu
NaOEt
K2CO3
Et3N
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
THF
Toluene
CH3CN
DMF
100
100
100
100
100
100
100
100
100
100
100
90
15
12
10
16
18
18
12
12
45[c]
73
72[d]
18
trace
trace
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81
89
80
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
–
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12
10
11
12
13
14
30 min
10 min
20 min
5 min
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DMSO
DMSO
DMSO
DMSO
110
100
88
nr[e]
[a] Reaction conditions: 1a (0.5 mmol, 1.0 equiv.), 2a
(1.5 equiv.), base (2.0 equiv.) and solvent (2 mL).
[b] Isolated yield.
[c] 1.0 equiv. of 2a was used.
Next, substrate scope with respect to diaryl disul-
fides was investigated and results are shown in
Table 3. Electron-donating group containing diary-
ldisulfides underwent insertion smoothly and afforded
the product in good yields (3ad–af). Strong electron-
54 [d] 3.0 equiv. of TBAC was used.
[e] nr=no reaction.
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Table 2. Reaction of various N-tosylhydrazone with diphenyl
Table 3. Reaction of various diaryl disulfides with N-tosylhy-
disulfide.[a,b]
drazones.[a,b]
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[a] Reaction conditions: 1 (1.0 mmol), 2 (1.5 mmol) and
KOtBu (2.0 equiv.) in DMSO (3 mL) at 1008C for 10–
30 min.
[b] Isolated yields.
the product in 86% yield within 15 minutes
(Scheme 2).
Scheme 2. Gram-scale synthesis.
The successful carbene insertion into SÀS bond
prompted to investigate this transformation in a one-
pot manner where tosylhydrazone could be generated
in situ from corresponding aldehyde and tosylhydra-
zide. This process would be step economic as it avoids
isolation of intermediate N-tosylhydrazone. At first,
benzaldehyde and tosylhydrazide were stirred at room
temperature in DMSO for 1 h. Then Ph2S2 and KOtBu
were added and the reaction was heated at 1008C. As
[a] Reaction conditions: 1 (1.0 mmol), 2 a (1.5 mmol) and
KOtBu (2.0 equiv.) in DMSO (3 mL) at 1008C for 10–
30 min.
[b] Isolated yields.
46 withdrawing group (F) and weak electron-withdrawing expected, the reaction proceeded well in one-pot
47 substituents (Cl and Br) could also be employed as condition and comparable yield was observed. Few
48 suitable substrates affording the corresponding prod- more substrates were employed in this reaction
49 ucts (3ag–ak) in moderate to good yields. Substrate conditions and the results are shown in Table 4.
50 bearing pyridine moiety was also compatible with
To validate the stability of bis(arylthio)acetal, 3l
51 reaction conditions, giving 3al in 68% isolated yield. was subjected to palladium catalyzed cross-coupling
52 The insertion rection was unsuccessful when bis(4- reaction with arylboronic acid 5 (Scheme 3). Thioace-
53 nitrophenyl) disulphide was used as substrate.
tal undergone the arylation and corresponding prod-
54
A scale-up reaction was performed to showcase the uct 6 was obtained in good yield. Notably, the
55 synthetic utility of this new methodology. To our thioacetal group was very stable and remained un-
56 delight, reaction of N-tosylhydrazone 1a with diphe- affected.
57 nyldisulfide 2a under the standard condition provided
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2 forms an ylide intermediate C. Finally, 1,2-migration
or Stevens rearrangement of C with XÀX bond
cleavage affords the desired product.
Table 4. One-pot reaction through in situ synthesis of N-
tosylhydrazones.
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Scheme 4. Possible reaction pathway.
To cast light on the reaction mechanism of this
insertion process, few control experiments were
carried out (Scheme 5). Pre-formed diazo compound 8
was subjected to insertion reaction at room temper-
ature and the corresponding thioacetal 3u was
obtained as a sole product (Scheme 5, eq 4). This
Scheme 3. Derivatization of thioacetal.
After exploration of carbene insertion into SÀS result proves that the reaction proceeds via diazo
26 bond, we turned our attention to SeÀSe bond since intermediate A. But, the same reaction did not
27 selenoacetals found utility in various areas including proceed without base which shows that base is
28 organo-selenium chemistry.[17] Diphenyldiselenide was necessary not only for diazo compound A formation,
29 subjected under the optimized reaction conditions. As it is also essential for subsequent steps as well.[18] Next,
30 anticipated, carbene insertion proceeded smoothly to diazo intermediate could be decomposed into alde-
31 provide bis(phenylseleno)acetals 7 in good yields. hyde which can undergo deoxygenative thioacetaliza-
32 Substrates bearing electron donating groups (7b and tion with disulfides. To check this hypothesis, a
33 7c), halogen and withdrawing groups were well competitive experiment was designed between benzal-
34 tolerated and gave the desired product in moderate dehyde 4a and p-ethoxybenzaldehyde derived tosylhy-
35 yields (7d and 7e) (Table 5).
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drazone 1f (Scheme 5, eq 5). However, formation of
3a was not detected by HNMR analysis of crude
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reaction mixture and 3f was isolated with 86% yield.
It clearly supports that the reaction does not proceed
via deoxygenative thioacetalization. To examine the
Table 5. Carbene insertion across SeÀSe bond.
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A possible reaction mechanism for the metal-free
52 carbene insertion reaction is shown in Scheme 4.
53 Initially, diazo compound A could be generated in situ
54 from corresponding tosylhydrazone upon heating with
55 base through BamfordÀStevens reaction. Thermally
56 induced exclusion of N2 would lead to the formation
57 of free carbene species[7a] B which upon reacting with
Scheme 5. Control experiments.
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successively added to oven dried reaction tube. DMSO
(3 mL) was added and closed with glass-stopper. The
reaction tube was then immersed in a 100 8C pre-heated oil
bath. The reaction was heated with stirring till complete
consumption of 1. Upon cooling down to room temperature,
water was added to the reaction mixture and extracted with
ethyl acetate (33 5 mL). Brine wash (13 10 mL) was given to
the combined organic extractions and dried over anhydrous
Na2SO4. Removal of solvent and neutral alumina column
separation of crude using hexanes and ethyl acetate mixture
(49:1) afforded the corresponding bis(arylthio)acetal 3.
(Phenylmethylene)bis(phenylsulfane)[12] (3a): 275 mg, 89%
yield; colourless oil; Rf 0.71 (2% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.42 (s, 1H), 7.19–7.25 (m,
9H), 7.30–7.37 (m, 6H); 13CNMR (CDCl3, 100 MHz) d 60.5,
127.9, 128.0, 128.2, 128.6, 129.0, 132.6, 134.6, 139.7; FTIR
(neat) 691, 742, 1024, 1438, 1479, 1581, 3025 cmÀ1; HRMS
(m/z): [M+Na]+ calcd for C19H16S2Na: 331.0591; found
331.0591.
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possibility of whether a sulfur radical (ArS·) is
involved in the insertion process,[11d] a radical trapping
experiment was carried out (Scheme 5, eq 6). The
addition of 2 equiv. of TEMPO (2,2,6,6-tetramethylpi-
peridine-1-oxyl) under our standard reaction condi-
tions had no effect, as the inserted product 3a was
isolated in 82% yield. Hence, we propose that
insertion mainly proceeds through formation of ylide
C.[11b]
10
In conclusion, a new procedure involving carbene
11 insertion into SÀS and SeÀSe bonds have been
12 developed using N-tosylhydrazone as a safe, stable
13 and readily synthesizable carbene precursor. This
14 protocol paves a way to synthesize thio- and selenoa-
15 cetals under thiol and selenol-free conditions in good
16 to excellent yields. This new protocol features with
17 short reaction time, high functional group tolerance
18 and wide substrate scope. Scale-up reaction and one-
19 pot synthesis involving in situ generation of tosylhy-
20 drazone were demonstrated to show the applicability
21 of this protocol.
(p-Tolylmethylene)bis(phenylsulfane)[12] (3b): 297 mg, 92%
yield; white solid; mp 56–588C; Rf 0.41 (2% ethyl acetate in
1
hexanes); HNMR (CDCl3, 400 MHz) d 2.30 (s, 3H), 5.41 (s,
22
23
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1H), 7.07 (d, J=8.0 Hz, 2H), 7.19–7.25 (m, 6H), 7.26 (d, J=
8.0 Hz, 2H), 7.31–7.36 (m, 4H); 13CNMR (CDCl3, 100 MHz)
d 21.3, 60.3, 127.8, 127.9, 128.9, 129.3, 132.4, 134.9, 136.8,
138.0; FTIR (KBr) 689, 736, 1024, 1438, 1479, 3019 cmÀ1;
HRMS (m/z): [M+H]+ calcd for C20H19S2: 323.0928; found
323.0925.
Experimental Section
25 General information
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All reactions were carried out in oven-dried reaction tubes.
Reactions were monitored by thin-layer chromatography
(TLC) using Merck silica gel 60 F254 precoated plates
(0.25 mm) and visualized by UV fluorescence quenching
using appropriate mixture of ethyl acetate and hexanes.
Aluminium oxide (neutral) was purchased from Thermo
((4-Ethylphenyl)methylene)bis(phenylsulfane)[12]
(3c):
280 mg, 83% yield; colourless oil; Rf 0.40 (2% ethyl acetate
in hexanes); 1HNMR (CDCl3, 400 MHz) d 1.25 (t, J=7.6 Hz,
3H), 2.66 (q, J=7.6 Hz, 2H), 5.46 (s, 1H), 7.14 (d, J=8.0 Hz,
2H), 7.24–7.30 (m, 6H), 7.33 (d, J=8.0 Hz, 2H), 7.35–7.42
(m, 4H); 13CNMR (CDCl3, 100 MHz) d 15.5, 28.7, 60.4,
127.8, 127.9, 128.1, 128.9, 132.5, 135.0, 137.0, 144.3; FTIR
(neat) 688, 737, 840, 1024, 1438, 1479, 2964, 3057 cmÀ1;
HRMS (m/z): [M+Na]+ calcd for C21H20S2Na: 359.0904;
found 359.0896.
32 Fisher scientific and used for column chromatography using
hexanes and ethyl acetate mixture as eluent. All the
reactions were carried out in temperature controlled IKA
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magnetic stirrers. H and 13CNMR spectra were recorded on
a Bruker 400 MHz and 500 MHz (100 MHz and 125 MHz for
1
13C) instrument. HNMR spectra were reported relative to
residual CDCl3 (d 7.26 ppm) and DMSO-d6 (d 2.50 ppm).
When the residual peak overlapping with compound, spectra
was reported to residual TMS. 13CNMR were reported
relative to CDCl3 (d 77.16 ppm). Chemical shifts were
reported in parts per million and multiplicities are as
indicated: s (singlet), d (doublet), t (triplet), q (quartet), sep
((4-Isopropylphenyl)methylene)bis(phenylsulfane)
(3d):
337 mg, 96% yield; colorless semi solid; Rf 0.45 (2% ethyl
1
acetate in hexanes); HNMR (CDCl3, 400 MHz) d 1.26 (d,
J=6.8 Hz, 6H), 2.91 (sep, J=6.8 Hz, 1H), 5.46 (s, 1H), 7.16
(d, J=8.0 Hz, 2H), 7.24–7.29 (m, 6H), 7.31–7.35 (m, 2H),
7.35–7.40 (m, 4H); 13CNMR (CDCl3, 100 MHz) d 24.0, 33.9,
60.4, 126.7, 127.8, 127.9, 128.9, 132.5, 135.0, 137.1, 148.9;
FTIR (neat) 689, 736, 1024, 1438, 1479, 1582, 2869, 2959,
3057 cmÀ1; HRMS (m/z): [M+H]+ calcd for C22H23S2:
351.1241; found 351.1222.
(septet) and
m (multiplet). Coupling constants, J are
reported in Hertz. Melting points were recorded on a Guna
capillary melting point apparatus and uncorrected. Infrared
spectra were recorded on a FTIR 4000 Series Spectrometer
using KBr. The wave numbers of recorded IR signals are
quoted in cmÀ1. High resolution mass spectra (HRMS) were
recorded on Waters-Q-Tof Micro mass spectrometer. Diaryl
disulfides[19] and N-tosylhydrazones[15b] were synthesized
using a reported literature procedure.
((4-(Tert-butyl)phenyl)methylene)bis(phenylsulfane) (3e):
332 mg, 91% yield; colourless oil; Rf 0.32 (2% ethyl acetate
1
in hexanes); HNMR (CDCl3, 400 MHz) d 1.21 (s, 9H), 5.35
(s, 1H), 7.12–7.16 (m, 6H), 7.19–7.21 (m, 4H), 7.24–7.28 (m,
4H); 13CNMR (CDCl3, 100 MHz) d 31.4, 34.7, 60.4, 125.6,
127.6, 127.7, 128.9, 132.4, 135.0, 136.7, 151.2; FTIR (neat)
689, 736, 1024, 1267, 1479, 1582, 2984, 3057 cmÀ1; HRMS (m/
z): [M+Na]+ calcd for C23H24S2Na: 387.1217; found
387.1203.
General procedure for carbene insertion into SÀS
bond to synthesis of thioacetals 3
Under open atmosphere, N-tosylhydrazone 1 (1.0 mmol),
diaryl disulfide 2 (1.5 mmol) and KOtBu (2.0 mmol) were
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((4-Ethoxyphenyl)methylene)bis(phenylsulfane)
(3f):
(s, 1H), 7.22–7.32 (m, 8H), 7.34–7.44 (m, 6H); 13CNMR
1
2
3
4
5
6
7
8
9
318 mg, 90% yield; white solid; mp 74–768C; Rf 0.29 (2%
ethyl acetate in hexanes); 1HNMR (CDCl3, 400 MHz) d 1.43
(t, J=7.2 Hz, 3H), 4.04 (q, J=7.2 Hz, 2H), 5.47 (s, 1H), 6.80–
6.85 (m, 2H), 7.23–7.31 (m, 6H), 7.31–7.35 (m, 2H), 7.36–7.42
(m, 4H); 13CNMR (CDCl3, 100 MHz) d 14.9, 59.9, 63.6,
114.5, 127.8, 128.9, 129.2, 131.6, 132.5, 134.9, 158.8; FTIR
(KBr) 687, 738, 1024, 1245, 1508, 1607, 2926, 2677, 3067 cmÀ1;
HRMS (m/z): [M+Na]+ calcd for C21H20OS2Na: 375.0853;
found 375.0828.
(CDCl3, 100 MHz) d 59.9, 122.0, 128.2, 129.1, 129.7, 131.7,
132.9, 134.1, 138.9; FTIR (KBr) 700, 750, 1025, 1484, 1590,
1642, 3042 cmÀ1; HRMS (m/z): [M+H]+ calcd for C19H16
BrS2: 386.9877; found 386.9874.
((4-Chlorophenyl)methylene)bis(phenylsulfane)[12]
(3m):
295 mg, 86% yield; white solid; 68–708C; Rf 0.55 (2% ethyl
1
acetate in hexanes); HNMR (CDCl3, 400 MHz) d 5.37 (s,
1H), 7.19–7.28 (m, 10H), 7.30–7.35 (m, 4H); 13CNMR
(CDCl3, 100 MHz) d 59.9, 128.2, 128.7, 129.1, 129.4, 132.9,
133.8, 134.1, 138.4; FTIR (KBr) 647, 689, 719, 1015, 1438,
1475, 3047 cmÀ1; HRMS (m/z): [M+K]+ calcd for C19H15ClS2
K: 380.9941; found 380.9939.
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4-(Bis(phenylthio)methyl)-N,N-dimethylaniline
(3g):
292 mg, 83% yield; white solid; mp 124–1268C; Rf 0.39 (5%
ethyl acetate in hexanes); 1HNMR (CDCl3, 400 MHz) d 2.97
(s, 6H), 5.47 (s, 1H), 6.66 (d, J=8.8 Hz, 2H), 7.22–7.34 (m,
8H), 7.35–7.42 (m, 4H); 13CNMR (CDCl3, 100 MHz) d 40.6,
60.0, 112.3, 127.0, 127.5, 128.9 (for 2C), 132.1, 135.5, 150.4;
FTIR (KBr) 680, 727, 1065, 1362, 1524, 1612, 2892,
3052 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C21H21NS2Na:
374.1013; found 374.1026.
((4-Fluorophenyl)methylene)bis(phenylsulfane)[12]
(3n):
261 mg, 80% yield; white solid; mp 48–508C; Rf 0.55 (2%
ethyl acetate in hexanes); 1HNMR (CDCl3, 400 MHz) d 5.40
(s, 1H), 6.89–6.96 (m, 2H), 7.21–7.26 (m, 6H), 7.28–7.35 (m,
6H); 13CNMR (CDCl3, 100 MHz) d 59.8, 115.5 (d, J=21 Hz),
128.1, 129.0, 129.7 (d, J=8 Hz), 132.9, 134.3, 135.6 (d, J=
4 Hz), 162.4 (d, J=246 Hz); FTIR (KBr) 688, 739, 842, 1024,
1222, 1506, 3064 cmÀ1; HRMS (m/z): [M+H]+ calcd for C19
H16FS2: 327.0677; found 327.0670.
((3-Methoxyphenyl)methylene)bis(phenylsulfane)[12]
(3h):
183 mg, 54% yield; colourless oil; Rf 0.32 (2% ethyl acetate
1
in hexanes); HNMR (CDCl3, 400 MHz) d 3.78 (s, 3H), 5.43
(s, 1H), 6.82 (d, J=8.0 Hz, 1H), 6.92–7.01 (m, 2H), 7.21 (t,
J=8.0 Hz, 1H), 7.24–7.32 (m, 6H), 7.35–7.43 (m, 4H);
13CNMR (CDCl3, 100 MHz) d 55.4, 60.6, 113.2, 114.2, 120.4,
127.9, 129.0, 129.6, 132.7, 134.7, 141.3, 159.7; FTIR (neat)
688, 739, 1262, 1437, 1488, 1590, 2835, 3056 cmÀ1; HRMS (m/
z): [M+Na]+ calcd for C20H18OS2Na: 361.0697; found
361.0663.
((3-Bromophenyl)methylene)bis(phenylsulfane)
(3o):
310 mg, 80% yield; colourless oil; Rf 0.35 (2% ethyl acetate
1
in hexanes); HNMR (CDCl3, 400 MHz) d 5.38 (s, 1H), 7.15
(t, J=8.0 Hz, 1H), 7.26–7.32 (m, 7H), 7.34–7.40 (m, 5H), 7.51
(t, J=1.6 Hz, 1H); 13CNMR (CDCl3, 100 MHz) d 60.1, 122.5,
126.6, 128.3, 129.1, 130.0, 131.1, 131.2, 133.0, 134.0, 142.1;
FTIR (neat) 689, 737, 1024, 1438, 1478, 1583, 3056 cmÀ1;
HRMS (m/z): [M+H]+ calcd for C19H16BrS2: 386.9877;
found 386.9864.
(o-Tolylmethylene)bis(phenylsulfane) (3i): 287 mg, 89%
yield; colourless oil; Rf 0.40 (2% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 2.30 (s, 3H), 5.66 (s, 1H), 7.06–
7.11 (m, 1H), 7.11–7.17 (m, 2H), 7.19–7.25 (m, 6H), 7.29–7.36
(m, 4H), 7.58–7.67 (m, 1H); 13CNMR (CDCl3, 100 MHz) d
19.4, 57.2, 126.6, 127.8, 128.0, 128.4, 129.0, 130.5, 132.4, 135.0,
135.2, 137.5; FTIR (neat) 687, 737, 1024, 1265, 1437, 1481,
1582, 3064 cmÀ1; HRMS (m/z): [M+H]+ calcd for C20H19S2:
323.0928; found 323.0916.
((3-Fluorophenyl)methylene)bis(phenylsulfane)
(3p):
275 mg, 84% yield; colourless oil; Rf 0.68 (2% ethyl acetate
1
in hexanes); HNMR (CDCl3, 400 MHz) 5.38 (s, 1H), 6.91
(tdd, J=8.4, 2.4, 1.2 Hz, 1H), 7.06–7.12 (m, 2H), 7.16–7.21
(m, 1H). 7.21–7.26 (m, 6H), 7.31–7.36 (m, 4H); 13CNMR
(CDCl3, 100 MHz) d 60.1, 115.0 (d, J=22 Hz), 115.1 (d, J=
21 Hz), 123.7 (d, J=3 Hz), 128.2, 129.1, 130.0 (d, J=9 Hz),
132.9, 134.1, 142.4 (d, J=7 Hz), 162.8 (d, J=245 Hz); FTIR
(neat) 689, 739, 1251, 1440, 1480, 1586, 3059 cmÀ1; HRMS
(m/z): [M+Na]+ calcd for C19H15FS2Na: 349.0497; found
349.0475.
((2-Methoxyphenyl)methylene)bis(phenylsulfane)
(3j):
295 mg, 87% yield; colourless oil; Rf 0.32 (2% ethyl acetate
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in hexanes); HNMR (CDCl3, 400 MHz) d 3.82 (s, 3H), 6.13
(s, 1H), 6.86 (d, J=8.4 Hz, 1H), 6.95 (t, J=7.6 Hz, 1H), 7.22–
7.30 (m, 7H), 7.37–7.43 (m, 4H), 7.57–7.62 (m, 1H); 13CNMR
(CDCl3, 100 MHz) d 52.6, 55.8, 110.8, 120.9, 127.5, 128.0,
128.8, 129.0, 129.2, 132.1, 135.2, 155.8; FTIR (neat) 689, 744,
1024, 1245, 1437, 1487, 2835, 3062 cmÀ1; HRMS (m/z): [M+
Na]+ calcd for C20H18OS2Na: 361.0697; found 361.0696.
((2-Bromophenyl)methylene)bis(phenylsulfane)
(3q):
306 mg, 79% yield; colourless oil; Rf 0.48 (2% ethyl acetate
1
in hexanes); HNMR (CDCl3, 400 MHz) d 6.07 (s, 1H), 7.12
(td, J=7.6, 1.6 Hz, 1H), 7.24–7.30 (m, 7H), 7.37–7.43 (m,
4H), 7.54 (dd, J=8.0 Hz, 1.2 Hz, 1H), 7.72–7.79 (m, 1H);
13CNMR (CDCl3, 100 MHz) d 58.8, 123.7, 127.9, 128.0, 129.0,
129.5, 130.2, 132.4, 132.8, 134.3, 138.6; FTIR (neat) 689, 739,
1024, 1438, 1479, 1582, 3056 cmÀ1; HRMS (m/z): [M+H]+
calcd for C19H16BrS2: 386.9877; found 386.9870.
47 ((4-(Methylthio)phenyl)methylene)bis(phenylsulfane) (3k):
309 mg, 87% yield; off white solid; mp 88–908C; Rf 0.32 (2%
ethyl acetate in hexanes); 1HNMR (CDCl3, 400 MHz) d 2.38
(s, 3H), 5.32 (s, 1H), 7.02–7.10 (m, 2H), 7.12–7.23 (m, 8H),
7.23–7.31 (m, 4H); 13CNMR (CDCl3, 100 MHz) d 15.8, 60.1,
116.4, 128.0, 128.4, 129.0, 132.6, 134.6, 136.5, 138.5; FTIR
(KBr) 688, 749, 1024, 1087, 2920, 3069 cmÀ1; HRMS (m/z):
[M+K]+ calcd for C20H18S3K: 393.0208; found 393.0197.
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((2-Chlorophenyl)methylene)bis(phenylsulfane)
(3r):
292 mg, 85% yield; colourless oil; Rf 0.48 (2% ethyl acetate
in hexanes); 1HNMR (CDCl3, 400 MHz) d 6.03 (s, 1H), 7.13–
7.21 (m, 2H), 7.21–7.25 (m, 6H), 7.28–7.32 (m, 1H), 7.33–7.37
(m, 4H) 7.68 (dd, J=8.0, 2.0 Hz, 1H); 13CNMR (CDCl3, 100
MHz) d 56.1, 127.3, 128.0, 129.0, 129.2, 129.5, 130.0, 132.5,
132.9, 134.3, 137.1; FTIR (neat) 688, 742, 1024, 1438, 1468,
((4-Bromophenyl)methylene)bis(phenylsulfane)[12]
(3l):
318 mg, 82% yield; white solid; mp 92–948C; Rf 0.73 (2%
ethyl acetate in hexanes); 1HNMR (CDCl3, 400 MHz) d 5.40
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1479, 1582, 3061 cmÀ1; HRMS (m/z): [M+K]+ calcd for C19
H15ClS2K: 380.9941; found 380.9918.
((4-(Trifluoromethyl)phenyl)methylene)bis(phenylsulfane)
(3y): 287 mg, 76% yield; white solid; mp 76–788C; Rf 0.32
(2% ethyl acetate in hexanes); 1HNMR (CDCl3, 500 MHz) d
5.34 (s, 1H), 7.11–7.19 (m, 6H), 7.20–7.28 (m, 4H), 7.34 (d,
J=6.4 Hz, 2H), 7.41 (d, J=6.4 Hz, 2H); 13CNMR (CDCl3,
125 MHz) d 60.1, 124.1 (q, J=270 Hz), 125.5 (q, J=3.75 Hz),
128.3, 128.4, 129.1, 130.1 (q, J=32.5 Hz), 133.0, 133.8, 143.9;
FTIR (KBr) 688, 733, 1071, 1109, 1161, 1331, 1438, 2919,
3069 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C20H15F3S2Na:
399.0465; found 399.0491.
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((2-Fluorophenyl)methylene)bis(phenylsulfane)
(3s):
262 mg, 80% yield; colourless oil; Rf 0.42 (2% ethyl acetate
in hexanes); 1HNMR (CDCl3, 400 MHz) d 5.91 (s, 1H), 6.97–
7.05 (m, 1H), 7.12 (td, J=7.6, 1.2 Hz, 1H), 7.21–7.26 (m, 1H),
7.26–7.32 (m, 6H), 7.39–7.45 (m, 4H), 7.61 (td, J=7.6, 1.6 Hz,
1H); 13CNMR (CDCl3, 100 MHz) d 52.4 (d, J=2 Hz), 115.3
(d, J=22 Hz), 124.4 (d, J=4 Hz), 127.1 (d, J=13 Hz), 128.1,
129.0, 129.6, 129.7 (d, J=4 Hz), 132.7, 134.2, 159.2 (d, J=
243 Hz); FTIR (neat) 689, 748, 1024, 1237, 1484, 1583, 2924,
3057 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C19H15FS2Na:
349.0497; found 349.0468.
Methyl-4-(bis(phenylthio)methyl)benzoate (3z): 268 mg,
73% yield; white solid; mp 66–688C; Rf 0.26 (2% ethyl
1
acetate in hexanes); HNMR (CDCl3, 400 MHz) d 3.93 (s,
3H), 5.45 (s, 1H), 7.24–7.30 (m, 6H), 7.33–7.39 (m, 4H), 7.39–
7.43 (m, 2H), 7.92–7.98 (m, 2H); 13CNMR (CDCl3, 100 MHz)
d 52.3, 60.3, 128.1, 128.3, 129.1, 129.8, 129.9, 133.1, 133.9,
144.9, 166.8; FTIR (KBr) 689, 741, 1019, 1108, 1277, 1435,
1702, 3057 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C21H18O2
S2Na: 389.0646; found 389.0660.
14 ((2-(Phenylethynyl)phenyl)methylene)bis(phenylsulfane)
(3t): 376 mg, 92% yield; pale yellow oil; Rf 0.42 (2% ethyl
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acetate in hexanes); HNMR (CDCl3, 400 MHz) d 6.29 (s,
1H), 7.20–7.25 (m, 6H), 7.25–7.29 (m, 1H), 7.31–7.39 (m,
4H), 7.9–7.45 (m, 6H), 7.52 (dd, J=7.6, 1.6 Hz, 1H), 7.74–
7.82 (m, 1H); 13CNMR (CDCl3, 100 MHz) d 57.6, 87.0, 95.3,
122.1, 123.1, 127.6, 127.9, 128.0, 128.5, 128.7, 128.9, 129.0,
131.7, 131.9, 132.1, 135.1, 141.3; FTIR (neat) 689, 756, 1024,
1438, 1479, 1492, 1582, 3054 cmÀ1; HRMS (m/z): [M+Na]+
calcd for C27H20S2Na: 431.0904; found 431.0874.
2-(Bis(phenylthio)methyl)furan (3aa): 221 mg, 74% yield;
pale yellow oil; Rf 0.39 (2% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.47 (s, 1H), 6.16 (d, J=
3.2 Hz, 1H), 6.24 (dd, J=3.2, 3.2 Hz, 1H), 7.26–7.30 (m, 6H),
7.35–7.40 (m, 5H); 13CNMR (CDCl3, 100 MHz) d 53.3, 109.1,
110.6, 128.3, 129.0, 133.2, 133.8, 142.6, 151.4; FTIR (neat)
688, 739, 1024, 1438, 1479, 1582, 2924, 3055 cmÀ1; HRMS (m/
z): [M+Na]+ calcd for C17H14OS2Na: 321.0384; found
321.0382.
((4-Nitrophenyl)methylene)bis(phenylsulfane) (3u): 287 mg,
81% yield; pale yellow oil; Rf 0.42 (5% ethyl acetate in
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hexanes); HNMR (CDCl3, 400 MHz) d 5.46 (s, 1H), 7.24–
7.32 (m, 6H), 7.34–7.39 (m, 4H), 7.44–7.50 (m, 2H), 8.04–8.14
(m, 2H); 13CNMR (CDCl3, 100 MHz) d 60.0, 123.8, 128.7,
128.9, 129.2, 133.2, 133.4, 147.3, 147.4; FTIR (neat) 689, 739,
1024, 1109, 1344, 1517, 2925, 3068 cmÀ1; HRMS (m/z): [M+
Na]+ calcd for C19H15NO2S2Na: 376.0442; found 376.0428.
3-(Bis(phenylthio)methyl)pyridine (3ab): 257 mg, 83% yield;
colourless oil; Rf 0.48 (30% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.34 (s, 1H), 7.07–7.14 (m,
1H), 7.14–7.21 (m, 6H), 7.21–7.31 (m, 4H), 7.58–7.66 (m,
1H), 8.32–8.40 (m, 2H); 13CNMR (CDCl3, 100 MHz) d 58.0,
123.4, 128.5, 129.1, 133.3, 133.5, 135.4, 135.8, 149.1, 149.3;
FTIR (neat) 690, 749, 1024, 1420, 1478, 1573, 3053 cmÀ1;
HRMS (m/z): [M+H]+ calcd for C18H16NS2: 310.0724; found
310.0721.
4-(Bis(phenylthio)methyl)benzonitrile (3v): 237 mg, 71%
yield; colourless oil; Rf 0.29 (5% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.42 (s, 1H), 7.25–7.32 (m,
6H), 7.33–7.38 (m, 4H), 7.39–7.44 (m, 2H), 7.52–7.57 (m,
2H); 13CNMR (CDCl3, 100 MHz) d 60.2, 111.7, 118.6, 128.6,
128.7, 129.2, 132.3, 133.3, 133.4, 145.2; FTIR (neat) 688, 743,
850, 1024, 1438, 1478, 2228, 2924, 3055 cmÀ1; HRMS (m/z):
[M+Na]+ calcd for C20H15NS2Na: 356.0544; found 356.0564.
2-(Bis(phenylthio)methyl)thiophene (3ac): 145 mg, 46%
yield; pale yellow oil; Rf 0.32 (2% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.72 (s, 1H), 6.88 (dd, J=4.8,
3.8 Hz, 1H), 6.97 (d, J=3.6 Hz, 1H), 7.25 (dd, J=4.8, 1.2 Hz,
1H), 7.28–7.33 (m, 6H), 7.39–7.46 (m, 4H); 13CNMR (CDCl3,
100 MHz) d 55.9, 125.9, 126.6, 126.7, 128.2, 129.0, 132.9,
134.3, 143.8; FTIR (neat) 690, 749, 1024, 1420, 1478, 1573,
3053 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C17H14S3Na:
337.0155; found 337.0164.
3-(Bis(phenylthio)methyl)benzonitrile (3w): 264 mg, 79%
yield; colourless oil; Rf 0.32 (5% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.31 (s, 1H), 7.16–7.22 (m,
6H), 7.22–7.31 (m, 5H), 7.42 (dt, J=7.6, 1.2 Hz, 1H), 7.45–
7.51 (m, 2H); 13CNMR (CDCl3, 100 MHz) d 59.8, 112.5,
118.5, 128.6, 129.2, 129.4, 131.5, 131.6, 132.4, 133.3, 133.4,
141.5; FTIR (neat) 688, 742, 1024, 1438, 1479, 1581, 2230,
3058 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C20H15NS2Na:
(Phenylmethylene)bis(p-tolylsulfane) (3ad): 290 mg, 86%
yield; white solid; mp 64–668C; Rf 0.47 (2% ethyl acetate in
hexanes); 1H NMR (CDCl3, 400 MHz) d 2.29 (s, 6H), 5.31 (s,
1H), 7.00–7.07 (m, 4H), 7.18–7.26 (m, 7H), 7.28–7.34 (m,
4H); 13C NMR (CDCl3, 100 MHz) d 21.3, 61.4, 128.0, 128.5,
129.7, 131.0, 133.3, 134.8, 138.1, 140.1; FTIR (KBr) 697, 808,
1017, 1450, 1490, 2974, 3059 cmÀ1; HRMS (m/z): [M+Na]+
calcd for C21H20S2Na: 359.0904; found 359.0919.
47 356.0544; found 356.0529.
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((3-Nitrophenyl)methylene)bis(phenylsulfane) (3x): 297 mg,
84% yield; pale yellow oil; Rf 0.39 (5% ethyl acetate in
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hexanes); HNMR (CDCl3, 400 MHz) d 5.40 (s, 1H), 7.16–
7.22 (m, 6H), 7.24–7.30 (m, 4H), 7.34 (t, J=8.8 Hz, 1H), 7.58
(dt, J=8.0, 1.6 Hz, 1H), 8.00 (ddd, J=8.0, 1.6, 0.8 Hz, 1H),
8.05 (t, J=2.0 Hz, 1H); 13CNMR (CDCl3, 100 MHz) d 59.9,
54 123.0, 123.1, 128.7, 129.2, 129.5, 133.3, 133.4, 134.0, 142.1,
((4-(Tert-butyl)phenyl)methylene)bis((3-methoxyphenyl)sul-
fane) (3ae): 311 mg, 73% yield; colourless oil; Rf 0.49 (5%
ethyl acetate in hexanes); 1H NMR (CDCl3, 400 MHz) d 1.31
(s, 9H), 3.70 (s, 6H), 5.47 (s, 1H), 6.78 (ddd, J=8.0, 2.4, 0.8
148.2; FTIR (neat) 689, 739, 1024, 1351, 1526, 2924,
3066 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C19H15NO2S2
Na: 376.0442; found 376.0447.
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Hz, 2H), 6.83–6.87 (m, 2H), 6.96–7.01 (m, 2H), 7.13–7.20 (m,
2H), 7.30–7.32 (m, 4H); 13C NMR (CDCl3, 100 MHz) d 31.4,
34.7, 55.3, 59.9, 114.0, 117.0, 124.4, 125.6, 127.7, 129.7, 136.1,
136.8, 151.2, 159.7; FTIR (neat) 686, 773, 1041, 1246, 1477,
1588, 2960 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C25H28O2
S2Na: 447.1428; found 447.1423.
2,2’-((Phenylmethylene)bis(sulfanediyl))dipyridine
(3al):
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212 mg, 68% yield; colourless oil; Rf 0.40 (15% ethyl acetate
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in hexanes); H NMR (CDCl3, 400 MHz) d 6.92–7.00 (m,
2H), 7.03 (s, 1H), 7.12–7.34 (m, 5H), 7.40–7.49 (m, 2H), 7.56–
7.72 (m, 2H), 8.38–8.49 (m, 2H); 13C NMR (CDCl3, 100
MHz) d 51.0, 120.3, 122.6, 128.0, 128.3, 128.6, 136.4, 140.0,
149.7, 158.0; FTIR (neat) 698, 985, 1117, 1560, 2992,
3046 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C17H14N2S2Na:
333.0496; found 333.0498.
(Phenylmethylene)bis(o-tolylsulfane) (3af): 277 mg, 82%
yield; colourless oil; Rf 0.55 (2% ethyl acetate in hexanes);
1H NMR (CDCl3, 400 MHz) d 2.29 (s, 3H), 5.29 (s, 1H),
7.03–7.10 (m, 2H), 7.11–7.16 (m, 4H), 7.21–7.28 (m, 3H),
7.31–7.41 (m, 4H); 13C NMR (CDCl3, 100 MHz) d 20.7, 60.1,
126.5, 127.9, 128.0, 128.1, 128.6, 130.4, 133.2, 134.1, 140.1,
140.3; FTIR (neat) 699, 751, 1061, 1468, 1588, 2921,
3059 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C21H20S2Na:
359.0904; found 359.0895.
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General procedure for one-pot reaction through
in situ synthesis of N-tosylhydrazones
To a rapidly stirred suspension of tosylhydrazide (1.0 mmol)
in DMSO (1 mL), aldehyde (1.0 mmol) was added dropwise
(solid aldehydes were added as portion wise) and the mixture
was stirred at room temperature for 1 h. Diphenyl disulfide
2a (1.5 mmol), K2CO3 (2.0 mmol) and DMSO (2 mL) were
added successively in open atmosphere. Reaction tube was
stoppered and heated to 1008C in pre-heated oil bath.
Reaction was monitored by TLC. After completion of
reaction, reaction mixture was cooled to room temperature,
water was added and extracted with EtOAc (33 5 mL). Brine
wash (13 5 mL) was given to combined organic extractions
and dried over Na2SO4. Solvent was evaporated and the
crude mixture was purified by column chromatography using
alumina (neutral) and hexanes/ethyl acetate (49:1) as eluent
to afford the corresponding product.
(Phenylmethylene)bis((4-fluorophenyl)sulfane)
(3ag):
262 mg, 76% yield; colourless oil; Rf 0.57 (2% ethyl acetate
in hexanes); 1H NMR (CDCl3, 400 MHz) d 5.23 (s, 1H),
6.89–6.96 (m, 4H), 7.22–7.26 (m, 5H), 7.27–7.34 (m, 4H); 13C
NMR (CDCl3, 100 MHz) d 62.2, 116.2 (d, J=22 Hz), 127.9,
128.3, 128.6, 129.2 (d, J=3 Hz), 135.9 (d, J=8 Hz), 139.4,
163.0 (d, J=247 Hz); FTIR (neat) 698, 826, 1012, 1452, 1589,
2924, 3063 cmÀ1; HRMS (m/z): [M+H]+ calcd for C19H15F2
S2: 345.0583; found 345.0582.
(Phenylmethylene)bis((4-chlorophenyl)sulfane)[12]
(3ah):
332 mg, 88% yield; colourless oil; Rf 0.38 (2% ethyl acetate
in hexanes); 1HNMR (CDCl3, 400 MHz) d 5.33 (s, 1H), 7.16–
7.18 (m, 1H), 7.18–7.23 (m, 6H), 7.23–7.27 (m, 4H), 7.28–7.32
(m, 2H); 13CNMR (CDCl3, 100 MHz) d 60.9, 127.9, 128.5,
128.7, 129.1, 132.6, 134.3, 134.4, 139.0; FTIR (neat) 697, 819,
1012, 1388, 1474, 1572, 2919, 3058 cmÀ1; [M+Na]+ calcd for
C19H14Cl2S2Na: 398.9811; found 398.9801.
((2,4-Dimethoxyphenyl)methylene)bis(phenylsulfane)
(3am): 336 mg, 91% yield; colourless oil; Rf 0.39 (2% ethyl
1
acetate in hexanes); HNMR (CDCl3, 400 MHz) d 3.80 (s,
3H), 3.81 (s, 3H), 6.04 (s, 1H), 6.42 (d, J=2.4 Hz, 1H), 6.45
(dd, J=8.8, 2.4 Hz, 1H), 7.20–7.29 (m, 6H), 7.34–7.41 (m,
4H), 7.50 (d, J=8.4 Hz, 1H); 13CNMR (CDCl3, 100 MHz) d
52.2, 55.5, 55.8, 98.5, 104.8, 120.5, 127.3, 128.8, 129.8, 131.9,
135.5, 157.0, 160.7; FTIR (neat) 688, 740, 1026, 1164, 1290,
1615, 2947, 3060 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C21
H20O2S2Na: 391.0802; found 391.0805.
3-(Bis((4-chlorophenyl)thio)methyl)benzonitrile
(3ai):
359 mg, 89% yield; colourless oil; Rf 0.50 (10% ethyl acetate
in hexanes); 1H NMR (CDCl3, 400 MHz) d 5.30 (s, 1H),
7.20–7.26 (m, 8H), 7.35–7.41 (m, 1H), 7.48–7.56 (m, 2H),
7.58–7.61 (m, 1H); 13C NMR (CDCl3, 100 MHz) d 60.2, 112.9,
118.4, 129.5, 129.6, 131.4, 131.5, 132.0, 132.3, 134.8, 135.2,
140.9; FTIR (neat) 687, 822, 1013, 1093, 1475, 2231, 2924,
3060 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C20H13NCl2S2
Na: 423.9764; found 423.9760.
((2-Ethoxyphenyl)methylene)bis(phenylsulfane)
(3an):
290 mg, 82% yield; colourless oil; Rf 0.32 (2% ethyl acetate
in hexanes); 1HNMR (CDCl3, 400 MHz) d 1.42 (t, J=6.8 Hz,
3H), 4.04 (q, J=6.8 Hz, 2H), 6.15 (s, 1H), 6.84 (d, J=8.4 Hz,
1H), 6.90–6.97 (m, 1H), 7.19–7.29 (m, 7H), 7.36–7.43 (m,
4H), 7.58–7.65 (m, 1H); 13CNMR (CDCl3, 100 MHz) d 15.0,
52.7, 64.1, 111.7, 120.8, 127.4, 128.2, 128.8, 129.0, 129.1, 131.9,
135.5, 155.2; FTIR (neat) 689, 753, 1024, 1248, 1478, 1582,
2978, 3057 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C21H20
OS2Na: 375.0853; found 375.0854.
3-(Bis((4-bromophenyl)thio)methyl)pyridine (3aj): 332 mg,
71% yield; colourless oil; Rf 0.48 (20% ethyl acetate in
1
hexanes); H NMR (CDCl3, 400 MHz) d 5.34 (s, 1H), 7.16–
7.24 (m, 5H), 7.33–7.42 (m, 4H), 7.60–7.69 (m, 1H), 8.41–8.51
(m, 2H); 13C NMR (CDCl3, 100 MHz) d 58.1, 123.2, 123.6,
132.2, 132.4, 134.9, 135.0, 135.4, 149.1, 149.7; FTIR (neat)
47 709, 812, 1008, 1472, 2919, 3058 cmÀ1; HRMS (m/z): [M+
4-(Bis(phenylthio)methyl)pyridine (3ao): 229 mg, 74% yield;
pale yellow oil; Rf 0.55 (30% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.33 (s, 1H), 7.20–7.24 (m,
2H), 7.27–7.31 (m, 6H), 7.33–7.39 (m, 4H), 8.47–8.53 (m,
2H); 13CNMR (CDCl3, 100 MHz) d 59.6, 122.7, 128.6, 129.2,
133.3, 148.7, 150.0, 151.1; FTIR (neat) 687, 738, 1023, 1438,
1476, 1577, 2919, 3069 cmÀ1; HRMS (m/z): [M+H]+ calcd
for C18H16NS2: 310.0724; found 310.0717.
H]+ calcd for C18H14NBr2S2: 465.8934; found 465.8927.
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((4-Nitrophenyl)methylene)bis((4-bromophenyl)sulfane)
(3ak): 404 mg, 79% yield; yellow solid; mp 92–948C; Rf 0.46
1
(10% ethyl acetate in hexanes); H NMR (CDCl3, 400 MHz)
d 5.36 (s, 1H), 7.16–7.22 (m, 4H), 7.35–7.42 (m, 4H), 7.44 (d,
J=8.4 Hz, 2H), 8.12 (d, J=8.8 Hz, 2H); 13C NMR (CDCl3,
54 100 MHz) d 60.0, 123.4, 124.0, 128.8, 132.0, 132.5, 135.0,
146.4, 147.6; FTIR (KBr) 732, 817, 1009, 1346, 1520, 2924,
3069 cmÀ1; HRMS (m/z): [M+H]+ calcd for C19H14NO2S2
Br2: 509.8833; found 509.8831.
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128.4, 128.6, 129.2, 129.5 (q, J=32.5 Hz), 130.4, 135.0, 145.5;
FTIR (KBr) 689, 740, 846, 1066, 1322, 1475, 2923, 3061 cmÀ1;
HRMS (m/z): [M+H]+ calcd for C20H16F3Se2: 472.9535;
found 472.9565.
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General procedure for carbene insertion into Se-Se
bond to synthesis of selenoacetal 7
Under open atmosphere, N-tosylhydrazone 1 (1.0 mmol),
diphenyl diselenide (1.5 mmol) and KOtBu (2.0 mmol) were
successively added to oven dried reaction tube. DMSO
(3 mL) was added and closed with glass-stopper. The
reaction tube was then immersed in a 100 8C pre-heated oil
bath. The reaction was heated with stirring till complete
consumption of 1. Generally reaction completes within 30
minutes. Upon cooling down to room temperature, water
was added to the reaction mixture and extracted with ethyl
acetate (33 5 mL). Brine wash (13 5 mL) was given to the
combined organic extractions and dried over anhydrous Na2
SO4. Removal of solvent and neutral alumina column
separation of crude using hexanes and ethyl acetate mixture
(49:1) afforded the corresponding bis(phenylseleno)acetal 7.
Procedure for synthesis of 6:
Under open atmosphere, ((4-bromophenyl)methylene)bis
(phenylsulfane) 3l (0.5 mmol), p-tolylboronic acid
5
(1.5 mmol), Pd(PPh3)4 (5 mol%) and K2CO3 (1.0 mmol) were
successively added to oven dried reaction tube. Degassed
1,4-dioxane (3 mL) was added and closed with glass-stopper.
The reaction tube was then immersed in a 100 8C pre-heated
oil bath. The reaction was heated with stirring till complete
consumption of 3l. The reaction progression was monitored
by TLC. After 6 h, reaction mixture was cooled down to
room temperature. Water was added to the reaction mixture
and extracted with ethyl acetate (33 5 mL). Brine wash (13
5 mL) was given to the combined organic extractions and
dried over anhydrous Na2SO4. Removal of solvent and
neutral alumina column separation of crude using hexanes
and ethyl acetate mixture (49:1) afforded coupled product 6.
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(Phenylmethylene)bis(phenylselane) (7a): 306 mg, 76%
yield; pale yellow oil; Rf 0.32 (2% ethyl acetate in hexanes);
1HNMR (CDCl3, 400 MHz) d 5.47 (s, 1H), 7.13–7.20 (m,
7H), 7.20–7.27 (m, 4H), 7.38–7.44 (m, 4H); 13CNMR (CDCl3,
100 MHz) d 43.9, 127.6, 128.1, 128.2, 128.4, 129.0, 131.1,
134.7, 141.3; FTIR (neat) 693, 737, 1022, 1065, 1265, 1475,
1577, 3025, 3054 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C19
H16Se2Na: 426.9480; found 426.9471.
((4’-Methyl-[1,1’-biphenyl]-4-yl)methylene)bis(phenylsu
lfane) (6): 178 mg, 89% yield; white solid; mp 100–1028C; Rf
1
0.29 (2% ethyl acetate in hexanes); HNMR (CDCl3, 400
((4-Isopropylphenyl)methylene)bis(phenylselane)
(7b):
MHz) d 2.31 (s, 3H), 5.39 (s, 1H), 7.14–7.19 (m, 8H), 7.27–
7.32 (m, 4H), 7.32–7.36 (m, 2H), 7.37–7.44 (m, 4H); 13CNMR
(CDCl3, 100 MHz) d 21.3, 60.4, 127.0, 127.1, 127.9, 128.4,
129.0, 129.6, 132.7, 134.7, 137.4, 137.7, 138.5, 140.9; FTIR
(KBr) 688, 751, 815, 1024, 1186, 1438, 1493, 2853, 2920,
3066 cmÀ1; HRMS (m/z): [M+Na]+ calcd for C26H22S2Na:
421.1061; found 421.1061.
352 mg, 79% yield; pale yellow oil; Rf 0.29 (2% ethyl acetate
in hexanes); 1HNMR (CDCl3, 400 MHz) d 1.20 (d, J=
6.4 Hz, 6H), 2.84 (sep, J=6.4 Hz, 1H), 5.48 (s, 1H), 7.05 (d,
J=6.8 Hz, 2H), 7.15–7.27 (m, 8H), 7.41 (d, J=7.2 Hz, 4H);
13CNMR (CDCl3, 100 MHz) d 24.1, 33.9, 44.0, 126.5, 127.9,
128.1, 129.0, 131.4, 134.6, 138.7, 148.4; FTIR (neat) 685, 735,
1022, 1475, 1574, 2959, 3053 cmÀ1; HRMS (m/z): [M+Na]+
calcd for C22H22Se2Na: 468.9949; found 468.9950.
Synthesis of 1-(diazomethyl)-4-nitrobenzene 8:
((3-Methoxyphenyl)methylene)bis(phenylselane)
(7c):
A reported procedure was followed to synthesize 1-(diazo-
methyl)-4-nitrobenzene.[20] 4-Nitrobenzaldehye (10.0 mmol)
was taken in 50 mL single necked round bottomed flask.
10 mL ethanol and hydrazine monohydrate (15.0 mmol)
were added. The reaction mixture was refluxed. Reaction
was monitored by TLC. After 12 h, reaction mixture was
allowed to cool to room temperature. The yellow colored
crystal formation was observed. Ethanol was removed by
filtration under vacuum to get yellow crystals as a desired
316 mg, 73% yield; pale yellow oil; Rf 0.29 (2% ethyl acetate
1
in hexanes); HNMR (CDCl3, 400 MHz) d 3.74 (s, 3H), 5.48
(s, 1H), 6.74 (ddd, J=8.4, 2.8, 1.2 Hz, 1H), 6.84 (t, J=2.0 Hz,
1H), 6.89 (dt, J=7.6, 1.2 Hz, 1H), 7.15 (t, J=8.0 Hz, 1H),
7.21–7.32 (m, 6H), 7.44–7.50 (m, 4H); 13CNMR (CDCl3, 100
MHz) d 43.9, 55.3, 113.2, 113.8, 120.4, 128.2, 129.1, 129.4,
131.2, 134.7, 142.9, 159.5; FTIR (neat) 696, 738, 1022, 1263,
1486, 1598, 2936, 3055 cmÀ1; HRMS (m/z): [M+Na]+ calcd
for C20H18OSe2Na: 456.9586; found 456.9614.
1
product in 74% yield (1.23 g). H and 13C data were in well
((3-Bromophenyl)methylene)bis(phenylselane)[10c]
(7d):
agreement with the literature data. (4-Nitrobenzylidene)
hydrazine was taken to next step without further purifica-
tion.
323 mg, 67% yield; pale yellow oil; Rf 0.32 (2% ethyl acetate
1
in hexanes); HNMR (CDCl3, 400 MHz) d 5.38 (s, 1H), 7.04
(t, J=8.0 Hz, 1H), 7.15 (dt, J=8.0, 1.2 Hz, 1H), 7.19–7.30 (m,
7H), 7.35 (t, J=1.6 Hz, 1H), 7.39–7.44 (m, 4H); 13CNMR
(CDCl3, 100 MHz) d 42.7, 122.3, 126.7, 128.6, 129.2, 129.9,
130.5, 130.6, 131.2, 135.0, 143.7; FTIR (neat) 687, 739, 1021,
1067, 1436, 1474, 1571, 2922, 3054 cmÀ1; HRMS (m/z): [M+
H]+ calcd for C19H16BrSe2: 482.8766; found 482.8738.
(4-Nitrobenzylidene)hydrazine (165 mg, 1.0 mmol) and
MgSO4 (482 mg, 4.0 mmol) were taken in dry DCM (3 mL)
under inert atmosphere. The reaction mixture was cooled to
08C. Then activated manganese dioxide (345 mg, 4.0 mmol)
was added slowly. After addition, reaction mixture was
stirred at same temperature for 2 h. Reaction mixture was
passed through a small pad of celite and 2 mL of DCM was
used for washing. Solvent was removed under vacuum (water
bath temperature was maintained at 258C in rotatory
evaporator) to get pure diazo compound as a yellow color
solid 8 in 56% yield (92 mg). Diazo compound was used to
((4-(Trifluoromethyl)phenyl)methylene)bis(phenylselane)
(7e): 339 mg, 72% yield; pale yellow solid; mp 58–608C; Rf
1
0.32 (2% ethyl acetate in hexanes); HNMR (CDCl3, 400
MHz) d 5.47 (s, 1H), 7.17–7.25 (m, 4H), 7.26–7.31 (m, 2H),
56 7.31–7.36 (m, 2H), 7.38–7.45 (m, 6H); 13CNMR (CDCl3, 125
MHz) d 42.7, 124.1 (q, J=270 Hz), 125.4 (q, J=3.75 Hz),
57
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next step without purification due to its facile decomposition.
(Caution: Appropriate precaution must be taken while
synthesizing the above mentioned diazo compound as it
prone to undergo facile decomposition).
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Y. Feng, L. Lin, G. Zou, J. Org. Chem. 2012, 77, 10991–
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Zhang, J. Wang, Angew. Chem., Int. Ed. 2015, 54, 3056–
3060; f) G. Wu, Y. Deng, H. Luo, J. Zhou, T. Li, Y.
Zhang, J. Wang, Chem. Commun. 2016, 52, 5266–5268;
g) C. Zhu, J. Li, P. Chen, W. Wu, Y. Ren, H. Jiang, Org.
Lett. 2016, 18, 1470–1473.
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Acknowledgements
We thank IIT Madras research student innovative project
(CHY/15–16/836/RFRI/GSEK) for financial support. D.A.
thanks CSIR, New Delhi for the SPM fellowship.
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[18] When the reaction was carried out in the absence of
base, diazo compound and disulfide were remained
unreactive even after 24h under our optimized reaction
conditions. Upon addition of base, formation of product
was observed. We believe that the base initiates the
decomposition of diazo compound into free carbene
through rapid nitrogen extrusion.
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[20] F. Friscourt, C. J. Fahrni, G.-J. Boons, Chem. - Eur. J.
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Adv. Synth. Catal. 2016, 358, 1–12
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

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UPDATES
A Transition-Metal-Free and Base-Mediated Carbene
Insertion into Sulfur-Sulfur and Selenium-Selenium
Bonds: An Easy Access to Thio- and Selenoacetals
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Adv. Synth. Catal. 2016, 358, 1–12
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D. Arunprasath, G. Sekar*
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