One Pot Sequential Synthesis of N-[2-(Phenylsulfinyl)phenyl]acetamides: A Ring Opening Rearrangement Functionalization (RORF)

Article abstract of DOI:10.1002/ejoc.201801597

A Cu^II catalyzed one-pot sequential synthesis of N-[2-(phenylthio)phenyl]acetamides from benzo[d]thiazol-2-amines, iodoarenes and carboxylic acids (RCOOH) has been accomplished via ring opening rearrangement functionalization (RORF). Here, the ring opening is associated with the loss of carbon and nitrogen atoms with concurrent S-arylation and N-acylation leading to ortho-bifunctionalized products. A further sequential addition of tert-butyl hydroperoxide (TBHP) results in the formation of a sulfur oxidized product, N-[2-(phenylsulfinyl)phenyl]acetamide. A plausible mechanism has been proposed for this unprecedented ring opening rearrangement functionalization (RORF).

Full text of DOI:10.1002/ejoc.201801597

A Journal of
Accepted Article
Title: One Pot Sequential Synthesis of N-(2-
(Phenylsulfinyl)phenyl)acetamides: A Ring Opening
Rearrangement Functionalization (RORF)
Authors: Ahalya Behera, Amitava Rakshit, Ashish Kumar Sahoo, and
Bhisma Kumar Patel
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801597
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801597
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10.1002/ejoc.201801597
European Journal of Organic Chemistry
UPDATE
DOI: 10.1002/ejoc.201801597
One Pot Sequential Synthesis of N-(2-
(Phenylsulfinyl)phenyl)acetamides: A Ring Opening
Rearrangement Functionalization (RORF)
Ahalya Behera,[a] Amitava Rakshit,[a] Ashish K. Sahoo,[a] and Bhisma K. Patel*[a]
Received: ((will be filled in by the editorial staff))
opening in the presence of appropriate nucleophiles.5 Although
five membered heterocycles such as thiazole,
Abstract: A Cu(II) catalyzed one-pot sequential synthesis
of N-(2-(phenylthio)phenyl)acetamides from benzo[d]thiazol-2-
amines, iodoarenes and carboxylic acids (RCOOH) has been
accomplished via ring opening rearrangement functionalization
(RORF). Here, the ring opening is associated with the loss of
carbon and nitrogen atoms with concurrent S-arylation and N-
acylation leading to ortho-bifunctionalized products. A further
sequential addition of tert-butyl hydroperoxide (TBHP) results
imidazole,oxazole and some of their benzo fused heterocycles
viz. benzothiazole, benzoimidazole, benzoxazole and
benzoisothiazole are more stable in terms of ring strain but are
susceptible to ring opening.6-8 The ring opening reactions are
not only restricted to simple benzothiazoles and 1,3-azoles but
also observed in 2-aminobenzothiazoles. In a coupling reaction
between 2-aminobenzothiazole and terminal alkyne resulted in
the formation of benzo[b][1,4]thiazine-4-carbonitrile.9a Here, the
ring opening is followed by an oxidative coupling with an alkyne
and finally the reaction terminates via an intermolecular
cyclization process. In yet another method, the synthesis of 2-
in the formation of
a sulfur oxidized product, N-(2-
(phenylsulfinyl)phenyl)acetamide. A plausible mechanism has
been proposed for this unprecedented ring opening
rearrangement functionalization (RORF).
Keywords: Carboxylic acids; Cross-coupling; Isotopic
labeling;
Oxidation;
Ring
opening
rearrangement
(phenylthio)phenylcyanamide
from
2-halothiourea
and
functionalization (RORF).
iodobenzene in the presence of CuI/ligand or CuSO4.5H2O has
been established by our group and Punniyamurthy group via the
intermediacy of 2-aminobenzothiazole.9b,c In 2015, a non-
enzymatic decomposition of guanidine derivatives into anilides
with the loss of a –CN moiety has been developed by Shi group
[Scheme1, (i)]. Here, a combination of catalyst Pd(OAc)2, an
equivalent of Cu(OAc)2 and CO were utilized for the
transformation of 1,3-diarylguanidines to acetanilides via the
cleavage of CN bond.10 Very recently, our group has developed
Introduction
The transition-metal catalyzed concurrent construction of
CS and CN bonds leading to functionally diverse structural
motifs are in great demand.1 Recently the C–N bond formations
have attracted much attention and become one of the most
promising strategy in organic reactions.2 Similarly, owing to the
importance of organo-sulfur compounds in biological,
pharmaceutical and material chemistry, the CS bond forming
process has also gained considerable attention in organic
synthesis.3 On the other hand one-pot sequential strategies are
effective as several bond-forming process can be carried out in
a single-pot, circumventing purification at each step, thereby
creating high diversity per step. A further appealing aspects of
this strategy is to produce large molecular diversity and
complexity in a single transformation.4
another
quinoline/isoquinoline
-CN
sacrificial
arylthio-arylamination
where,
of
2-
N-oxides
(arylthio)arylcyanamides serves as efficient arylaminating
agents [Scheme1, (ii)].11 The later proceeds via the attack of a
nucleophilic N-oxide onto electrophilic cyano (-CN) group of the
2-(arylthio)arylcyanamide followed by a rearrangement to
provide
an
auto-reduced
C2-arylaminated
quinoline/isoquinoline. In both these examples the -CN bearing
moiety viz. 2-(arylthio)arylcyanamides and guanidines, loses
their cyano group in the presence of respective nucleophiles viz.
quinoline N-oxides and acetate anions.
Due to the associated ring strains in three and four
membered carbo- and heterocycles, they often undergo ring
Inspired by the recent advances in transition-metal
catalyzed one-pot sequential reactions,12 ring opening
processes5-8 and NCN bond activation strategies,13 we
envisaged a telescopic protocol for the synthesis of N-(2-
(phenylthio)phenyl)acetamides (1aaʹ) (Scheme 1). 2-
(Phenylthio)phenylcyanamide (A) can be obtained from 2-
aminobenzothiazole (1) and iodobenzene (a) in the presence of
CuSO4.5H2O via a ring opening intermolecular CS cross
coupling reaction (Scheme 1).9c We anticipated that the in situ
generated cyanamide (X) possesses an electrophilic carbon,14
and a fragile NCN bond which may undergo a similar cyano
[a] A. Behera, A. Rakshit, A. K. Sahoo, Prof. Dr. B.K.Patel
Department of Chemistry, Indian Institute of Technology
Guwahati, North Guwahati 781 039, Assam, India
Fax: (+91)361-26909762,
E-mail: patel@iitg.ac.in
http://www.iitg.ac.in/patel/
Supporting information and ORCID(s) from the author(s) for
this
article
is
available
on
the
WWW
under
http://dx.doi.org/10.1002/ejoc.201801597.
1
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10.1002/ejoc.201801597
European Journal of Organic Chemistry
CS and CN ortho to each other providing
a 1,2-
sacrificial acetolysis to that of 1,3-diarylguanidine to generate an
bifunctionalized product N-(2-(phenylthio)phenyl)acetamide
(1aaʹ).
acetamide
(1aaʹ)
(Scheme
1).
The
N-(2-
(phenylthio)phenyl)acetamide (1aaʹ) having
a
diarylsulfide
moiety can be further oxidized to its sulfoxide (1aaʹʹ) analogue
in the presence of a suitable oxidant [Scheme 1, (iii)].
Figure 1. ORTEP diagram of N-(2-(phenylthio)phenyl)acetamide
(1aaʹ) with 40% ellipsoid contour probability.15
Inspired by this positive outcome, various reaction
parameters were again scrutinized to achieve an improved yield
of the 1,2-bifunctionalized product (1daʹ). The investigation was
commenced by using benzo[d]thiazol-2-amine (1) and 4-
methyliodobenzene (d) as the reacting partners (Table 1, entry
1). As most of the NCN bond cleaving reactions proceeds in
the presence of a metal catalyst,10,13 the quantity of CuSO4.5H2O
was first optimized. An increase in the catalyst (CuSO4.5H2O)
loading to 10 mol% improve the yield to 47 % (Table 1, entry 3).
However, the yield (48%) remained virtually unchanged even
using 15 mol% of the catalyst loading (Table 1, entry 4). The use
of base K2CO3 (2 equiv.) is found to be equally effective to that
of Cs2CO3 (1.5 equiv.) for the ring opening leading to the
formation of intermediate cyanamide (X) in DMSO (Table 1,
entry 5). Use of solvent DMF (58%) (Table 1, entry 6) was found
to be marginally superior to DMSO (53%). Keeping all other
parameters constant, the addition of 10 and 20 equivalents of
AcOH improved the yield of the final product (1daʹ) to 63% and
69% respectively (Table 1, entry 7 and 8). The yield of the
product improved progressively when the reaction was carried
out at 100 oC (76%), 110 oC (79%) and 120 oC (84%) (Table 1,
entries 9-11). Finally, a two-step optimized process was
developed for the ring opening rearrangement functionalization
(RORF) strategy. In the first step the combination of
CuSO4.5H2O (10 mol%), K2CO3 (2 equiv.) and DMF (1 mL) at
120 C for 4 h and in the second step addition of AcOH (20 equiv,
Scheme 1. Cyano sacrificial functionalization strategies.
Results and Discussion
An initial experiment was carried out using 2-
aminobenzothiazole (1) and iodobenzene (a) in the presence of
CuSO4.5H2O and Cs2CO3. The exclusive formation of
cyanamide (X) was observed after 4 h, which is consistent with
the previous literature reports.9b,c To check whether the
envisioned cyano sacrificial acetolysis could be accomplished in
one pot, AcOH (5 equiv.) was added to the same reaction
mixture after the initial formation of cyanamide (X) and heating
was continued further. To our delight, the expected N-acetylated
product 2-(phenylthio)phenylacetamide (1aaʹ, 29%) was
obtained via the loss of a cyano (-CN) group. The structure of
the product (1aaʹ) was further confirmed by X-ray
crystallographic analysis (Figure 1). Thus, herein, we report a
one pot sequential ring opening rearrangement functionalization
(RORF) using 2-aminobenzothiazole (1), iodobenzene (a) and
acetic acid (aʹ). The notable features of this transformation is the
sequential formation of two new Cheteroatom bonds such as

0.6 mL) at 120 C for 5 h was found to be the best optimal
condition for this telescopic synthesis (Table 1, entry 11).
Table 1. Optimization for N-acetylation.[a,b]
Entry
1
Catalyst (mol %)
Base (equiv.)
Cs2CO3 (1.5)
Solvent
DMSO
AcOH
Temp oC
90
Yield (%)
37
CuSO4.5H2O (2.5)
5 equiv.
2
3
4
5
6
7
8
9
CuSO4.5H2O (5)
CuSO4.5H2O (10)
CuSO4.5H2O (15)
CuSO4.5H2O (10)
CuSO4.5H2O (10)
CuSO4.5H2O (10)
CuSO4.5H2O (10)
CuSO4.5H2O (10)
CuSO4.5H2O (10)
CuSO4.5H2O (10)
Cs2CO3 (1.5)
Cs2CO3 (1.5)
Cs2CO3 (1.5)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
DMSO
DMSO
DMSO
DMSO
DMF
DMF
DMF
DMF
DMF
5 equiv.
5 equiv.
5 equiv.
5 equiv.
5 equiv.
10 equiv.
20 equiv.
20 equiv.
20 equiv.
20 equiv.
90
90
90
90
90
90
90
100
110
120
39
47
48
53
58
63
69
76
79
84
10
11
DMF
[a] Reaction conditions: benzo[d]thiazol-2-amine (1) (0.5 mmol), 4-iodotoluene (d) (0.5 mmol), solvent (1 mL) for 4 h. (ii) acetic
acid(aʹ) for 5 h was add. [b] Yields of isolated pure product.
2
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10.1002/ejoc.201801597
European Journal of Organic Chemistry
With this stepwise optimal reaction conditions in hand, the
generality and versatility of this one pot sequential 1,2-
difunctionalization strategy was demonstrated using different
benzo[d]thiazol-2-amines (1-3) with various aryl iodides (a-k)
bearing electron-donating and electron-withdrawing groups in
the presence of acetic acid (aʹ) (Scheme 2). Here, the
iodoarenes having electron-neutral –H (a) and electron-donating
substituents such as m-CH3 (b) and m-OCH3 (c), all yielded their
desired ring opened N-acetylated products (1aaʹ, 68%), (1baʹ,
73%) and (1caʹ, 81%) in good yields (Scheme 2). Further, aryl
Subsequently, presence of substituents on the 2-
aminobenzothiazole
was
investigated.
Benzothiazoles
possessing 6-NO2 (2) and 6-F (3), all experienced efficient
RORF giving their respective 1,2-bifunctionalized products. The
6-nitrobenzo[d]thiazol-2-amine (2) reacted smoothly with
iodobenzene (a) in presence of AcOH (a΄), providing its N-
acetylated product (2aa)́ in 41% yield. Further, the presence of
a least deactivating substituent 6-F (3) in the benzothiazole ring
underwent the N-acetylation with a variety of substituted
iodoarenes. The electron-donating p-CH3 (d) and electron-
withdrawing p-Cl (f) iodoarenes, all endured the present one pot
RORF strategy with 6-fluorobenzo[d]thiazol-2-amine (3) and
acetic acid (aʹ) furnishing their bi-functionalized products (3daʹ,
69%) and (3faʹ, 40%) respectively. From the trend in the yields
obtained in Scheme 2, no appropriate correlation between the
nature of substituents and their position of attachment with the
actual yield obtained could be rationalized. To check the
iodides
possessing
moderately
electron-withdrawing
substituents such as p-F (e), p-Cl (f), p-Br (g) and strongly-
electron-withdrawing substituent m-CF3 (h) all furnished their
respective 1,2-bifunctionalized N-acetylated products (1eaʹ,
53%), (1faʹ, 70%), (1gaʹ, 76%) and (1haʹ, 46%) (Scheme 2). A
o-phenyl
substituted iodobenzene (i)
reacted with
benzo[d]thiazol-2-amine (1) in the presence of acetic acid (aʹ)
affording its corresponding bi-functionalized product (1iaʹ, 49%).
In addition to these mono-substituted aryl iodides, the di-
substituted aryl iodides, such as 2-CH3-4-Cl (j) and 3-F-4-OCH3
(k) all underwent efficient transformations with benzo[d]thiazol-
2-amine (1) and acetic acid (aʹ) giving the desired N-acetylated
products (1jaʹ, 50%) and (1kaʹ, 67%) respectively.
scalability of the present methodology,
a
reaction of
benzo[d]thiazol-2-amine (1) (1 mmol), 4-methyliodobenzene (d)
(1 mmol) and acetic acid (aʹ) (20 equiv.), under the standard
optimized reaction condition provided a 79% yield of product
(1daʹ) (Scheme 2).
Scheme 2. Demonstration of RORF using AcOH and other carboxylic acids. [a] Reaction conditions: (i) benzo[d]thiazol-2-amine
(1) (0.5 mmol), aryl iodide (ak) (0.5 mmol), CuSO4.5H2O (10 mol%), K2CO3 (2 equiv.) and DMF (1 mL) for 4 h, (ii) AcOH (aʹ)
(20 equiv.), (1 mmol scale)c, TFA (b՛) (20 equiv. ), propanoic acid (cʹ) (10 equiv.)d, pivalic acid (dʹ) (8 equiv.)e and hexanoic acid
(eʹ) (10 equiv.)f, benzoic acids (fʹ) (6 equiv.)g, for another 5 h at 120 oC. [b] Yields of isolated pure products.
Now a query arises whether the acetic acid could be
replaced with its halogen analogue such as trifluoroacetic acid
to provide their corresponding N-trifluoroacylated products. With
this objective, when acetic acid (a՛) was substituted with
trifluoroacetic acid (b՛), using benzo[d]thiazol-2-amine (1) and
iodobenzene (a) as the reacting partners under otherwise
identical condition, the reaction furnished the anticipated N-
trifluoroacetylated product (1ab՛) in 62% yield. Inspired by the
positive outcome, several other iodoarenes (c-f) bearing
electron-donating and electron-withdrawing groups were
3
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10.1002/ejoc.201801597
European Journal of Organic Chemistry
examined with benzo[d]thiazol-2-amine (1) using TFA (b՛) as the
trifluoroacylation partner (Scheme 2). Initially, aryliodides
bearing electron-donating substituents such as m-OCH3 (c) and
p-CH3 (d) were employed with benzo[d]thiazol-2-amine (1) and
TFA (b՛) under the present reaction condition, all provided their
corresponding products (1cb՛, 56%) and (1db՛, 65%)
respectively. Similarly, iodoarenes bearing moderately electron-
withdrawing substituents such as p-F (e) and p-Cl (f), all yielded
their corresponding rearranged diaryl-sulfide products (1eb՛)
and (1fb՛) in 52% and 57% yields respectively. Besides these
substituted iodoarenes, 6-F-2-aminobenzothiazole (3) also
successfully underwent the present transformation with
iodobenzene (a) and TFA (b՛) to result the corresponding
trifluoroacetamide (3ab՛) in 54% yield. Here, similar to acetic
acid, no proper correlation between the nature of substituents
and their position of attachment with the actual yield obtained
could be ascertained. Besides AcOH and TFA this protocol is
also applicable to other aliphatic acids such as propanoic acid
(cʹ), pivalic acid (dʹ) and hexanoic acid (eʹ), all afforded their
corresponding ortho-bifunctionalized products (1dcʹ), (1adʹ)
and (1deʹ) in 52%, 71% and 74% yields respectively (Scheme
2). An aromatic carboxylic acid such as p-methoxy benzoic acid
(f՛) also provided a decent yield of the bi-functionalized amidic
product (1dfʹ, 63%) (Scheme 2).
We believe that the bi-functionalized acetamides obtained
after the addition of carboxylic acids, possessing a diarylsulfide
moiety, can be further oxidized to their corresponding sulfoxide
analogue in the same pot using a suitable oxidant. The in situ
treatment of K2S2O8 (3 equiv.) provided the sulfoxide product
(1da΄ʹ) in a modest 21% yield after 17 h at 120 oC leaving behind
substantial amount of unoxidized product (1da΄) (Table 2, entry
1). Spectroscopic and HRMS analysis of the product confirmed
its structure to be N-(2-(p-tolylsulfinyl)phenyl)acetamide (1da΄ʹ).
This positive outcome is interesting because, sulfoxides exhibit
a broad range of biological properties, including anticancer,16a-d
anti-viral16e and anti-bacterial activities.16f They are also
important structural motifs in marketed therapeutic drugs, such
as Nexium for heartburn and esophagitis17a and Provigil for
narcolepsy (Figure 2).17b
Since the final yield (21%) of the oxidized product (1da΄ʹ)
obtained was not promising, various other oxidants were then
examined to achieve an improve yield of (1da΄ʹ) (Table 2).
Among the oxidants such as (NH4)2S2O8 (08%), TBHP (56 M in
decane) (59%), aq.TBHP (32%), benzoylperoxide (BPO) (00%),
tert-butylperoxy benzoate (TBPB) (18%), di-tert-butyl peroxide
(DTBP) (26%) and H2O2 (48%) tested (Table 2, entries 28),
TBHP (56 M in decane) was found to be the most suitable
oxidant for the conversion of sulfide (1da΄) to sulfoxide (1da΄ʹ)
analogue (Table 2, entry 3). Gratifyingly, using 6 equiv. of TBHP,
an improved yield (67%) of product (1da΄ʹ) was observed (Table
2, entry 9). A further increase in the oxidant quantity to 8 equiv.,
gave no significant enhancement in the product (1da΄ʹ) yield
(Table 1, entry 10). Thus, TBHP (56 M in decane) (6 equiv.)
was used for the in situ oxidation of rest of the diarylsulfides in
Scheme 3.
The above optimized oxidative condition was then
implemented to explore the scope and generality of the
developed RORF strategy via the in situ oxidation of sulfide to
sulfoxide and the results are summarized in Scheme 3. Initially,
the variation of both electron-donating and electron-withdrawing
substituents on aryliodides (ai) with unsubstituted
benzo[d]thiazol-2-amine (1) using acetic acid (a΄) was surveyed.
Here again, the iodoarenes bearing electron neutral –H (a) and
electron-donating substituents such as m-OCH3 (c) provided
their corresponding bifunctionalized sulfoxide products (1aa΄ʹ,
60%) and (1ca΄ʹ, 58%) respectively (Scheme 3). Further, the
iodoarenes possessing moderately electron-withdrawing
substituents such as p-F (e), p-Cl (f), p-Br (g) and strongly
electron-withdrawing substituent m-CF3 (h) all resulted their
corresponding oxidized 1,2-disubstituted products (1ea΄ʹ, 52%),
(1fa΄ʹ, 63%), (1ga΄ʹ, 65%) and (1ha΄ʹ, 27%) respectively
(Scheme 3). Besides this, o-phenyl substituted iodobenzene (i)
provided its corresponding sulfoxide product (1ia΄ʹ) in 36% yield.
A
fluoro
substituted
2-aminobenzothiazole
viz.
6-
fluorobenzo[d]thiazol-2-amine (3) reacted smoothly with various
substituted iodoarenes bearing electron neutral -H (a), electron-
donating p-CH3 (d) and electron-withdrawing p-Cl (f) groups in
the presence of AcOH (a΄) and TBHP affording their N-
acetylated sulfoxides (3aa΄ʹ), (3da΄ʹ) and (3fa΄ʹ) in 50%, 58%
and 37% yields respectively.
Analogous to acetic acid, the one pot sequential RORF
protocol was also performed in the presence of TFA (b՛) under
an identical reaction condition. Surprisingly, oxidation of the in
situ generated sulfide (1ab՛) to sulfoxide (1ab՛՛) failed
completely. May be under a strongly acidic condition, the oxidant
TBHP rapidly decomposes, thereby failed to oxidize the sulfide.
However, the sulfoxide products (1ab՛՛) could be obtained in a
decent yield (58%) by oxidizing the isolated sulfide analogue
(1ab՛) using TBHP as the oxidant in CH3CN at room temperature
for 24 h. The same strategy was applied for other diarylsulfides
(1cb՛-1fb՛ and 3ab՛). The yields of the sulfoxide products (1cb՛΄-
Figure 2. Representative sulfoxide containing therapeutics.
Table 2. Optimization for sulfoxide formation.[a,b]
1fb՛́ and 3ab՛)́ reported in Scheme 3 are from the oxidation of
their respective diarylsulfides. The structure of the product
(1ab՛՛) was further reconfirmed by X-ray crystallographic
analysis (Figure S1).15 Other biaryl-sulfoxides (1ac΄ʹ, 50%),
(1ad΄ʹ, 70%) (1de΄ʹ, 55%), (1df΄ʹ,47%) and (1dg΄ʹ, 42%) were
also obtained via this one pot sequential RORF strategy using
other aliphatic and aromatic acids such as propanoic (c΄), pivalic
(d΄), hexanoic acid (e΄), p-methoxy benzoic acid (f΄) and p-chloro
benzoic acid (g΄) as shown in Scheme 3. It may be noted here,
that the yields of the unoxidized products in Scheme 2 are
generally superior to their corresponding oxidized products in
Scheme 3.
Entry
Oxidant (equiv.)
Temp (oC)
Yield (%)
1
2
K2S2O8 (3)
120
120
21
08
59h
32
00
18
(NH4)2S2O8 (3)
3
4
5
6
7
8
9
10
TBHP (3)
aq. TBHP (3)
BPO (3)
TBPB (3)
DTBP (3)
H2O2 (3)
120
120
120
120
120
120
120
120
26
48
TBHP (6)
TBHP (8)
67h
68g
[a] Reaction conditions: (i) benzo[d]thiazol-2-amine (1) (0.5
mmol), 4-iodotoluene (d) (0.5 mmol), CuSO4.5H2O (10
mol%), K2CO3 (2 equiv.) and DMF (1 mL) at 120 C for 4
h, (ii) AcOH (a)
́
(20 equiv.) for 5 h. hTBHP (5-6 M in
decane). [b] Yields of isolated pure product.
4
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10.1002/ejoc.201801597
European Journal of Organic Chemistry
Based on the literature reports9b,c and experimental findings,
a plausible reaction mechanism is depicted in Scheme 5. In this
reaction, aryliodide undergoes an oxidative addition with Cu to
form species (A). The 2-aminobenzothiazole opens up to a
carbodiimide in the presence of a base which then reacts with
the species (A) via the soft sulfur atom to generate intermediate
(B). The intermediate (B) undergoes reductive elimination to
form the diarylsulfide cyanamide intermediate (C). The resultant
cyanamide intermediate (C) is attacked by the acetate ion which
is assisted via the metal co-ordination to form a metal bound
carbamimidic anhydride species (D). The intermediate (D) is
hydrolyzed to a carbamic anhydride (E). The final acylated
product (1aa΄) is obtained via the loss of a CO2 moiety. The
acylated diarylsulfide (1aa΄) is oxidized to sulfoxide (1aa΄՛) in the
presence of an oxidant.
Scheme 3. Demonstration of RORF using AcOH and other
carboxylic acids under oxidative condition.[a] Reaction conditions:
(i) benzo[d]thiazol-2-amine (1) (0.5 mmol), aryl iodide (an) (0.5
mmol), CuSO4.5H2O (10 mol%), K2CO3 (2 equiv.), DMF (1 mL)
for 4 h, (ii) AcOH (a΄) (20 equiv.), propanoic acid (c΄) (10 equiv.)d,
pivalic acid (d΄) (8 equiv.)e, hexanoic acid (e΄) (10 equiv.)f and
benzoic acids (f΄ and g΄) (6 equiv.)g for 5 h (iii) TBHP (56 M in
Scheme 5. Plausible Mechanism for one pot sequential RORF.
o
decane) (6 equiv. ) for 17 h at 120 C. iReaction conditions: N-
To further extend the functionalization, the isolated
bifunctionalized product so obtained can be subsequently
functionalized via aromatic electrophilic substitution reactions
viz. bromination18a and nitration18b as demonstrated in Scheme
6.
trifluoroacetylated diarylsulfides (1cb՛-1fb՛ and 3ab՛) (0.25
mmol), TBHP (56 M in decane) (6 equiv. ), CH3CN (1 mL), time
(24 h) at room temp. [b] Yields of isolated pure product.
To illuminate the probable mechanism of this one pot sequential
ring opening rearrangement functionalization (RORF), some
control experiments were carried out. When the reaction was
performed in the presence of 18O labeled water no 18O
incorporated product was observed suggesting none of the
oxygen in the product originates from water. However, when a
reaction was carried out using 18O labeled acetic acid, the
product was found to have an 18O labeled oxygen (Scheme 4).
This result confirms carboxylic acids to be the acyl or aryl
sources in this transformation.
Scheme 6. Further functionalization of the product (1aa΄́ ).
Conclusion
In conclusion, a one pot sequential synthesis of N-(2-
(phenylthio)phenyl)acetamides has been developed using
benzo[d]thiazol-2-amine, aryliodide and carboxylic acid via a
copper catalyzed ring opening rearrangement functionalization
(RORF). The sequential addition of TBHP leads to the formation
of N-(2-(phenylsulfinyl)phenyl)acetamide. This RORF process is
accompanied with the loss of C and N atoms with S-arylation
followed by N-acylation leading to a bifunctionalized amidic
product.
Scheme 4. Isotopic labelling experiment.
5
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801597
European Journal of Organic Chemistry
1182, 1160, 1096, 1069, 1038, 947, 858, 759, 652, 590, 546,
487 cm-1; HRMS (ESI): calcd. for C15H16NO2S [M+H]+ 274.0896;
found 274.0903.
Experimental Section
General Information: All the reagents were of commercial
grade and purified according to the established procedures.
Organic extracts were dried over anhydrous sodium sulphate.
Solvents were removed in a rotary evaporator under reduced
pressure. Silica gel (60–120 mesh size) was used for the column
chromatography. Reactions were monitored by TLC on silica gel
60 GF254 (0.25 mm). NMR spectra were recorded in CDCl3and
DMSO with tetramethylsilane as the internal standard for 1H
NMR (400 MHz and 600 MHz) CDCl3 solvent as the internal
standard for 13C NMR (100 MHz and 150 MHz) and. Mass
spectra were recorded using ESI mode and APCI mode (Q-TOF
MS analyzer). IR spectra were recorded in KBr or neat.
N-(2-(p-Tolylthio)phenyl)acetamide (1da՛): Brownish solid;
mp 7476 C; 1H NMR (600 MHz, CDCl3):  (ppm) 2.06 (s, 3H),
2.29 (s, 3H), 7.01 (d, 2H, J = 8.4 Hz), 7.067.10 (m, 3H), 7.41 (t,
1H, J = 7.2 Hz), 7.54 (d, 1H, J = 7.2 Hz), 8.20 (s, 1H), 8.40 (d,
1H, J = 8.4 Hz); 13C NMR (100 MHz, CDCl3):  (ppm) 21.2, 25.0,
121.0, 124.5, 127.7, 128.0, 130.3, 130.8, 132.0, 136.2, 136.7,
139.7, 168.5; IR (KBr) 3306, 2918, 2861, 1670, 1577, 1525,
1460, 1435, 1367, 1301, 1244, 1164, 1103, 1036, 1017, 960,
835, 809, 753, 709, 669, 597, 544, 505, 450 cm-1; HRMS (ESI):
calcd. for C15H16NOS [M+H]+ 258.0947; found 258.0958.
N-(2-((4-Fluorophenyl)thio)phenyl)acetamide (1ea՛): White
solid; mp 9395 C; 1H NMR (600 MHz, CDCl3):  (ppm) 2.08 (s,
3H), 6.96 (t, 2H, J = 8.4 Hz), 7.077.11 (m, 3H), 7.41 (t, 1H, J =
7.8 Hz), 7.52 (d, 1H, J = 7.2 Hz), 8.16 (s, 1H), 8.39 (d, 1H, J =
8.4 Hz); 13C NMR (100 MHz, CDCl3):  (ppm) 25.0, 116.7 (d, J
= 22.1 Hz), 120.8, 121.2, 124.7, 129.7 (d, J = 7.7 Hz), 130.7,
131.1, 136.2, 139.7, 160.6, 163.1, 168.5; 19F NMR (CDCl3 +
hexafluorobenzene): δ -118.4 (s); IR (KBr) 3291, 2924, 2853,
1893, 1662, 1584, 1525, 1487, 1436, 1395, 1370, 1270, 1223,
1156, 1036, 1014, 943, 867, 833, 814, 758, 676, 636, 599, 543,
515, 473 cm-1; HRMS (ESI): calcd. for C14H13FNOS [M+H]+
262.0696; found 262.0722.
General Procedure for the Formation of N-(2-
(phenylthio)phenyl)acetamide (1aa՛): An oven-dried round
bottom flask was charged with benzo[d]thiazol-2-amine (1) (75
mg, 0.5 mmol), iodobenzene (a) (102 mg, 0.5 mmol),
CuSO4.5H2O (10 mol%, 12.5 mg), K2CO3 (1 mmol, 138 mg) and
DMF (1 mL). The flask was fitted with a condenser and the
resultant reaction mixture was stirred in a pre-heated oil bath
maintained at 120 C. The reaction progress was monitored by
TLC. The formation of N-(2-(phenylthio)phenyl)cyanamide (X)
was observed with the consumption of benzo[d]thiazol-2-amine
(1) and iodobenzene (a). After 4 h, AcOH (20 equiv., 0.6 mL)
was added to the same reaction mixture. The heating of the
reaction mixture was continued at 120 oC. The reaction progress
was monitored by TLC. After 5 h, the reaction mixture was
cooled to room temperature. Then the reaction mixture was
admixed with ethyl acetate (35 mL) and washed successively
with ice cold saturated NaHCO3 solution (2 × 20 mL). The ethyl
acetate layer was separated and dried over anhydrous Na2SO4
and the solvent was removed under reduced pressure. The
crude product so obtained was purified over a column of silica
gel using hexane:EtOAc (89:11) as the eluents to afford the
desired bi-functionalized product (1aa՛) in an isolated yield of
68% (83 mg).
N-(2-((4-Chlorophenyl)thio)phenyl)acetamide (1fa՛): Light

brownish solid; mp 7880 C; 1H NMR (600 MHz, CDCl3): 
(ppm) 2.07 (s, 3H), 6.98 (d, 2H, J = 8.4 Hz), 7.11 (t, 1H, J = 7.8
Hz), 7.20 (d, 2H, J = 8.4 Hz), 7.44 (t, 1H, J = 7.8 Hz), 7.54 (d,
1H, J = 7.2 Hz), 8.15 (s, 1H), 8.42 (d, 1H, J = 8.4 Hz); 13C NMR
(100 MHz, CDCl3):  (ppm) 25.0, 119.6, 121.2, 124.8, 128.4,
129.6, 131.4, 132.4, 134.5, 136.6, 140.0, 168.6; IR (KBr) 3447,
3827, 2924, 2853, 1663, 1577, 1520, 1473, 1433, 1369, 1298,
1251, 1092, 1013, 822, 760, 676, 601, 551, 504, 457 cm-1;
HRMS (ESI): calcd. for C14H13ClNOS [M+H]+ 278.0401; found
278.0408.
N-(2-(Phenylthio)phenyl)acetamide (1aa՛): Brownish solid;
mp 7577 C; 1H NMR (600 MHz, CDCl3):  (ppm) 2.04 (s, 3H),
7.087.13 (m, 3H), 7.17 (t, 1H, J = 7.2 Hz), 7.24 (d, 2H, J = 7.8
Hz), 7.44 (t, 1H, J = 7.8 Hz), 7.57 (d, 1H, J = 7.2 Hz), 8.20 (s,
1H), 8.43 (d, 1H, J = 8.4 Hz); 13C NMR (100 MHz, CDCl3): 
(ppm) 25.0, 120.0, 121.05, 124.6, 126.5, 127.3, 129.5, 131.2,
135.9, 136.6, 140.0, 168.6; IR (KBr) 3319, 2925, 2853, 1675,
1576, 1511, 1476, 1435, 1370, 1295, 1240, 1164, 1068, 1008,
944, 870, 757, 689, 672, 597, 543, 502 cm-1; HRMS (ESI): calcd.
for C14H14NOS [M+H]+ 244.0791; found 244.0783.
N-(2-((4-Bromophenyl)thio)phenyl)acetamide (1ga՛): White
solid; mp 121123 C; 1H NMR (600 MHz, CDCl3):  (ppm) 2.07
(s, 3H), 6.91 (d, 2H, J = 8.4 Hz), 7.12 (t, 1H, J = 7.8 Hz), 7.35 (d,
2H, J = 8.4 Hz), 7.45 (t, 1H, J = 7.2 Hz), 7.54 (d, 1H, J = 7.8 Hz),
8.14 (s, 1H), 8.43 (d, 1H, J = 8.4 Hz); 13C NMR (150 MHz,
CDCl3):  (ppm) 25.0, 119.4, 120.3, 121.3, 124.8, 128.7, 131.5,
132.6, 135.3, 136.7, 140.1, 168.5; IR (KBr) 3284, 2925, 2854,
1661, 1579, 1513, 1464, 1433, 1376, 1297, 1265, 1086, 1008,
815, 741, 589 cm-1; HRMS (ESI): calcd. for C14H13BrNOS
[M+H]+ 321.9896; found 321.9892.
N-(2-(m-Tolylthio)phenyl)acetamide (1ba՛): Brownish solid;
mp 7173 C; 1H NMR (600 MHz, CDCl3):  (ppm) 2.05 (s, 3H),
2.27 (s, 3H), 6.87 (d, 1H, J = 7.8 Hz), 6.92 (s, 1H), 6.98 (d, 1H,
J = 7.8 Hz), 7.107.14 (m, 2H), 7.43 (t, 1H, J = 7.8 Hz), 7.56 (d,
1H, J = 7.2 Hz), 8.21 (s, 1H), 8.42 (d, 1H, J = 7.8 Hz); 13C NMR
(100 MHz, CDCl3):  (ppm) 21.5, 25.0, 120.2, 121.0, 124.6,
127.5, 128.0, 129.4, 131.0, 135.5, 136.5, 139.5, 140.0, 168.6;
IR (KBr): 3290, 3056, 2923, 1666, 1576, 1517, 1473, 1434, 1362,
1297, 1245, 1163, 1037, 1017, 964, 938, 876, 853, 781, 756,
685, 601, 548, 525, 470 cm-1; HRMS (ESI): calcd. for
C15H16NOS [M+H]+ 258.0947; found 258.0939.
N-(2-((3-(Trifluoromethyl)phenyl)thio)phenyl)acetamide
(1ha՛): Brownish solid; mp 8183 C; 1H NMR (600 MHz,
CDCl3):  (ppm) 2.07 (s, 3H), 7.10 (d, 1H, J = 7.8 Hz), 7.14 (t,
1H, J = 7.8 Hz), 7.33 (t, 1H, J = 7.8 Hz), 7.41 (d, 2H, J = 7.2 Hz),
7.48 (t, 1H, J = 7.8 Hz), 7.57 (d, 1H, J = 7.2 Hz), 8.16 (s, 1H),
8.46 (d, 1H, J = 8.4 Hz); 13C NMR (100 MHz, CDCl3): (ppm)
25.0, 118.5, 121.3, 123.1, 123.7, 124.9, 129.9 (d, J = 14.1 Hz),
131.9 (t, J = 13.3 Hz), 136.9, 137.7, 140.3, 168.5; 19F NMR
(CDCl3 + hexafluorobenzene): δ -66.1 (d, J = 0.9 Hz); IR (KBr):
3265, 2925, 2853, 1660, 1582, 1524, 1438, 1423, 1365, 1321,
1272, 1188, 1167, 1118, 1069, 1016, 971, 945, 905, 880, 854,
791, 763, 694, 649, 606, 550, 492 cm-1; HRMS (ESI): calcd. for
C15H13F3NOS [M+H]+ 312.0664; found 312.0649.
N-(2-((3-Methoxyphenyl)thio)phenyl)acetamide
(1ca՛):
Brownish gummy; 1H NMR (600 MHz, CDCl3):  (ppm) 2.04 (s,
3H), 3.69 (s, 3H), 6.60 (s, 1H), 6.64 (d, 1H, J = 7.8 Hz), 6.69 (d,
1H, J = 7.8 Hz), 7.09 (t, 1H, J = 7.2 Hz), 7.14 (t, 1H,J = 7.8 Hz),
7.41 (t, 1H, J = 7.8 Hz), 7.55 (d, 1H, J = 7.8 Hz), 8.20 (s, 1H),
8.41 (d, 1H, J = 7.8 Hz); 13C NMR (100 MHz, CDCl3):  (ppm)
25.0, 55.4, 112.0, 112.8, 119.4, 119.8, 121.0, 124.6, 130.3,
131.2, 136.7, 137.2, 140.1, 160.3, 168.6; IR (KBr): 3549, 3292,
2934, 2835, 1700, 1588, 1520, 1477, 1426, 1367, 1299, 1230,
N-(2-([1,1'-Biphenyl]-2-ylthio)phenyl)acetamide (1ia՛): Light

brownish solid; mp 5860 C; 1H NMR (600 MHz, CDCl3): 
(ppm) 2.0 (s, 3H), 6.93 (d, 1H, J = 7.8 Hz), 7.10 (t, 1H, J = 7.2
Hz), 7.21 (t, 1H, J = 7.2 Hz), 7.28 (d, 1H, J = 7.8 Hz), 7.32 (d,
1H, J = 7.8 Hz), 7.42 (t, 1H, J = 7.8 Hz), 7.46 (d, 3H, J = 6.6 Hz),
7.497.53 (m, 3H), 7.95 (s, 1H), 8.39 (d, 1H, J = 7.8 Hz); 13C
NMR (100 MHz, CDCl3):  (ppm) 25.0, 120.9, 124.5, 126.6,
6
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801597
European Journal of Organic Chemistry
128.1, 128.2, 128.5, 129.5, 130.7, 130.9, 134.4, 136.7, 139.9,
140.3, 141.6, 168.5; IR (KBr): 3363, 2925, 2853, 1700, 1579,
1511, 1460, 1430, 1368, 1298, 1235, 1160, 1073, 1036, 1007,
752, 702, 677, 652, 686, 548, 493, 455 cm-1; HRMS (ESI): calcd.
for C20H18NOS [M+H]+ 320.1104; found 320.1101.
CDCl3):  (ppm) 114.7, 116.7, 121.3, 122.5, 126.6, 127.2, 128.2,
129.7, 131.3, 132.0, 134.6, 136.8, 137.3, 154.8 (q, J = 37.3 Hz);
19F NMR (CDCl3 + hexafluorobenzene): δ -79.2 (m); IR (KBr):
3451, 2926, 2855, 1637, 1534, 1443, 1154, 1024, 742, 690 cm-
1; HRMS (ESI): calcd. for C14H11F3NOS [M+H]+ 298.0508; found
298.0519.
N-(2-((4-Chloro-2-methylphenyl)thio)phenyl)acetamide
(1ja՛): Brownish solid; mp 9799 C; 1H NMR (600 MHz, CDCl3):
 (ppm) 2.08 (s, 3H), 2.40 (s, 3H), 6.61 (d, 1H, J = 8.4 Hz), 7.0
(d, 1H, J = 7.8 Hz), 7.11 (t, 1H, J = 7.2 Hz), 7.19 (s, 1H),
7.427.45 (m, 2H), 8.05 (s, 1H), 8.42 (d, 1H, J = 8.4 Hz); 13C
NMR (150 MHz, CDCl3): (ppm) 20.3, 25.0, 119.6, 121.3, 124.9,
127.2, 128.3, 130.5, 131.1, 132.2, 133.4, 136.1, 137.8, 139.9,
168.5; IR (KBr): 3239, 2924, 2853, 1681, 1654, 1577, 1528,
1466, 1437, 1367, 1297, 1257, 1199, 1158, 1098, 1050, 940,
870, 819, 749, 681, 599, 576, 548, 481, 457 cm-1; HRMS (ESI):
calcd. for C15H15ClNOS [M+H]+ 292.0557; found 292.0551.
2,2,2-Trifluoro-N-(2-((3-
methoxyphenyl)thio)phenyl)acetamide (1cb՛): Brownish
gummy; 1H NMR (400 MHz, CDCl3):  (ppm) 3.73 (s, 3H),
6.646.75 (m, 3H), 7.17 (t, 1H, J = 8.0 Hz), 7.247.28 (m, 1H),
7.50 (t, 1H, J = 8.8 Hz), 7.68 (d, 1H, J = 8.0 Hz), 8.39 (d, 1H, J
= 8.4 Hz), 9.08 (s, 1H); 13C NMR (100 MHz, CDCl3):  (ppm)
55.5, 112.9, 113.8, 120.4, 121.4, 122.4, 126.6, 130.6, 131.4,
135.9, 136.9, 137.5, 160.6; 19F NMR (CDCl3
+
hexafluorobenzene): δ -79.2 (s); IR (KBr): 3329, 2924, 2854,
1720, 1587, 1540, 1444, 1413, 1148, 1095, 1025, 801, 690, 621
cm-1; HRMS (ESI): calcd. for C15H13F3NO2S [M+H]+ 328.0614;
found 328.0632.
N-(2-((3-Fluoro-4-methoxyphenyl)thio)phenyl)acetamide

1
(1ka՛): Dark brownish solid; mp 7678 C; H NMR (400 MHz,
CDCl3):  (ppm) 2.10 (s, 3H), 3.84 (s, 3H), 6.826.91 (m, 3H),
7.09 (t, 1H, J = 7.2 Hz), 7.40 (t, 1H, J = 7.6 Hz), 7.50 (d, 1H, J =
7.2 Hz), 8.16 (s, 1H), 8.38 (d, 1H, J = 7.6 Hz); 13C NMR (150
MHz, CDCl3):  (ppm) 25.0, 56.5, 114.4 (d, J = 2.2 Hz), 116.7 (d,
J = 20.1 Hz), 121.2 (d, J = 11.1 Hz), 124.7 (d, J = 9.1 Hz), 126.9
(d, J = 6.0 Hz), 130.9, 135.9, 139.5, 147.0 (d, J = 10.5 Hz), 151.9,
153.5, 168.5; 19F NMR (CDCl3 + hexafluorobenzene): δ -135.9
(s); IR (KBr): 3360, 2927, 2849, 1696, 1580, 1510, 1432, 1368,
1300, 1269, 1209, 1181, 1133, 1077, 1025, 894, 865, 808, 758,
687, 645, 593, 547, 477 cm-1; HRMS (ESI): calcd. for
C15H15FNO2S [M+H]+ 292.0802; found 292.0809.
2,2,2-Trifluoro-N-(2-(p-tolylthio)phenyl)acetamide
(1db՛):
Light brownish solid; mp 100102 C; 1H NMR (600 MHz,
CDCl3):  (ppm) 2.30 (s, 3H), 7.07 (q, 4H, J = 7.6 Hz), 7.23 (t,
1H, J = 7.8 Hz), 7.47 (t, 1H, J = 6.6 Hz), 7.64 (d, 1H, J = 7.8 Hz),
8.37 (d, 1H, J = 8.4 Hz), 9.13 (s, 1H); 13C NMR (150 MHz,
CDCl3):  (ppm) 21.2, 114.8, 116.7, 121.2, 123.5, 126.6, 129.0,
130.5, 130.8, 130.9, 136.4, 137.0, 137.6, 154.8 (q, J = 37.3 Hz);
19F NMR (CDCl3 + hexafluorobenzene): δ -79.2 (s); IR (KBr):
3254, 2920, 1670, 1581, 1512, 1433, 1400, 1292, 1185, 1018,
803, 756, 535 cm-1; HRMS (ESI): calcd. for C15H13F3NOS [M+H]+
312.0464; found 312.0461.
N-(4-Nitro-2-(phenylthio)phenyl)acetamide (2aa՛): Brownish
2,2,2-Trifluoro-N-(2-((4-fluorophenyl)thio)phenyl)acetamide
(1eb՛): Light brownish solid; mp 73 C; H NMR (400 MHz,
solid; mp 116118 C; 1H NMR (400 MHz, CDCl3):  (ppm) 2.13
(s, 3H), 7.16 (d, 2H, J = 6.8 Hz), 7.287.33 (m, 3H), 8.27 (dd,
1H, J = 9.2, 2.8 Hz), 8.46 (d, 2H, J = 2.4 Hz), 8.68 (d, 1H, J =
9.2 Hz); 13C NMR (100 MHz, CDCl3):  (ppm) 25.1, 120.1, 126.4,
127.4, 127.5, 128.6, 129.6, 130.0, 131.4, 133.6, 145.1, 168.8;
IR (KBr): 3447, 2924, 2854, 1621, 1577, 1499, 1337, 1262, 1092,
1022, 802, 742, 690 cm-1; HRMS (ESI): calcd. for C14H13N2O3S
[M+H]+ 289.0641; found 289.0641.

1
CDCl3):  (ppm) 6.98 (t, 2H, J = 8.4 Hz), 7.137.16 (m, 2H),
7.237.27 (m, 1H), 7.49 (t, 1H, J = 7.2 Hz), 7.63 (d, 1H, J = 7.6
Hz), 8.37 (d, 1H, J = 8.0 Hz), 9.06 (s, 1H); 13C NMR (100 MHz,
CDCl3):  (ppm) 114.4, 117.0 (d, J = 22.2 Hz), 117.2, 121.5,
123.3, 126.7, 129.6 (d, J = 3.3 Hz), 130.8 (d, J = 8.2 Hz), 131.3,
136.4, 137.0, 154.6, 155.0, 162.3 (d, J = 246.5 Hz); 19F NMR
(CDCl3 + hexafluorobenzene):  -117.2 (s), -79.1 (s); IR (KBr):
3318, 2924, 1713, 1588, 1490, 1261, 1154, 1093, 1018, 800,
622, 515 cm-1; HRMS (ESI): calcd. for C14H10F4NOS [M+H]+
316.0414; found 316.0425.
N-(4-Fluoro-2-(p-tolylthio)phenyl)acetamide
(3da՛):

1
Brownish solid; mp 118120 C; H NMR (400 MHz, CDCl3): 
(ppm) 2.07 (s, 3H), 2.31 (s, 3H), 7.027.15 (m, 6H), 7.93 (s, 1H),
8.25 (dd, 1H, J = 9.2, 5.6 Hz); 13C NMR (100 MHz, CDCl3): 
(ppm) 21.2, 24.6, 116.6 (d, J = 21.8 Hz), 120.9 (d, J = 23.3 Hz),
123.1 (d, J = 7.8 Hz), 125.0 (d, J = 7.8 Hz), 130.1 (d, J = 95.5
N-(2-((4-Chlorophenyl)thio)phenyl)-2,2,2-trifluoroacetamide

1
(1fb՛): Light brownish solid; mp 8486 C; H NMR (600 MHz,
CDCl3):  (ppm) 7.04 (d, 2H, J = 8.4 Hz), 7.237.29 (m, 3H), 7.52
(t, 1H, J = 8.4 Hz), 7.66 (d, 1H, J = 7.8 Hz), 8.40 (d, 1H, J = 8.4
Hz), 9.06 (s, 1H); 13C NMR (150 MHz, CDCl3):  (ppm) 114.7,
116.7, 121.5, 122.1, 126.8, 129.4, 129.9, 131.6, 133.2, 133.3,
Hz), 135.0, 137.7, 157.6, 160.0, 168.4; 19F NMR (CDCl3
+
hexafluorobenzene): δ -120.3 (s); IR (KBr): 3232, 2924, 2854,
1647, 1544, 1474, 1392, 1302, 1239, 1190, 1018, 899, 853, 811,
738, 608, 504 cm-1; HRMS (ESI): calcd. for C15H15FNOS [M+H]+
276.0856; found 276.0872.
136.8, 137.3, 154.8 (q, J = 37.5 Hz); 19F NMR (CDCl3
+
hexafluorobenzene): δ -79.1 (s); IR (KBr): 3261, 2920, 1695,
1583, 1434, 1294, 1152, 1092, 1036, 815, 757, 535 cm-1; HRMS
(ESI): calcd. for C14H10ClF3NOS [M+H]+ 332.0118; found
332.0139.
N-(2-((4-Chlorophenyl)thio)-4-fluorophenyl)acetamide
1
(3fa՛): Brownish gummy; H NMR (400 MHz, CDCl3):  (ppm)
2.07 (s, 3H), 7.06 (d, 2H, J = 8.4 Hz), 7.107.15 (m, 1H),
7.197.21 (m, 1H), 7.257.27 (m, 2H), 7.89 (s, 1H), 8.33 (dd, 1H,
J = 8.8, 5.2 Hz); 13C NMR (100 MHz, CDCl3):  (ppm) 24.8, 117.7
(d, J = 21.7 Hz), 121.8 (d, J = 23.3 Hz), 122.9, 123.2 (d, J = 8.3
Hz), 129.8 (d, J = 25.8 Hz), 133.3 (d, J = 18.6 Hz), 135.7, 157.6,
160.0, 168.4; 19F NMR (CDCl3 + hexafluorobenzene):  -119.9
(s); IR (KBr): 3437, 2963, 2856, 1646, 1526, 1475, 1392, 1261,
1094, 1021, 801, 700, 505 cm-1; HRMS (ESI): calcd. for
C14H12ClFNOS [M+H]+ 296.0307; found 296.0337.
2,2,2-Trifluoro-N-(4-fluoro-2-(phenylthio)phenyl)acetamide
(3ab՛): Brownish gummy; H NMR (400 MHz, CDCl3):  (ppm)
1
7.157.21 (m, 3H), 7.287.34 (m, 4H), 8.31 (dd, 1H, J = 9.2, 5.2
Hz), 8.85 (s, 1H); 13C NMR (100 MHz, CDCl3):  (ppm) 117.2,
117.6 (d, J = 22.1 Hz), 122.4 (d, J = 23.4 Hz), 123.2 (d, J = 8.1
Hz), 125.9 (d, J = 8.0 Hz), 128.0, 129.4, 130.0, 132.9 (d, J = 3.2
Hz), 133.4, 154.7, 155.0, 159.9 (d, J = 248.2 Hz); 19F NMR
(CDCl3 + hexafluorobenzene): δ -117.0 (s), -79.1 (s); IR (KBr):
3314, 2923, 1708, 1584, 1485, 1253, 1150, 1089, 1015, 797,
618, 511 cm-1; HRMS (ESI): calcd. for C14H10F4NOS [M+H]+
316.0414; found 316.0418.
2,2,2-Trifluoro-N-(2-(phenylthio)phenyl)acetamide
(1ab՛):
Light brownish solid; mp 5355 C; 1H NMR (600 MHz, CDCl3):
 (ppm) 7.12 (d, 2H, J = 7.2 Hz), 7.21 (t, 1H, J = 7.2 Hz),
7.257.28 (m, 3H), 7.51 (t, 1H, J = 8.4 Hz), 7.68 (d, 1H, J = 7.8
Hz), 8.40 (d, 1H, J = 7.8 Hz), 9.11 (s, 1H); 13C NMR (150 MHz,
N-(2-(p-Tolylthio)phenyl)propionamide (1dc՛): Yellowish
gummy; 1H NMR (600 MHz, CDCl3):  (ppm) 1.11 (t, 3H, J = 7.8
Hz), 2.272.30 (m, 5H), 7.00 (d, 2H, J = 8.4 Hz), 7.06 (d, 2H, J
7
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801597
European Journal of Organic Chemistry
= 7.8 Hz), 7.09 (t, 1H, J = 7.8 Hz), 7.41 (t, 1H, J = 7.8 Hz), 7.55
(d, 1H, J = 7.8 Hz), 8.25 (s, 1H), 8.45 (d, 1H, J = 8.4 Hz); 13C
NMR (150 MHz, CDCl3):  (ppm) 9.6, 21.1, 31.2, 120.8, 120.9,
124.4, 127.8, 130.3, 130.9, 132.0, 136.3, 136.6, 139.8, 172.2;
IR (KBr) 3367, 2975, 2921, 1695, 1579, 1410, 1433, 1294, 1182,
1083, 1016, 805, 756 cm-1; HRMS (ESI): calcd. for C16H18NOS
[M+H]+ 272.1104; found 272.1091.
N-(2-(Phenylsulfinyl)phenyl)acetamide
(1aa՛՛):
Dark
1
brownish gummy; H NMR (600 MHz, CDCl3):  (ppm) 2.04 (s,
3H), 7.17 (t, 1H, J = 7.2 Hz), 7.437.47 (m, 3H), 7.477.50 (m,
3H), 7.57 (d, 1H, J = 7.2 Hz), 8.31 (d, 1H, J = 8.4 Hz), 10.04 (s,
1H); 13C NMR (150 MHz, CDCl3):  (ppm) 24.8, 123.4, 123.5,
124.4, 128.2, 129.4, 131.0, 133.4, 140.2, 142.9, 159.3, 168.7;
IR (KBr): 3270, 2925, 2856, 1694, 1586, 1527, 1473, 1439, 1371,
1303, 1252, 1159, 1082, 1019, 925, 754, 692, 599, 553, 490,
486, 457 cm-1; HRMS (ESI): calcd. for C14H14NO2S [M+H]+
260.0740; found 260.0741.
N-(2-(Phenylthio)phenyl)pivalamide
(1ad՛):
Yellowish
gummy; 1H NMR (400 MHz, CDCl3):  (ppm) 1.10 (s, 9H), 7.03
(d, 2H, J = 7.2 Hz), 7.097.15 (m, 2H), 7.22 (t, 2H, J = 7.2 Hz),
7.447.49 (m, 1H), 7.61 (d, 1H, J = 8.0 Hz), 8.52 (d, 1H, J = 8.4
Hz), 8.57 (s, 1H); 13C NMR (100 MHz, CDCl3):  (ppm) 27.4,
40.2, 119.6, 120.8, 124.3, 126.3, 126.6, 129.5, 130.3, 131.4,
135.7, 136.1, 136.9, 140.3, 176.9; IR (KBr) 3384, 2926, 1690,
1580, 1511, 1478, 1421, 1301, 1175, 1025, 741, 691 cm-1;
HRMS (ESI): calcd. for C17H20NOS [M+H]+ 286.1260; found
286.1238.
N-(2-((3-Methoxyphenyl)sulfinyl)phenyl)acetamide (1ca՛՛):
Dark brownish solid; mp 121123 C; 1H NMR (600 MHz,
CDCl3):  (ppm) 2.05 (s, 3H), 3.78 (s, 3H), 6.93 (d, 1H, J = 8.4
Hz), 6.98 (d, 1H, J = 7.8 Hz), 7.08 (s, 1H), 7.16 (t, 1H, J = 7.2
Hz), 7.33 (t, 1H, J = 7.8 Hz), 7.48 (t, 1H, J = 7.8 Hz), 7.54 (d, 1H,
J = 7.8 Hz), 8.31 (d, 1H, J = 8.4 Hz), 10.04 (s, 1H); 13C NMR
(150 MHz, CDCl3):  (ppm) 24.8, 55.7, 109.8, 116.5, 116.6,
123.3, 123.5, 128.09, 128.1, 130.5, 133.3, 140.2, 144.3, 160.4,
168.6; IR (KBr) 3242, 3050, 2926, 2852, 1693, 1592, 1539, 1471,
1428, 1365, 1307, 1285, 1230, 1184, 1164, 1072, 1040, 1020,
956, 915, 841, 772, 688, 600, 568, 515, 493, 468 cm-1; HRMS
(ESI): calcd. for C15H16NO3S [M+H]+ 290.0845; found 290.0848.
N-(2-(p-Tolylthio)phenyl)hexanamide
(1de՛):
Brownish
gummy; 1H NMR (400 MHz, CDCl3):  (ppm) 0.840.89 (m, 3H),
1.221.26 (m, 4H), 1.511.58 (m, 2H), 2.24 (t, 2H, J = 7.6 Hz),
2.29 (s, 3H), 6.997.11 (m, 5H), 7.42 (t, 1H, J = 8.4 Hz), 7.56 (d,
1H, J = 7.6 Hz), 8.22 (s, 1H), 8.46 (d, 1H, J = 8.0 Hz); 13C NMR
(100 MHz, CDCl3):  (ppm) 14.1, 19.4, 21.1, 22.5, 25.3, 31.4,
115.5, 118.9, 127.3, 130.0, 130.3, 130.9, 131.0, 133.2, 135.7,
137.7, 148.8; IR (KBr) 3368, 2924, 2855, 1699, 1510, 1459,
1262, 1092, 1021, 803, 702, 501 cm-1; HRMS (ESI): calcd. for
C19H24NOS [M+H]+ 314.1573; found 314.1590.
N-(2-(p-Tolylsulfinyl)phenyl)acetamide
(1da՛՛):
Dark

brownish solid; mp 8587 C; 1H NMR (600 MHz, CDCl3): 
(ppm) 2.05 (s, 3H), 2.36 (s, 3H), 7.16 (t, 1H, J = 7.2 Hz), 7.25 (d,
2H, J = 8.4 Hz), 7.37 (d, 2H, J = 8.4 Hz), 7.467.49 (m, 1H), 7.53
(d, 1H, J = 7.2 Hz), 8.32 (d, 1H, J = 8.4 Hz), 10.11 (s, 1H); 13
C
4-Methoxy-N-(2-(p-tolylthio)phenyl)benzamide
(1df՛):
NMR (150 MHz, CDCl3):  (ppm) 21.5, 24.9, 120.0, 123.2, 123.5,
124.4, 127.9, 128.3, 130.2, 133.2, 139.7, 140.2, 141.6, 168.7;
IR (KBr): 3451, 3259, 2925, 2853, 1700, 1589, 1532, 1467, 1435,
1370, 1302, 1249, 1161, 1082, 1021, 894, 811, 760, 705, 619,
597, 549, 533, 494, 468 cm-1; HRMS (ESI): calcd. for
C15H16NO2S [M+H]+ 274.0896; found 274.0907.

1
Brownish solid; mp 115117 C; H NMR (400 MHz, CDCl3): 
(ppm) 2.27 (s, 3H), 3.85 (s, 3H), 6.90 (d, 2H, J = 8.8 Hz), 7.05
(s, 4H), 7.12 (t, 1H, J = 7.2 Hz), 7.47 (t, 1H, J = 8.0 Hz), 7.61 (d,
1H, J = 7.6 Hz), 7.65 (d, 2H, J = 8.8 Hz), 8.66 (d, 1H, J = 8.0 Hz),
9.04 (s, 1H); 13C NMR (100 MHz, CDCl3):  (ppm) 21.1, 55.6,
114.1, 120.6, 120.9, 124.4, 127.2, 127.8, 129.1, 130.3, 131.1,
132.0, 136.5, 136.7, 140.2, 162.7, 165.0; IR (KBr) 3366, 2927,
2839, 1677, 1606, 1575, 1502, 1432, 1303, 1251, 1177, 1100,
1030, 837, 843, 806, 760, 692, 579, 507 cm-1; HRMS (ESI):
calcd. for C21H20NO2S [M+H]+ 350.1209; found 350.1202.
N-(2-((4-Fluorophenyl)sulfinyl)phenyl)acetamide
(1ea՛՛):
Dark brownish solid; mp 99101 C; 1H NMR (600 MHz, CDCl3):
 (ppm) 2.05 (s, 3H), 7.147.19 (m, 3H), 7.477.51 (m, 3H), 7.53
(d, 1H, J = 7.8 Hz), 8.31 (d, 1H, J = 7.8 Hz), 10.0 (s, 1H); 13C
NMR (150 MHz, CDCl3):  (ppm) 24.8, 116.8 (d, J = 22.6 Hz),
123.6 (d, J = 21.1 Hz), 126.7 (d, J = 8.8 Hz), 128.0, 133.5, 138.5
(d, J = 3.0 Hz), 140.2, 163.5, 165.1, 168.6; 19F NMR (CDCl3 +
hexafluorobenzene): δ -111.9 (s); IR (KBr) 3441, 2925, 2853,
1697, 1589, 1532, 1492, 1466, 1436, 1372, 1032, 1230, 1156,
1082, 1021, 837, 813, 761, 673, 650, 594, 533, 474 cm-1; HRMS
(ESI): calcd. for C14H13FNO2S [M+H]+ 278.0646; found 278.0658.
General Procedure for the Formation of N-(2-
(phenylsulfinyl)phenyl)acetamide (1aa՛՛): An oven-dried
round bottom flask was charged with benzo[d]thiazol-2-amine
(1) (75 mg, 0.5 mmol), iodobenzene (a) (102 mg, 0.5 mmol),
CuSO4.5H2O (10 mol%, 12.5 mg), K2CO3 (1 mmol, 138 mg) and
DMF (1 mL). The flask was fitted with a condenser and the
resultant reaction mixture was stirred in a pre-heated oil bath
maintained at 120 C. The reaction progress was monitored by
TLC. The formation of N-(2-(phenylthio)phenyl)cyanamide (X)
was observed with the consumption of benzo[d]thiazol-2-amine
(1) and iodobenzene (a). After 4 h, AcOH (20 equiv., 0.6 mL)
was added to the same reaction mixture. The heating of the
reaction mixture was continued at 120 oC. The reaction progress
was monitored by TLC. After 5 h, the consumption of the in situ
generated cyanamide was observed with the formation of N-(2-
(phenylthio)phenyl)acetamide (1aa՛). To the same reaction,
TBHP (5-6 M in decane) (6 equiv.) was added. Again the
N-(2-((4-Chlorophenyl)sulfinyl)phenyl)acetamide
(1fa՛՛):
Dark brownish solid; mp 106108 C; 1H NMR (600 MHz,
CDCl3):  (ppm) 2.04 (s, 3H), 7.17 (t, 1H, J = 7.8 Hz), 7.42 (s,
4H), 7.487.51 (m, 1H), 7.54 (d, 1H, J = 7.8 Hz), 8.30 (d, 1H, J
= 5.4 Hz), 9.95 (s, 1H); 13C NMR (150 MHz, CDCl3):  (ppm)
24.8, 119.9, 123.5, 123.7, 125.8, 128.0, 129.7, 133.6, 137.4,
140.2, 141.5, 168.6; IR (KBr) 3443, 2925, 2853, 1661, 1587,
1525, 1473, 1434, 1371, 1302, 1250, 1169, 1090, 1034, 1009,
825, 762, 741, 703, 650, 600, 559, 526, 507, 464 cm-1; HRMS
(ESI): calcd. for C14H13ClNO2S [M+H]+ 294.0350; found
294.0363.
o
reaction was heated at 120 C. The formation of the sulfoxide
was observed from the TLC. After 17 h, the reaction mixture was
cooled to room temperature. Then the reaction mixture was
admixed with ethyl acetate (35 mL) and the organic layer was
washed successively with ice cold saturated NaHCO3 solution
(2 × 20 mL). The ethyl acetate layer was separated and dried
over anhydrous Na2SO4 and the solvent was removed under
reduced pressure. The crude product so obtained was purified
over a column of silica gel using hexane:EtOAc (60:40) as the
eluents to afford the desired sulfoxide product (1aa՛՛) in an
isolated yield of 60% (78 mg).
N-(2-((4-Bromophenyl)sulfinyl)phenyl)acetamide
(1ga՛՛):
Brownish solid; mp 9597 C; 1H NMR (600 MHz, CDCl3): 
(ppm) 2.05 (s, 3H), 7.18 (t, 1H, J = 7.2 Hz), 7.35 (d, 2H, J = 8.4
Hz), 7.50 (t, 1H, J = 7.8 Hz), 7.55 (d, 1H, J = 7.2 Hz), 7.58 (d,
2H, J = 8.4 Hz), 8.32 (d, 1H, J = 7.8 Hz), 9.95 (s, 1H); 13C NMR
(150 MHz, CDCl3):  (ppm) 24.8, 123.5, 123.6, 125.7, 125.9,
127.7, 128.0, 132.6, 133.6, 140.2, 142.1, 168.6; IR (KBr): 3477,
3278, 2924, 2852, 1697, 1659, 1587, 1521, 1470, 1434, 1370,
1301, 1248, 1172, 1127, 1064, 1036, 1005, 820, 762, 723, 650,
598, 555, 502 cm-1; HRMS (ESI): calcd. for C14H13BrNO2S
[M+H]+ 337.9845; found 337.9850.
8
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801597
European Journal of Organic Chemistry
N-(2-((3-(Trifluoromethyl)phenyl)sulfinyl)phenyl)acetamide
(1ha՛՛): Dark brownish solid; mp 8688 C; 1H NMR (600 MHz,
CDCl3):  (ppm) 2.03 (s, 3H), 7.20 (t, 1H, J = 7.2 Hz), 7.487.52
(m, 2H), 7.54 (t, 1H, J = 7.8 Hz), 7.61 (dd, 1H, J = 7.8, 1.3 Hz),
7.69 (d, 1H, J = 7.8 Hz), 7.96 (s, 1H), 8.27 (d, 1H, J = 8.4 Hz),
9.86 (s, 1H); 13C NMR (150 MHz, CDCl3):  (ppm) 24.5, 121.2
(q, J = 3.7 Hz), 122.6, 123.7 (d, J = 29.2 Hz), 124.4, 127.7 (t, J
= 3.3 Hz), 127.9, 128.1, 131.9 (q, J = 33.0 Hz), 133.9, 140.1,
144.5, 168.6; 19F NMR (CDCl3 + hexafluorobenzene): δ -66.0
(s); IR (KBr) 3487, 3255, 2924, 2852, 1664, 1585, 1523, 1467,
1433, 1375, 1327, 1304, 1280, 1173, 1129, 1098, 1069, 1035,
913, 806, 761, 695, 648, 626, 600, 578, 509, 476 cm-1; HRMS
(ESI): calcd. for C15H13F3NO2S [M+H]+ 328.0614; found
328.0621.
MHz, CDCl3):  (ppm) 114.8, 116.7, 123.1, 126.4, 127.3, 129.5,
129.9, 130.2, 134.4, 135.6, 140.5, 155.0 (q, J = 37.8 Hz); 19F
NMR (CDCl3 + hexafluorobenzene): δ -79.1 (s); IR (KBr): 3441,
2924, 2854, 1728, 1614, 1554, 1462, 1441, 1280, 1186, 1160,
1138, 1018, 897, 800, 758, 738, 682, 549, 530, 494 cm-1; HRMS
(ESI): calcd. for C14H11F3NO2S [M+H]+ 314.0457; found
314.0461.
2,2,2-Trifluoro-N-(2-((3-
methoxyphenyl)sulfinyl)phenyl)acetamide (1cb՛՛): Brownish
solid; mp 9597 C; 1H NMR (600 MHz, CDCl3):  (ppm) 3.81 (s,
3H), 6.956.99 (m, 2H), 7.14 (s, 1H), 7.307.33 (m, 1H), 7.35 (t,
1H, J = 7.8 Hz), 7.547.57 (m, 1H), 7.62 (dd, 1H, J = 7.8, 1.3
Hz), 8.36 (d, 1H, J = 8.4 Hz), 11.59 (s, 1H); 13C NMR (100 MHz,
CDCl3):  (ppm) 55.7, 108.9, 116.4, 117.5, 123.4, 125.6, 128.0,
129.3, 130.7, 133.3, 138.1, 143.4, 155.1 (d, J = 37.8 Hz), 160.6;
19F NMR (CDCl3 + hexafluorobenzene): δ -79.1 (s); IR (KBr):
3434, 2923, 2852, 1734, 1595, 1467, 1440, 1282, 1248, 1158,
1037, 896, 762, 683, 613, 593, 513, 464 cm-1; HRMS (ESI):
calcd. for C15H13F3NO3S [M+H]+ 344.0563; found 344.0558.
N-(2-([1,1'-Biphenyl]-2-ylsulfinyl)phenyl)acetamide (1ia՛՛):
Dark brownish solid; mp 7375 C; 1H NMR (400 MHz, CDCl3):
 (ppm) 2.09 (s, 3H), 6.17 (d, 1H, J = 7.6 Hz), 6.59 (t, 1H, J =
7.6 Hz), 7.09 (d, 2H, J = 7.2 Hz), 7.22 (t, 2H, J = 7.6 Hz),
7.327.42 (m, 3H), 7.49 (t, 1H, J = 7.6 Hz), 7.59 (t, 1H, J = 7.6
Hz), 8.09 (d, 1H, J = 8.0 Hz), 8.16 (d, 1H, J = 7.6 Hz), 9.67 (s,
1H); 13C NMR (150 MHz, CDCl3):  (ppm) 24.8, 122.8, 122.84,
123.9, 126.7, 127.7, 128.4, 128.5, 128.8, 129.5, 131.2, 131.5,
132.3, 138.1, 139.4, 139.9, 140.9, 168.3; IR (KBr) 3261, 2925,
1700, 1587, 1530, 1434, 1368, 1301, 1245, 1159, 1072, 1007,
756, 702, 552, 519, 489 cm-1; HRMS (ESI): calcd. for
C20H18NO2S [M+H]+ 336.1053; found 336.1068.
2,2,2-Trifluoro-N-(2-(p-tolylsulfinyl)phenyl)acetamide
(1db՛՛): Brownish solid; mp 8082 C; 1H NMR (600 MHz,
CDCl3):  (ppm) 2.37 (s, 3H), 7.27 (d, 2H, J = 8.4 Hz), 7.30 (t,
1H, J = 7.8 Hz), 7.40 (d, 2H, J = 7.8 Hz), 7.537.55 (m, 1H),
7.587.59 (m, 1H), 8.36 (d, 1H, J = 8.4 Hz), 11.68 (s, 1H); 13C
NMR (150 MHz, CDCl3):  (ppm) 21.6, 114.8, 116.7, 121.4,
123.5, 124.4, 125.6, 127.9, 129.5, 129.6, 132.2, 133.2, 138.0,
140.0, 141.8, 155.1 (q, J = 37.7 Hz); 19F NMR (CDCl3
+
N-(4-Fluoro-2-(phenylsulfinyl)phenyl)acetamide
(3aa՛՛):
Yellowish gummy; 1H NMR (400 MHz, CDCl3):  (ppm) 2.05 (s,
3H), 7.177.22 (m, 1H), 7.287.30 (m, 1H), 7.477.54 (m, 5H),
8.30 (dd, 1H, J = 9.2, 4.8 Hz), 9.87 (s, 1H); 13C NMR (100 MHz,
CDCl3):  (ppm) 24.7, 114.8 (d, J = 24.3 Hz), 119.9 (d, J = 21.6
Hz), 124.4, 125.0 (d, J = 4.4 Hz), 125.4 (d, J = 6.9 Hz), 129.3 (d,
J = 4.4 Hz), 129.7, 129.9 (d, J = 5.4 Hz), 131.3 (d, J = 5.8 Hz),
131.5, 136.4 (d, J = 2.9 Hz), 142.3, 156.8, 159.2, 168.6; 19F NMR
(CDCl3 + hexafluorobenzene): δ -119.8 (s); IR (KBr) 3258, 2926,
2856, 1690, 1602, 1485, 1396, 1301, 1244, 1193, 1124, 1080,
1025, 896, 812, 750, 689, 584, 545, 499 cm-1; HRMS (ESI):
calcd. for C14H13FNO2S [M+H]+ 278.0646; found 278.0647.
hexafluorobenzene): δ -79.1 (s); IR (KBr): 3441, 2926, 1733,
1604, 1547, 1444, 1281, 1199, 1158, 1080, 1012, 900, 808, 761,
619, 549, 530, 492 cm-1; HRMS (ESI): calcd. for C15H13F3NO2S
[M+H]+ 328.0614; found 328.0617.
2,2,2-Trifluoro-N-(2-((4-
fluorophenyl)sulfinyl)phenyl)acetamide
(1eb՛՛):
Dark

1
brownish solid; mp 99101 C; H NMR (600 MHz, CDCl3): 
(ppm) 7.18 (t, 2H, J = 8.4 Hz), 7.33 (t, 1H, J = 7.2 Hz), 7.507.52
(m, 2H), 7.567.59 (m, 1H), 7.617.62 (m, 1H), 8.37 (d, 1H, J =
8.4 Hz), 11.52 (s, 1H); 13C NMR (150 MHz, CDCl3):  (ppm)
114.8, 116.7, 117.1 (d, J = 22.6 Hz), 123.7, 125.7, 126.6 (d, J =
9.0 Hz), 127.8, 129.2, 133.5, 137.6 (d, J = 3.0 Hz), 138.1, 155.2
N-(4-Fluoro-2-(p-tolylsulfinyl)phenyl)acetamide
(3da՛՛):
Light brownish solid; mp 153155 C; 1H NMR (400 MHz,
CDCl3):  (ppm) 2.03 (s, 3H), 2.35 (s, 3H), 7.127.17 (m, 1H),
7.207.26 (m, 3H), 7.37 (d, 2H, J = 8.0 Hz), 8.27 (dd, 1H, J =
8.8, 4.8 Hz), 9.91 (s, 1H); 13C NMR (100 MHz, CDCl3):  (ppm)
21.5, 24.8, 114.6 (d, J = 24.2 Hz), 119.6 (d, J = 21.6 Hz), 124.5,
125.2 (d, J = 6.9 Hz), 130.1 (d, J = 4.9 Hz), 130.4, 136.3 (d, J =
3.0 Hz), 139.1, 142.1, 156.7, 159.2, 168.6; 19F NMR (CDCl3 +
hexafluorobenzene): δ -120.0 (s); IR (KBr) 3434, 3272, 2925,
2856, 1663, 1598, 1517, 1471, 1391, 1265, 1242, 1181, 1117,
1057, 1024, 888, 841, 815, 680, 632, 584, 506, 451 cm-1; HRMS
(ESI): calcd. for C15H15FNO2S [M+H]+ 292.0802; found 292.0802.
(q,
J = +
37.8 Hz), 163.7, 165.4; 19F NMR (CDCl3
hexafluorobenzene): δ -111.2 (s), -79.1 (s); IR (KBr): 3441, 3061,
2924, 1729, 1613, 1553, 1489, 1438, 1281, 1234, 1192, 1162,
1069, 899, 831, 758, 734, 531, 475 cm-1; HRMS (ESI): calcd. for
C14H10F4NO2S [M+H]+ 332.0363; found 332.0372.
N-(2-((4-Chlorophenyl)sulfinyl)phenyl)-2,2,2-
trifluoroacetamide (1fb՛՛): Brownish solid; mp 100102 C; 1H
NMR (600 MHz, CDCl3):  (ppm) 7.33 (t, 1H, J = 7.2 Hz), 7.45
(s, 4H), 7.57 (t, 1H, J = 9.0 Hz), 7.617.63 (m, 1H), 8.36 (d, 1H,
J = 8.4 Hz), 11.48 (s, 1H); 13C NMR (150 MHz, CDCl3): (ppm)
118.0, 118.2, 123.6, 125.6, 125.7, 127.9, 128.5, 129.0, 129.5,
130.0, 133.6, 137.9, 138.1, 140.6, 155.1 (q, J = 37.8 Hz); 19F
NMR (CDCl3 + hexafluorobenzene): δ -79.1 (s); IR (KBr): 3459,
2925, 2855, 1717, 1615, 1551, 1474, 1446, 1391, 1281, 1243,
1200, 1161, 1090, 1024, 1009, 901, 823, 758, 741, 617, 578,
556, 523, 485, 455 cm-1; HRMS (ESI): calcd. for
C14H10ClF3NO2S [M+H]+ 348.0067; found 348.0065.
N-(2-((4-Chlorophenyl)sulfinyl)-4-fluorophenyl)acetamide
(3fa՛՛): Light brownish solid; mp 178180 C; 1H NMR (400 MHz,
CDCl3):  (ppm) 2.06 (s, 3H), 7.187.23 (m, 1H), 7.267.29 (m,
1H), 7.46 (s, 4H), 8.29 (dd, 1H, J = 9.2, 4.8 Hz), 9.77 (s, 1H); 13
C
NMR (100 MHz, CDCl3):  (ppm) 24.7, 114.7 (d, J = 24.3 Hz),
120.2 (d, J = 21.5 Hz), 125.6 (d, J = 7.0 Hz), 125.8, 129.7 (d, J
= 5.0 Hz), 129.9, 136.3, 137.9, 140.8, 156.8, 159.3, 168.5; 19F
NMR (CDCl3 + hexafluorobenzene): δ -119.4 (s); IR (KBr) 3423,
3273, 2926, 2855, 1661, 1598, 1515, 1476, 1391, 1373, 1245,
1184, 1089, 1058, 1015, 888, 825, 740, 679, 587, 506, 477 cm-
1; HRMS (ESI): calcd. for C14H12ClFNO2S [M+H]+ 312.0256;
found 312.0354.
(S)-2,2,2-Trifluoro-N-(4-fluoro-2-
(phenylsulfinyl)phenyl)acetamide (3ab՛՛): Brownish gummy;
1H NMR (600 MHz, CDCl3):  (ppm) 7.237.26 (m, 1H), 7.35 (dd,
1H, J = 6.9, 2.9 Hz), 7.497.52 (m, 3H), 7.537.55 (m, 2H), 8.35
(dd, 1H, J = 9.1, 4.6 Hz), 11.45 (s, 1H); 13C NMR (150 MHz,
DMSO-d6):  (ppm) 112.0 (d, J = 25.3 Hz), 114.8, 116.7, 119.5
(d, J = 22.8 Hz), 121.1, 129.7, 130.3 (d, J = 8.1 Hz), 132.0, 143.6,
143.8 (d, J = 5.7 Hz), 155.5, 155.7, 160.6, 162.2; 19F NMR
(DMSO-d6 + hexafluorobenzene): δ -112.9 (s), -76.4 (s); IR
(KBr): 3429, 1649, 1384, 1047, 1026, 997, 827, 766, 740, 640,
2,2,2-Trifluoro-N-(2-(phenylsulfinyl)phenyl)acetamide
(1ab՛՛): Brownish solid; mp 9294 C; 1H NMR (600 MHz,
CDCl3):  (ppm) 7.25 (t, 1H, J = 7.2 Hz), 7.40 (q, 3H, J = 6.3 Hz),
7.45 (d, 2H, J = 7.2 Hz), 7.48 (t, 1H, J = 7.2 Hz), 7.56 (d, 1H, J
= 7.8 Hz), 8.28 (d, 1H, J = 8.4 Hz), 11.51 (s, 1H); 13C NMR (150
9
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801597
European Journal of Organic Chemistry
431 cm-1; HRMS (ESI): calcd. for C14H10F4NO2S [M+H]+
332.0363; found 332.0566.
admixed with ethyl acetate (20 mL) and the organic layer was
washed with saturated NaHCO3 solution. The ethyl acetate layer
was separated and dried over anhydrous Na2SO4. The solvent
was then evaporated under reduced pressure and the residue
was purified by column chromatography with eluents
hexane:EtOAc (60:40) to afford the desired product (4aa՛՛) in an
isolated yield of 98% (66 mg).
N-(2-(Phenylsulfinyl)phenyl)propionamide (1ac՛՛): Dark

brownish solid; mp 8587 C; 1H NMR (400 MHz, CDCl3): 
(ppm) 1.12 (t, 3H, J = 7.6 Hz), 2.202.35 (m, 2H), 7.17 (t, 1H, J
= 7.6 Hz), 7.437.52 (m, 6H), 7.57 (d, 1H, J = 7.6 Hz), 8.38 (d,
1H, J = 8.4 Hz), 10.05 (s, 1H); 13C NMR (150 MHz, CDCl3): 
(ppm) 9.6, 31.2, 123.2, 123.3, 124.5, 124.9, 128.2, 129.4, 131.0,
133.4, 140.5, 143.0, 172.5; IR (KBr): 3403, 2924, 2852, 1695,
1586, 1531, 1466, 1439, 1380, 1297, 1261, 1188, 1155, 1086,
1019, 804, 753, 692, 542, 439 cm-1; HRMS (ESI): calcd. for
C15H16NO2S [M+H]+ 274.0896; found 274.0897.
N-(4-Bromo-2-(phenylsulfinyl)phenyl)acetamide
(4aa՛՛):
White solid; mp 147149 C; 1H NMR (400 MHz, CDCl3):  (ppm)
2.03 (s, 3H), 7.457.56 (m, 6H), 7.66 (s, 1H), 8.21 (d, 1H, J =
8.4 Hz), 10.0 (s, 1H); 13C NMR (150 MHz, CDCl3):  (ppm) 24.8,
115.8, 124.4, 124.7, 129.6, 129.9, 130.2, 131.4, 135.9, 139.1,
142.2, 168.5; IR (KBr) 3433, 3253, 2926, 2854, 1664, 1577,
1505, 1468, 1375, 1286, 1244, 1140, 1080, 1036, 929, 828, 751,
694, 662, 592, 559, 498, 484, 427 cm-1; HRMS (ESI): calcd. for
C14H13BrNO2S [M+H]+ 337.9845; found 337.9827.
N-(2-(Phenylsulfinyl)phenyl)pivalamide
(1ad՛՛):
Dark

1
brownish solid; mp 139141 C; H NMR (400 MHz, CDCl3): 
(ppm) 1.16 (s, 9H), 7.157.19 (m, 1H), 7.417.48 (m, 5H),
7.497.56 (m, 2H), 8.53 (d, 1H, J = 8.4 Hz), 10.3 (s, 1H); 13C
NMR (150 MHz, CDCl3): (ppm) 27.5, 40.1, 123.07, 123.1,
125.0, 127.3, 128.4, 129.4, 131.0, 133.4, 141.0, 143.3, 177.7;
IR (KBr): 3257, 2963, 2856, 1689, 1586, 1534, 1476, 1435, 1398,
1367, 1301, 1228, 1124, 1080, 1019, 919, 808, 754, 690, 592,
569, 532, 497 cm-1; HRMS (ESI): calcd. for C17H20NO2S [M+H]+
302.1209; found 302.1194.
General
Procedure
for
the
Nitration
of
N-(2-
N-(2-
(Phenylsulfinyl)phenyl)acetamide
(1aa՛՛):
(Phenylsulfinyl)phenyl)acetamide (1aa՛՛) (52 mg, 0.2 mmol),
Cu(NO3)2·3H2O (4.8 mg,0.02 mmol), TBN (0.029 mL, 0.24
mmol) and CH3CN (3.0 mL) were taken in an oven-dried round
bottom flask. The resulting mixture was heated in an oil bath at
80 °C for 2 h, and the progress of the reaction was monitored by
TLC. After cooling the mixture to room temperature, the volatiles
were removed in vacuo, and the residue was purified by column
chromatography with eluents hexane:EtOAc (53:47) to afford
the desired product (5aa՛՛) in an isolated yield of 84% (51 mg).
N-(2-(Phenylsulfinyl)phenyl)hexanamide
(1de՛՛):
Dark
1
brownish gummy; H NMR (600 MHz, CDCl3):  (ppm) 0.88 (t,
3H, J = 7.2 Hz), 1.231.32 (m, 4H), 1.561.61 (m, 2H),
2.172.22 (m, 1H), 2.262.31 (m, 1H), 2.35 (s, 3H), 7.14 (t, 1H,
J = 7.8 Hz), 7.23 (d, 2H, J = 8.4 Hz), 7.35 (d, 2H, J = 8.4 Hz),
7.47 (t, 1H, J = 7.8 Hz), 7.52 (d, 1H, J = 7.8 Hz), 8.39 (d, 1H, J
= 8.4 Hz), 10.12 (s, 1H); 13C NMR (150 MHz, CDCl3):  (ppm)
14.1, 21.4, 22.6, 25.1, 31.5, 38.1, 123.0, 123.2, 124.5, 127.8,
128.0, 130.1, 133.2, 139.7, 140.4, 141.5, 171.9; IR (KBr): 3358,
2927, 2857, 1706, 1588, 1526, 1465, 1440, 1378, 1315, 1225,
1148, 1092, 1041, 1019, 812, 734, 712, 653, 580, 554, 521 cm-
1; HRMS (ESI): calcd. for C19H24NO2S [M+H]+ 330.1522; found
330.9066.
N-(4-Nitro-2-(phenylsulfinyl)phenyl)acetamide
(5aa՛՛):

1
Brownish solid; mp 120122 C; H NMR (400 MHz, CDCl3): 
(ppm) 2.16 (s, 3H), 7.517.57 (m, 5H), 8.31 (dd, 1H, J = 9.2, 2.5
Hz), 8.44 (d, 1H, J = 2.8 Hz), 8.65 (d, 1H, J = 9.2 Hz), 10.64 (s,
1H); 13C NMR (100 MHz, CDCl3):  (ppm) 25.2, 122.4, 123.4,
124.4, 127.8, 128.4, 129.9, 131.9, 141.6, 142.3, 145.9, 169.1;
IR (KBr) 3421, 3200, 2924, 2854, 1711, 1611, 1587, 1500, 1400,
1348, 1318, 1284, 1226, 1131, 1076, 1020, 908, 858, 749, 686,
603, 555, 533, 497, 448 cm-1; HRMS (ESI): calcd. for
C14H13N2O4S [M+H]+ 305.0591; found 305.0577.
4-Methoxy-N-(2-(p-tolylsulfinyl)phenyl)benzamide
(1df՛՛):
Yellowish gummy; 1H NMR (400 MHz, CDCl3):  (ppm) 2.27 (s,
3H), 3.87 (s, 3H), 6.99 (d, 2H, J = 8.8 Hz), 7.12 (d, 2H, J = 8.0
Hz), 7.17 (d, 1H, J = 7.4 Hz), 7.34 (d, 2H, J = 8.0 Hz), 7.497.55
(m, 2H), 7.98 (d, 2H, J = 8.8 Hz), 8.60 (d, 1H, J = 8.0 Hz), 11.1
(s, 1H); 13C NMR (100 MHz, CDCl3):  (ppm) 21.4, 55.6, 114.1,
123.0, 123.2, 124.5, 126.4, 127.8, 127.9, 129.5, 130.1, 133.1,
139.6, 141.5, 141.6, 162.8, 164.8; IR (KBr) 3244, 2958, 2843,
1676, 1605, 1540, 1509, 1463, 1436, 1255, 1180, 1114, 1080,
1024, 896, 845, 810, 761, 735, 686, 624, 578, 543, 475 cm-1;
HRMS (ESI): calcd. for C21H20NO3S [M+H]+ 366.1158; found
366.1152.
Acknowledgements
B.K.P. acknowledges the support of this research by the
Department of Science and Technology (DST/SERB)
(EMR/2016/007042), DST-FIST, and MHRD: 5-5/2014-TS-VII.
CIF, IIT Guwahati for instrumental facilities.
Keywords: Carboxylic acids; Cross-coupling; Isotopic
labeling;
Oxidation;
Ring
opening
rearrangement
functionalization (RORF).
4-Chloro-N-(2-(p-tolylsulfinyl)phenyl)benzamide
(1dg՛՛):
Yellowish gummy; 1H NMR (400 MHz, CDCl3):  (ppm) 2.30 (s,
3H), 7.14 (d, 2H, J = 8.0 Hz), 7.20 (t, 1H, J = 7.2 Hz), 7.33 (d,
2H, J = 8.4 Hz), 7.47 (d, 2H, J = 8.8 Hz), 7.55 (d, 2H, J = 7.6 Hz),
7.94 (d, 2H, J = 8.4 Hz), 8.59 (d, 1H, J = 8.0 Hz), 11.30 (s, 1H);
13C NMR (100 MHz, CDCl3):  (ppm) 21.4, 123.1, 123.7, 124.5,
127.9, 128.0, 129.0, 129.2, 130.2, 132.5, 133.2, 138.6, 139.6,
140.7, 141.7, 164.1; IR (KBr) 3430, 3243, 2923, 1682, 1598,
1540, 1489, 1436, 1315, 1256, 1103, 1012, 893, 848, 808, 756,
674, 620, 547, 524, 477 cm-1; HRMS (ESI): calcd. for
C20H17ClNO2S [M+H]+ 370.0663; found 370.0645.
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General Procedure for the Bromination of N-(2-
(Phenylsulfinyl)phenyl)acetamide (1aa՛՛): An oven-dried
round
bottom
flask
was
charged
with
N-(2-
(phenylsulfinyl)phenyl)acetamide (1aa՛՛) (52 mg, 0.2 mmol),
KBrO3 (0.06 mmol, 11 mg), AcOH (0.3 mL) and stirred at room
temperature. Then 48% hydrobromic acid (0.04 mL) was added
to the stirred reaction mixture. The reaction progress was
monitored by TLC. After 30 min, the reaction mixture was
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This article is protected by copyright. All rights reserved.

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European Journal of Organic Chemistry
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(phenylsulfinyl)phenyl)acetamide
(1ab՛՛)
contain
the
supplementary crystallographic data for this paper. These data
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Crystallographic
Data
Centre
via
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11
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10.1002/ejoc.201801597
European Journal of Organic Chemistry
Graphical Abstract
Ring opening rearrangement
functionalization (RORF)
Ahalya Behera, Amitava
Rakshit, Ashish K. Sahoo
and Bhisma K. Patel*
Page No. – Page No.
One
Pot
Sequential
Synthesis
of
N-(2-
(Phenylsulfinyl)phenyl)aceta
mides: Ring Opening
A
Rearrangement
Functionalization (RORF)
A new telescopic synthesis of N-(2-(phenylthio)phenyl)acetamides has been
established using benzo[d]thiazol-2-amine, aryliodide and carboxylic acid via a
copper catalyzed ring opening rearrangement functionalization (RORF). The
Keywords: Carboxylic acids;
Cross-coupling;
Isotopic
labeling;
opening
Oxidation; Ring
sequential
addition
of
TBHP
leads
to
the
formation
of
N-(2-
rearrangement
(phenylsulfinyl)phenyl)acetamide.
functionalization (RORF).
12
This article is protected by copyright. All rights reserved.