Photo-Difunctionalization and Photo-Oxidative Cleavage of the C–C Double Bond of Styrenes in the Presence of Nanosized Cadmium Sulfide (CdS) as a Highly Efficient Photo-Induced Reusable Nanocatalyst

Article abstract of DOI:10.1002/ejoc.202000448

The synthesis of cyclic dithiocarbonates via photo-difunctionalization of the C–C double bond of styrene and aryl aldehydes via photo-oxidative cleavage of the C–C double bond of styrene was accomplished in the presence of CdS NPs at room temperature in air atmosphere under visible light irradiation without using any external oxidant. Some of the special advantages of these processes are the use of CdS NPs as a simple, accessible, safe, and visible-light-induced reusable catalyst, as well as the use of air as an easily attainable, inexpensive, and harmless oxidant, styrene as a readily accessible substrate, and visible-light as a renewable and safe energy source.

Full text of DOI:10.1002/ejoc.202000448

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Photo-difunctionalization and oxidative Cleavage of the C–C
Double Bond Using Nanosized Cadmium Sulfide (CdS) as Photo-
Induced Reusable Nanocatalyst
Authors: Somayeh Firoozi and Mona Hosseini-Sarvari
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202000448
Link to VoR: https://doi.org/10.1002/ejoc.202000448
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1/2020

European Journal of Organic Chemistry
10.1002/ejoc.202000448
FULL PAPER
Photo-difunctionalization and Photo-oxidative Cleavage of the C–
C Double Bond of Styrenes in the Presence of Nanosized Cadmium
Sulfide (CdS) as a Highly Efficient Photo-Induced Reusable
Nanocatalyst
[a]
[a]
Somayeh Firoozi , Mona Hosseini-Sarvari *
[a]
Department of Chemistry, College of Science, Shiraz University, Shiraz 7194684795, I.R. Iran
Corresponding author: Prof. Dr. Mona Hosseini-Sarvari, E-mail: hossaini@shirazu.ac.ir, Homepage URL: http://chem.shirazu.ac.ir/?page_id=546;
tweet@MonaHosseini72
Mrs. Somayeh Firoozi, PhD candidate.
Supporting informati on for this article is given via a link at the end of the document.
Abstract: The synthesis of cyclic dithiocarbonates via photo-
difunctionalization of the C–C double bond of styrene and aryl
aldehydes via photo-oxidative cleavage of the C–C double bond of
styrene was accomplished in the presence of CdS NPs at room
temperature in air atmosphere under visible light irradiation without
using any external oxidant. Some of the special advantages of these
processes can be mentioned the use of CdS NPs as a simple,
accessible, safe and visible-light-induced reusable catalyst, air as an
easily attainable, inexpensive and harmless oxidant, styrene as a
readily accessible substrate and visible-light as a renewable, available
and safe energy source.
usual doping processes are time-consuming, costly, and/or faced
with environmental pollution (For example, doping is done with
9
toxic heavy metals such as Pd, Au, Ni, Ag, etc, ...) . Hence, the
use of visible light absorbent semiconductors without requires
10
modifications is very important . The most important properties
of CdS as a good photocatalyst can be mentioned as appropriate
bandgap, efficient visible light absorption, high surface area, and
suitable redox potential for the interaction with organic
10c, 11
compounds
.
Styrenes as readily accessible substrates can easily trap
the radicals, hence, it can perform important chemical
transformations via cleavage or difunctionalization of the C-C
double bond. The structure of styrenes allows adding two
functional groups at the same time and in a single step. Moreover,
several studies have been reported for the oxidative cleavage of
12
13
a C-C double bond and the difunctionalization of styrenes
.
Introduction
Interestingly, carbonyl products obtained from cleavage of
alkenes applied for the synthesis of biologically active and natural
st
14
The onset of the 21 century has been accompanied by a
significant increase in research in the field of visible light
compounds . They are also used as important precursors for the
1
5
synthesis of many organic compounds . Many processes have
been reported to perform this momentous transformation. The
most famous of them are ozonolysis and oxidation reactions using
1
photocatalysis . A combination of visible light and catalysts can
be used for developing selective and efficient chemical
transformations (like the unrivaled process of photosynthesis in
OsO
reagents in combination with a transition metal catalyst
Besides, investigations have been done into equivalent oxygen
4 4 4
, RuO , KMnO , peracids, peroxides, and other oxidizing
2
16-18
nature) . Hereon, the organic compounds are synthesized with
.
the minimal environmental impact using mild conditions. So, one
of the aims of green chemistry is being achieved. Visible-light can
irritate photocatalysts as a safe, easily available, inexpensive, and
19
and oxidants in combination with organic molecules
electrochemical alternatives
and
. The use of homogeneous,
20
3
renewable energy source . The light absorbent photocatalysts
expensive or toxic metals catalysts and excess amounts of
poisonous oxidants along with the production of great quantities
of by-products are the main disadvantages of these processes,
which pose safety hazards and environmental pollution. In the
past decade, chemists have centralized more on the synthesis of
such as organic dyes, metal complexes, and semiconductors can
operate as an initiator for the chemical transformations.
Whenever organic dyes and metal complexes are used as
photocatalysts, the environmental pollutions challenges are
inescapable.
In the last decade, many organic reactions have been
accomplished with expensive and toxic metal complexes such as
Au, Pd, Ni, Ir, Cu, Rh, and Ru in the presence of light . The
synthesis of these metal complexes is confronted with problems
such as toxicity, expensive, time-consuming, and the preparation
of them are difficult . Therefore, the use of semiconductors
without the need for modification is more important (such as Metal
oxides and metal sulfides) . However, semiconductors as
photocatalyst alone are rarely used in important organic reactions
for several reasons such as non-absorption of visible light, the fast
recombination of electron and hole, and lack of suitable redox
potential for the interaction with organic substrates. So usually,
the direct use of them is not possible and requires modifications
2
1,
22
organic compounds via photochemical methods
Unfortunately, there are few reports in the field of photochemical
.
23
cleavage of C-C double bonds . Although these methods are
superior to other methods, however, this process suffers from the
challenges of low selectivity, solvent and catalyst toxicity, costly
catalyst, contamination, and homogeneity of the photocatalyst.
Dithiocarbonates are the principal backbone of numerous
bioactivities and natural compounds. They demonstrate
antibacterial, neuroprotective, antifungal, and tuberculostatic
activities and have applications in the materials science and also
used in the organic synthesis as a versatile radical source and
intermediates for the preparation of thiols, alkenes, alkanes,
4
5
6
24, 25
photosensitizers, and S-activated carbanions
. The most
popular strategy for the synthesis of five-membered cyclic
dithiocarbonates is based on the nucleophilic attack of carbon
disulfide salt (such as O-methyl carbonodithioate salt) on the
oxiranes in the presence of a base catalyst. For instance,
7
to increase the photocatalytic effect . Morphological, structural,
optical and electric properties of metal oxides and sulfides can be
tailored through doping with anions or cations . Most of the
8
9
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1

European Journal of Organic Chemistry
10.1002/ejoc.202000448
FULL PAPER
pyridine-based organocatalysts, tertiary amines, alcoholates, or
alkali metals halides under the non-photochemical conditions
have been reported . These methods restrain their synthetic
utilization on the causes of the organization of regioisomeric
products, high catalyst loading, low efficiency, the requirement of
high pressure and harsh reaction conditions.
cesium carbonate was present as a base. Unfortunately, the yield
was reduced due to the low solubility of cesium carbonate and
cesium methyl xanthate salt (A) in EtOH. (Table 1, Entry 2). By
using a mixture of water and ethanol to increase the solubility, but
2
6
it did not help (Table 1, Entry 3). A batch of bases including K
PO , NaHCO , NaH, and NaOMe was replaced (Table 1,
Entries 4-8). As it can be perused in Table 1, Cs CO acts more
effectively to produce the desired product. Furthermore, different
amounts of Cs CO and methanol were also applied (Table 1,
Entries 1, 11-14). Using less than 3 mL of MeOH and 1 eq of
Cs CO were reduced efficiency. Investigation of other
photocatalysts such as ZnO and TiO were revealed the special
2 3
CO ,
In 2016, the Yadav and co-workers have published the
first photochemical approach for the synthesis of 1,3-oxathiolane-
K
3
4
3
2
3
2
-thiones in the presence of eosin Y via the difunctionalization of
27
styrenes (Scheme 1) . The drawback of this report is the use of
eosin Y as a homogeneous organic photocatalyst but the
prefunctionalization of styrenes is superior to the ring-opening of
oxiranes.
2
3
2
3
2
performance of CdS for the synthesis of 1,3-oxathiolane-2-
thiones (Table 1, Entries 15, 16).
1
. CS2 , Cs CO3
MeOH, R.T., 3 h
S
S
2
O
Ar
2
. EosinY
Green LEDs,O2 Air, R.T.
Ar
1. CS
Solvent (3 mL), R.T., 3 h
2
(1 eq), base (1 eq)
S
Scheme 1. The report published in the synthesis of 1,3-oxathiolane-2-thiones
under the photochemical approach.
O
Ph
1
2
. photocatalyst(0.015 g)
S
Light,O2 Air, R.T.
Ph
According to the aforementioned topics and our
experience in the use of CdS NPs as visible-light-induced
(2a)
mmol
(3a)
6
Scheme 3. The synthesis of 5-phenyl-1,3-oxathiolane-2-thione (3a) as a model
reaction under different conditions.
reusable catalysts , we attempted to introduce the photo-
oxidative cleavage and the photo-difunctionalization of the C–C
double bond of styrenes for the synthesis of aryl aldehydes and
Table 1: The effect of various solvents, bases, and photocatalysts for the
synthesis of 5-phenyl-1,3-oxathiolane-2-thione (3a).
1
,3-oxathiolane-2-thiones, respectively. These processes are
easily accomplished in the presence of CdS as a visible-light-
induced nano photocatalyst under blue LEDs or sunlight in the air
atmosphere at room temperature without the use of any external
oxidants (Scheme 2). It is worth mentioning that the C–C double
bond of styrenes for the synthesis of aryl aldehydes occurred in
solvent-free conditions. According to the literature review, there is
not any report based on using the photo-induced catalyst in
solvent-free conditions for the synthesis of organic compounds,
Entry
Solvent
MeOH
EtOH
Base
Photocatalyst
CdS
CdS
Yield (%)
86
25
25
76
30
15
20
40
1
2
3
4
5
6
7
8
9
Cs
2
Cs
2
Cs
2
CO
CO
CO
3
3
3
EtOH/H
2
O (2:1)
CdS
CdS
CdS
CdS
CdS
CdS
CdS
CdS
CdS
CdS
CdS
CdS
ZnO
TiO
2
MeOH
MeOH
MeOH
MeOH
MeOH
K
K
2
CO
PO
3
3
4
NaHCO
NaH
NaOMe
NaOMe
NaOMe
3
6
CH
3
CN
35
30
except that our research team has recently published .
10
11
12
13
14
15
16
Solvent-Free
MeOH
MeOH
MeOH
MeOH
a
Cs
2
Cs
2
Cs
2
Cs
2
Cs
2
Cs
2
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
40
b
30
50
c
d
87
Trace
Trace
MeOH
MeOH
2
Reaction conditions: CS (1 mmol) and base (1.0 mmol) in the solvent (3 mL)
were taken in a closed test tube and stirred at room temperature for 3 hours
after that styrene (2a, 1 mmol) and photocatalyst (0.015 g) were added to the
open test tube and the reaction mixture was exposed under withe LEDs 12 W
a
lamp for 12 hours in the air atmosphere at room temperature. Cs
b
2
CO
3
(0. 5
c
d
mmol), MeOH (1.0 mmol), MeOH (2 mL), MeOH (4 mL).
As discussed in Table 1, the reaction proceeds very well in
the presence of CdS NPs and Cs CO (1.0 mmol) in methanol (3
2
3
mL) (Table 1, Entry 1). Next, the amount of CdS, wavelength of
light, and the atmosphere were examined. There is an
insignificant difference between 10–20 mol% of CdS (Table 2,
Entries 1-3), whereas less than 10 mol% was decreased the yield
Scheme 2. The synthesis of 1,3-oxathiolane-2-thiones and aryl aldehydes in
the presence of CdS as a visible-light-induced nano photocatalyst.
(Table 2, Entry 4) and no product was formed in the absence of
CdS NPs (Table 2, Entry 5). Also, no product was formed in the
dark which confirms the photocatalytic ability of CdS NPs for the
reaction progression (Table 2, Entry 6). A comparison of different
wavelengths showed that the reaction under blue LEDs light and
sunlight has made the best progress (Table 2, Entries 3, 7-10).
According to the UV-visible spectrum, this implies a maximum
absorption of CdS in the range of 400–480 nm (blue light range).
In other studies, reactions were carried out under argon and
oxygen gas, in which the formation of the trace amounts of the
desired product under the argon was proved that oxygen plays a
key role in the reaction (Table 2, Entries 11, 12).
Results and Discussion
In the beginning, CdS NPs were prepared according to our
6
previously reported method (see supporting information).
To find the best reaction conditions, styrene (1.0 mmol) and
carbon disulfide salt (1.0 mmol) were chosen as model
compounds for the synthesis of 5-phenyl-1,3-oxathiolane-2-
thione (3a) (Scheme 3).
According to the proposed mechanism, the solvent should
have both good nucleophilic character and be a good leaving
group, which will be discussed in the following pages. Therefore,
an attempt was made to replace methanol with ethanol when the
2
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European Journal of Organic Chemistry
10.1002/ejoc.202000448
FULL PAPER
Table 2: The effect of diverse amounts of photocatalyst, different wavelengths
of light, and atmospheres for the synthesis of 5-phenyl-1,3-oxathiolane-2-thione
(3a).
oxathiolane-2-thione and (cis)-4,5-diphenyl-1,3-oxathiolane-2-thione (The
HNMR spectrum of the reaction mixture shows that the trans-product (
3.33 times as much as cis-product ( 28%)).
̴ 65%) is
̴
Entry
Amount of photocatalyst (mol%)
CdS (20)
CdS (15)
Light
White
White
White
White
White
Dark
Red
Green
Blue
Sun
Blue
Blue
Yield (%)
1
2
3
4
5
6
7
8
9
87
86
86
73
0
In continuation, to explore optimal conditions for the
synthesis of aryl aldehydes through the photo-oxidative cleavage
of the styrene C–C double bond, styrene (2a) was elected as a
model compound (Scheme 5). After examining a series of
reaction parameters, it has been found that CdS NPs (10 mol%)
as a photocatalyst, blue LED light, solvent-free conditions, air
atmosphere, and at room temperature were the most appropriate
options for the establishment of the benzaldehyde (4a) formation.
To find a suitable media for the reaction, various solvents
CdS (10)
CdS (5)
Catalyst-Free
CdS (10)
CdS (10)
CdS (10)
CdS (10)
CdS (10)
CdS (10)
CdS (10)
0
65
76
89
90
10
11
12
a
Trace
b
90
such as H
2 3 2 2
O, EtOH, CH CN, MeOH, EtOAc, acetone, CH Cl ,
2 2 3
Reaction conditions: CS (1.0 mmol) and Cs CO (1.0 mmol) in MeOH (3 mL)
CHCl , DMF, DMSO, THF, dioxane, and solvent-free condition
3
were taken in a closed test tube and stirred at room temperature for 3 hours
after that styrene (2a, 1.0 mmol) and CdS (10 m0l%) was added to the open
test tube and the reaction mixture was exposed under LEDs 12 W lamp for 12
were examined (Table 4, Entries 1-12) and the best
consequences were captured under the solvent-free condition
(Table 4, Entry 13). Investigation of other photocatalysts such as
a
b
hours in the air atmosphere at room temperature. Argon balloon, oxygen
balloon.
ZnO and TiO
synthesis of benzaldehyde (4a) under the solvent-free condition
Table 4, Entries 14, 15).
2
reveals the special performance of CdS NPs for the
With optimization outcomes in hand, in order to appraise the
scope of 1,3-oxathiolane-2-thiones (3) through photo-
difunctionalization of the C–C double bond, diverse styrenes as
starting materials were used (Scheme 4). The obtained outcomes
are summarized in Table 3. Besides the 1,3-oxathiolane-2-thione
derivatives, relevant aldehydes were also formed in small
amounts (trace or less than 5%).
(
O
(
2a)
(3a)
Scheme 5. The synthesis of benzaldehyde (3a) from styrene (2a) as a model
reaction under different conditions.
S
1
. CS
2 2 3
(1 eq), Cs CO (1 eq)
R1
O
MeOH (3 mL), R.T., 3 h
O
1
Table 4: The effect of various solvents and different photocatalysts for the
synthesis of benzaldehyde (4a) from the styrene (2a).
R
R2
S
+
Ar
Ar
R1
2
. CdS (10 mol %)
Ar
Entry
Solvent
Photocatalyst
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
CdS NPs
ZnO
Yield (%)
5
40
80
40
5
30
35
30
40
0
45
Trace
90
Trace
Trace
Blue LEDs,O Air, R.T.
2
2
R
1
2
3
4
5
6
7
8
9
10
2
H O
(2a-l)
(3a-i)
76-93%)
(4a-i)
EtOH
CH CN
(
(Trace)
3
MeOH
EtOAc
Acetone
Scheme 4. The synthesis of 1,3-oxathiolane-2-thione derivatives (3) in the
presence of CdS NPs.
CH
CH
2
Cl
Cl
2
Table 3: The synthesis of 1,3-oxathiolane-2-thione derivatives (3) in the
presence of CdS NPs under blue LED or sunlight irradiation.
3
DMF
DMSO
THF
S
S
S
11
12
13
14
15
O
O
O
Dioxane
S
S
S
Solvent-Free
Solvent-Free
Solvent-Free
TiO
2
O
Reaction conditions: The reaction of styrene (2a, 1 mmol) in the presence of
photocatalyst (0.015 g) under the air atmosphere under the solvent at room
temperature for 12 h.
3
a, 89%
3b, 92%
3c, 85%
S
S
S
S
S
O
O
O
Table 5: The effect of diverse amounts of CdS NPs, wavelengths of light, and
atmospheres for the synthesis of benzaldehyde (4a).
S
Entry
Amount of photocatalyst (g)
CdS (0.020)
CdS (0.015)
Light
White
White
White
White
White
Red
Green
Blue
Sun
Yield (%)
1
2
3
4
5
6
7
8
9
92
90
90
82
0
Cl
Br
Cl
CdS (0.010)
CdS (0.005)
Catalyst-Free
CdS (0.010)
CdS (0.010)
CdS (0.010)
CdS (0.010)
CdS (0.010)
CdS (0.010)
CdS (0.010)
a
3
d, 83%
3e, 77%
3f, 80%
68
81
95
95
0
S
S
S
S
S
S
S
O
O
O
O
S
1
1
0
1
Dark
Blue
Blue
a
Trace
b
97
S
12
O
Reaction conditions: The reaction of styrene (2a, 1 mmol) in the presence of
CdS NPs under air atmosphere and solvent-free conditions at room temperature
for 12 h. Argon balloon, oxygen balloon.
g, 93% b
S
3
3h, 83%
3i, 76%
a
b
Reaction conditions: CS
were taken in a closed test tube and stirred at room temperature for 3 hours
2
(1.0 mmol) and Cs
2
3
CO (1.0 mmol) in MeOH (3 mL)
after that styrene derivative (2, 1.0 mmol) and CdS (10 mol%) were added to
the open test tube and the reaction mixture was exposed under Blue LEDs 12
After discovering CdS NPs a more efficient photocatalyst
and the solvent-free as the most appropriate reaction media,
diverse amounts of photocatalyst (Table 5, Entries 1-5), various
wavelengths of light (Table 5, Entries 6-10) and different
atmospheres (Table 5, Entries 8, 11, 12) were tested. As it can be
observed in Table 5, the best results were similar to the optimal
a
W lamp for 12 hours in the air atmosphere at room temperature.
precursors were
chloromethyl)-para-vinylbenzene, so the products have also obtained a mixture
of 5-(4-(chloromethyl)phenyl)-1,3-oxathiolane-2-thione and 5-(2-
chloromethyl)phenyl)-1,3-oxathiolane-2-thione. trans-stilbene precursor was
used and the products have obtained a mixture of (trans)-4,5-diphenyl-1,3-
The
a
mixture of 1-(chloromethyl)-ortho-vinylbenzene and 1-
(
b
(
3
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European Journal of Organic Chemistry
10.1002/ejoc.202000448
FULL PAPER
conditions for the synthesis of 1,3-oxathiolane-2-thiones (3).
Therefore, aldehyde derivatives can be synthesized with high
yields in the presence of CdS NPs (10 mol%) under blue LED 12
W or sunlight and solvent-free conditions at room temperature
under the air atmosphere.
was re-used five times without any remarkable efficiency
reduction. The results are summarized in Figure 1.
In the subsequent step, various styrene derivatives bearing
both electron releasing (ERG) and electron-withdrawing groups
(EWG) were used (Scheme 6). The photo-oxidative cleavage of
the C–C double bond of styrene derivatives having electron
releasing groups (ERG) carried out easier compared with those
bearing electron-withdrawing groups (EWG), probably due to the
stability of the intermediate radical cation. Obtained outcomes are
summarized in Table 6. Also, relevant benzoic acids were formed
in small amounts (less than 5%).
1
R
O
O
CdS (10 mol %)
R2
+
R1
(3a-l)
2
Ar
Slovent-Free
Ar
H
R
Blue LEDs, O2 Air, R.T.
(
2a-l)
1
2
2
2
2
2
2
a, 2d-l: R = H, R = H
b: R1 = H, R2 = Ph
c: R1 = Me, R2 = H
k: 1,4-divinylbenzene
l: 1,3-divinylbenzene
Scheme 6. The synthesis of aryl aldehyde derivatives (4) from styrenes (2a-l)
in the presence of CdS NPs.
Table 6: The synthesis of aryl aldehyde derivatives (4) from styrenes (2a-l) in
the presence of CdS NPs.
Figure 1. (A): The recovered CdS NPs for the synthesis of 5-phenyl-1,3-
oxathiolane-2-thione (3a). (B): The recovered CdS NPs for the synthesis of
benzaldehyde (4a)
O
O
O
H
H
H
H
H
H
A possible mechanism for the synthesis of 1,3-oxathiolane-
-thiones (3) and aryl aldehyde (4) is proposed in Scheme 7.
O
2
4
a, 95%
b, 88%
4c, 93%
4d, 90%
Based on our knowledge, CdS acts as a visible-light-induced
photocatalyst. With the visible light collision to the CdS
nanoparticles surface, the electrons are transferred from the
valence band (VB) to the conduction band (CB). Therefore, holes
in the VB and electrons in the CB are created. Two paths can be
suggested for the preparation of 1,3-oxathiolane-2-thiones 3. It is
speculated that electron transfer from styrene 2 and cesium
methyl xanthate A to the holes in the VB, intermediates B and C
are generated, respectively. Radical intermediate C could be
reacted with styrene 2 (it causes intermediate formation D) or
traps radical cation B (it causes intermediate formation E). On the
other hand, oxygen could be received an electron from the CB of
4
O
O
O
H
Cl
Cl
Br
4
e, 88% a
4f 85%
4g, 87%
O
O
O
H
N
H
F
O N
2
4
h, 82%
4i, 69%
4j, 64%
CdS to generate superoxide radical anion (O
2
). Through path a:
superoxide radical anion (O ), can couple with intermediates D
O
O
O
2
or E to form F or G, respectively, which ultimately, intermediate H
forms 1,3-oxathiolane-2-thiones (cyclic dithiocarbonates, 3)
H
H
28
H
through an intramolecular cyclization . Through path b: after the
formation of intermediates D and E, the more probable pathway
is to perform an intramolecular cyclization reaction to create
intermediates (I) and (J). Ultimately with interference superoxide
radical anion, the desired cyclic dithiocarbonates (3) are formed.
Whereas, in the absence of cesium methyl xanthate A
oxygen radical anion accomplishes [2+2] cycloaddition with
radical cation B for the synthesis of 3-phenyl-1,2-dioxetane K.
Then, 3-aryl-1,2-dioxetane compound I perform the oxidative
cleavage of a C-C and O-O bonds for the synthesis of desired aryl
aldehyde (4) (Scheme 7).
O
4k, 83%
4l, 77%
Reaction conditions: styrene derivatives (2, 1.0 mmol) and CdS (10 mol%) were
added to the open test tube and the reaction mixture was exposed under blue
LEDs 12 W lamp and the solvent-free conditions for 12 hours in the air
a
atmosphere at room temperature.
(
The precursors were a mixture of 1-
chloromethyl)-ortho-vinylbenzene and 1-(chloromethyl)-para-vinylbenzene, so
the products were also obtained a mixture of ortho-(chloromethyl)benzaldehyde
and para-(chloromethyl)benzaldehyde.
To establish the reusability of CdS as a heterogeneous
nano photocatalyst, the model reactions for the synthesis of 5-
phenyl-1,3-oxathiolane-2-thione (3a) and benzaldehyde (4a)
Based on the results obtained during optimization reactions
for the synthesis of 5-phenyl-1,3-oxathiolane-2-thione 3a and
benzaldehyde 4a, the necessity of photocatalysts (Table 2, Entry
5 and Table 5, Entry 5), light (Table 2, Entry 10 and Table 5, Entry
10), and oxygen (Table 2, Entry 11 and Table 5, Entry 11) for the
progression of the reaction were obvious. Besides these, to
confirm the proposed mechanism, some supplementary control
experimental studies were also performed. Accordingly, the
model reactions (Scheme 3 and 5) were accomplished in the
(
Scheme 3 and 5) were surveyed in the presence of the recovered
nano photocatalyst under optimal conditions. After the completion
of the reaction, EtOH (3 mL) was added to the reaction mixture
and stirred for 3-5 min. The insoluble CdS NPs were separated
from the solution by centrifuge, washed by EtOH (2 mL, 2 times),
o
dried at 50 C, and re-used. The recovered nano photocatalyst
4
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202000448
FULL PAPER
presence of the hole and radical scavengers to prove the creation
of hole/electron pairs and also a radical pathway of the reaction
E). But the Scheme 8 / Test F shows that radical cation B was not
converted to oxirane L in the presence of oxygen, whereas, along
with cesium methyl xanthate A, 1,3-oxathiolane-2-thione
compound 3a was prepared. In other words, in the absence of
cesium methyl xanthate A, the oxidation of styrene to 2-
phenyloxirane L did not occur, whereas, the oxidative cleavage of
a C-C double bond of styrene has mainly undergone for the
synthesis of benzaldehyde (Scheme 8, F).
(Scheme 8).
Cs
2
CO
3
S
S
C
S
+
2 3
H CO
C
MeOH
MeO
SCs
(1)
(A)
S
S
O
O
S
or
S
Ar
Ar
(J)
(I)
O
2
1. CS
2
(1 eq), Cs
2
CO
3
(1 eq)
S
P
O
at
MeOH (3 mL), R.T., 3 h
h
b
O
(
A):
Ph
1
O
O
S
O
O
S
O
O
+
or
2. CdS (10 mol %), TEMPO
S
Ph
H
S
S
Ar
Ar
Path
Blue LEDs,O
Air, R.T.
Ph
2
(2a)
mmol
(G)
(F)
a
(3a)
(4a)
(
A
1
2
): TEMPO (1 eq) : (3a, 15%)+ (4a, 35%)
): TEMPO (2 eq) : (3a, Trace) + (4a, Trace)
HO
Ar
O
S
O
S
O
S
O
or
(A
S
S
Ar
S
Ar
(E)
(D)
(H)
O
O
O
2
1. CS2 (1 eq), Cs CO (1 eq)
2 3
MeOH (3 mL), R.T., 3 h
Ar
S
(
K)
+e
O
(
2)
or
(B)
O
(
(B):
Ph
1
e
e
e
+
2
. CdS (10 mol %), TEA
S
O
2
CdS
Ph
H
Blue LEDs, O Air, R.T.
2
Ph
(2a)
mmol
3a)
(4a)
S
O
S
(B
1
): TEA (1 eq) : (3a, 10%) + (4a, Trace)
S
C
(B ): TEA (2 eq) : (3a, 5%) + (4a, Trace)
2
Ar
Ar
O
Ar
S
O
(3)
(4)
(B)
h
h
h
(C)
-e
-
e
S
C
CdS (10 mol %), TEMPO
Solvent-Free
O
Ar
CsS
O
(2)
(A)
(C): Ph
Ph
H
2
Blue LEDs,O Air, R.T.
(2a)
Scheme 7. The proposed mechanism for the synthesis of 1,3-oxathiolane-2-
thiones (3) and aryl aldehyde (4) in the presence of CdS nanoparticles as a
photocatalyst and air atmosphere.
(4a)
1
mmol
(
(
C
1
): TEMPO (1 eq) : (4a, 5%)
C
2
): TEMPO (2 eq) : (4a, Trace)
The study of the model reaction (Scheme 3) in the presence
of TEMPO (1 equivalent) as a radical scavenger demonstrated
that only 15% of 5-phenyl-1,3-oxathiolane-2-thione 3a and 35%
of benzaldehyde 4a was formed, respectively. Probably, the
electron transfer from both reactants (cesium methyl xanthate A
and styrene 2a) is taken place into the photocatalytic hole.
Undoubtedly, TEMPO can traps both radical cation B and radical
methyl xanthate C, respectively. Radical methyl xanthate C is
mostly inhibited by TEMPO because it has a faster rate of
formation than radical cation B. The efficiency of the product 3 is
decreased compared to byproduct 4, due to the increase in the
efficacious collisions and contacts between the C and TEMPO
caused by the enhancement in the concentration of C (Scheme 8,
O
CdS (10 mol %), TEA
(
D): Ph
Solvent-Free
Ph
H
Blue LEDs,O2 Air, R.T.
(
2a)
mmol
(4a)
1
(D): TEA (1 eq) : (4a, Trace)
S
S
PET
PET
C
CsS
OMe
O
O
(
E):
Ar
Ar
S
Ar
Ar
(2)
(B)
(L)
(3)
A
1
). Consequently, 2 equivalents of TEMPO traps both radical
cation B and radical methyl xanthate C, and both products 3 and
were obtained in trace (Scheme 8, A ). The model reaction
Scheme 3) in the presence of triethylamine (TEA, 1 equivalent)
O
CdS (10 mol %)
O
(
F):
+
Ph
4
(
2
MeOH (3 mL)
Blue LEDs
Ph
H
Ph
(2a)
1 mmol
(4a)
40 %
(L)
Trace
2
O Air, R.T.
as a hole scavenger under optimized conditions demonstrated
that only 10% of 5-phenyl-1,3-oxathiolane-2-thione (3a) is formed,
whereas trace amount of benzaldehyde (4a) is produced.
Probably, cesium methyl xanthate A has been able to compete
slightly with TEA in electron transfer to the photocatalyst hole
CdS (10 mol %)
Cs CO (1 mmol)
S
S
O
2
3
O
(G):
CS2
+
+
Ph
MeOH (3 mL)
Blue LEDs
Ph
H
(
Scheme 8,
equivalent) leads to a decrease in the efficiency of the product (3a,
%) (Scheme 8, B ).
In a further study, the model reaction (Scheme 5) was
carried out in the presence of a hole and radical scavengers
Scheme 8, C, and D). The lack of target molecule formation (4a)
1
B ). Increasing the concentration of TEA (2
Ph
(1)
(2a)
mmol
(3a)
(4a)
40 %
O2 Air, R.T.
1
mmol
1
20 %
5
2
Scheme 8. The mechanism studies: The model reaction for the synthesis of 5-
phenyl-1,3-oxathiolane-2-thione (3a) (Scheme 5) under optimization conditions:
(A) In the presence of TEMPO as a radical scavenger ( TEMPO 1 eq,
TEMPO 2 eq). (B) In the presence of TEA as hole scavenger ( TEA 1 eq,
A1
A2
(
B1
B2
by TEMPO (Scheme 8, C) as well as TEA (Scheme 8, D) was
confirmed the hole-electron formation and radical pathway.
There was an assumption for the formation of 1,3-
TEA 2 eq). The model reaction for the synthesis of benzaldehyde (4a) (Scheme
C1
7) under optimized conditions: (C) In the presence of TEMPO ( TEMPO 1 eq,
C2
TEMPO 2 eq). (D) In the presence of TEA. (E) The mechanism of preparation
of 1,3-oxathiolane-2-thiones (3a) through the formation of oxirane. (F) The
oxidation of styrene in the presence of CdS in the MeOH solvent. (G) The
synthesis of 5-phenyl-1,3-oxathiolane-2-thione (3a), when all the reagents were
added at the concurrent.
oxathiolane-2-thione compounds 3 that, the radical cation B is
converted to oxirane L in the presence of oxygen. Accordingly,
the opening of the oxirane ring is occurred by the nucleophilic
attack of the cesium methyl xanthate A and is eventually formed
the desired product 3 via intramolecular cyclization (Scheme 8,
5
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202000448
FULL PAPER
In another study, to ensure that 1,3-oxathiolane-2-thiones
nanoparticles (yellow solid) were gathered and laundered with
o
deionized water and ethanol and dried at 50 C for 24 hours.
synthesis is not dependent on 2-phenyloxirane L formation, the
reaction between styrene and CS
2
in the presence of CdS and
General procedure for the
dithiocarbonate
derivatives)
synthesis of cyclic
(1,3-oxathiolane-2-thione
Cs CO under blue LEDs in MeOH was investigated
2
3
derivatives
simultaneously (all the reagents were added at the concurrent). It
was observed that 1,3-oxathiolane-2-thiones 3a was formed with
low efficiency and benzaldehyde was a major product (Scheme 8,
G). As it is shown in scheme 7, it was speculated that electron
transfer from cesium methyl xanthate A and styrene 2a to the
photocatalytic holes have also occurred. When initially, the
styrene 2a concentration is more than the carbon disulfide salt A,
styrene undergoes the oxidative cleavage of a C-C double bond
leads to the formation of benzaldehyde and the concentration of
styrene or radical cation B to interact with the radical intermediate
C is reduced. Correspondingly, the efficiency of 5-phenyl-1,3-
oxathiolane-2-thione 3a formation is reduced. Nevertheless, the
reaction between carbon disulfide (1, 1.0 mmol), cesium
carbonate (1.0 mmol), and methanol (3 mL) were taken in a
closed test tube and stirred at room temperature for 3 hours to
perfect the formation of cesium methyl xanthate salt A. In the next
step, CdS (10 mol%) and styrene (2a, 1.0 mmol) were added to
the open test tube and the reaction mixture was exposed under
blue LEDs 12 W lamp for 12 hours under the air atmosphere at
room temperature. Interestingly, the efficiency of 5-phenyl-1,3-
oxathiolane-2-thione 3a formation is greatly increased. Indeed,
cesium methyl xanthate A wins in competition with styrene for the
electron transfer to the photocatalyst hole, or simultaneously with
styrene conducts electron to the photocatalyst hole (the formation
of intermediates B and C).
In a test tube equipped with a magnetic stir, the bar was added
Cs CO (1.0 mmol) and MeOH (3 mL), and the obtained mixture
was stirred until the complete dissolving of Cs CO . CS (1.0
2
3
2
3
2
mmol) was added into the obtained solution and the test tube was
completely sealed and the reaction mixture was magnetically
stirred for 3 hours at room temperature until the production of
cesium methyl xanthate (A). In the next step, CdS NPs (10 mol%)
and styrene (1.0 mmol) were added. The open test tube
containing the reaction mixture was placed under irradiation of
blue LEDs (12 W, in the distance about 6 cm) or sunlight and was
permitted to stir at room temperature under the air atmosphere for
12 hours. The reaction progress was controlled by thin-layer
chromatography (TLC). After the completion of the reaction,
2
EtOAc (3 mL) and H O (5 mL) were added to the reaction mixture
and insoluble CdS NPs were separated by centrifuge, washed
with EtOAc (2 mL, 2 times), dried under the vacuum and reused.
2 4
The organic phase (EtOAc) was separated, dried over Na SO
and evaporated under reduced pressure. The raw products were
purified using silica gel column chromatography to afford pure
cyclic dithiocarbonates (1,3-oxathiolane-2-thiones).
General procedure for the synthesis of aryl aldehydes
In an open test tube armed with a magnetic stir bar, styrene (1.0
mmol) and CdS NPs (10 mol%) were added. After that, the open
test tube was placed under irradiation of blue LEDs (12 W, in the
distance about 6 cm) or sunlight and was permitted to stir at room
temperature under the air atmosphere for 12-24 hours under
solvent-free conditions. The reaction progress was controlled by
thin-layer chromatography (TLC). After the completion of the
reaction, EtOH (3 mL) was added to the reaction mixture and
insoluble CdS NPs were separated by centrifuge, washed with
EtOH (2 mL, 2 times), dried under the vacuum and reused. The
ethanol solvent was evaporated under reduced pressure. The raw
products were purified using silica gel column chromatography to
afford pure aryl aldehydes.
Conclusion
So briefly, we have successfully presented the oxidant-free
process for the synthesis of cyclic dithiocarbonate and aryl
aldehyde derivatives. photo-oxidative cleavage and photo-
difunctionalization of C-C double bonds have occurred in the
presence of CdS nanoparticles as a visible-light-induced reusable
nanocatalyst at room temperature under air and blue LEDs or
sunlight irradiation. The present work is the second report of a
photo-difunctionalization process for the synthesis of desired
compounds and is superior to the previous report. Also, this work
is the first report of a photo-oxidative cleavage in the solvent-free
conditions along with a milder and superior process. Furthermore,
direct use of styrene as a readily accessible substrate, excellent
regioselectivity, greatly decreasing the byproducts, improving the
reaction efficiency, reaction safety, photocatalyst recyclability,
and operational simplicity represented prominent advantages of
the presented method.
Characterization of compounds
2
6b
5
8
1
3
5
=
-Phenyl-1,3-oxathiolane-2-thione (3a) : Yellow solid, Yield:
o
o
9%, M.P = 116-117 C (115-117 C). IR (KBr) νmax 1604, 1559,
478, 1432, 1396, 1086 cm . HNMR (٣00 MHz, CDCl ) δ (ppm);
3
.95 (dd, 1H, J = 12.0, 5.7, Hz), 4.10 (dd, 1H, J = 12.0, 10.5 Hz),
.57 (dd, 1H, J = 10.5, 5.7 Hz), 7.32-7.37 (m, 3H), 7.42 (dd, 2H, J
-1 1
13
3
8.1, 1.5 Hz). CNMR (75 MHz, CDCl ), δ (ppm); 49.79, 64.24,
127.53, 129.24, 129.28, 135.15, 2٢٧.٢٥. Anal. Calcd for C H OS :
٩
٨
2
C 55.07, H 4.11. Found: C 54.89, H 4.23.
-Methyl-5-phenyl-1,3-oxathiolane-2-thione
viscous liquid, Yield: 92%. IR (KBr) νmax 1613, 1521, 1453, 1417,
5
(3b):
Yellow
-
1 1
1
3
3
4
406, 1105 cm . HNMR (250 MHz, CDCl
3
) δ (ppm); 2.04 (s, 3H),
.58 (d, 1H, J = 12.0 Hz), 4.03 (d, 1H, J = 12.0 Hz), 7.26-7.35 (m,
13
H), 7.46-7.50 (m, 2H). CNMR (75 MHz, CDCl
8.29, 68.15, 128.19, 128.32, 129.02, 141.87, 227.24. Anal.
: C 57.11, H 4.79. Found: C 57.02, H 4.82.
3
), δ (ppm); 29.38,
Experimental Section
Calcd for C10
-(4-Methoxyphenyl)-1,3-oxathiolane-2-thione (3c) : Yellow
viscous liquid, Yield: 85%. IR (KBr) νmax 1702, 1651, 1486, 1394,
H10OS
2
27
5
General procedure for the synthesis of cadmium sulfide
nanoparticles (CdS NPs)
The CdS NPs were readied according to the previously reported
-1 1
1
289, 1129 cm . HNMR (250 MHz, CDCl
3
) δ (ppm); 3.84 (s, 3H),
3.96 (dd, 1H, J = 12.1, 5.7 Hz), 4.12 (dd, 1H, J = 12.0 Hz), 5.57
(dd, 1H, J = 10.5, 5.7 Hz), 6.98 (d, 2H, J = 7.0 Hz), 7.78 (d, 2H, J
6
method by our research group . Accordingly, sodium sulfide
1
3
hexahydrate and N-cetyl N, N, N-trimethylammonium bromide
were dissolved in deionized water and cadmium nitrate
tetrahydrate was added dropwise. The mixture was stirred for 1
hour at room temperature. Then, the reaction temperature was
raised to the reflux temperature for 36 hours. Finally, CdS
= 7.0 Hz). CNMR (75 MHz, CDCl
114.55, 127.86, 135.89, 160.33, 227.13. Anal. Calcd for
: C 53.07, H 4.45. Found: C 53.19, H 4.38.
3
), δ (ppm); 49.84, 55.49, 64.45,
10 10 2 2
C H O S
5-(4-(Chloromethyl)phenyl)-1,3-oxathiolane-2-thione and 5-
(2-(Chloromethyl)phenyl)-1,3-oxathiolane-2-thione (3d): The
6
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202000448
FULL PAPER
precursors were a mixture of 1-(chloromethyl)-ortho-vinylbenzene
and 1-(chloromethyl)-para-vinylbenzene, so the products were
(75 MHz, CDCl
3
),
δ
190.83. Anal. Calcd for C
(ppm); 55.58, 114.30, 129.91, 131.98, 164.5,
8 8 2
H O : C 70.58, H 5.92. Found: C 70.32,
also obtained
oxathiolane-2-thione
oxathiolane-2-thione. Yellow viscose liquid, Yield: 83%. IR (KBr)
a
mixture of 5-(4-(chloromethyl)phenyl)-1,3-
H 6.11.
and 5-(2-(chloromethyl)phenyl)-1,3-
Para-(chloromethyl)benzaldehyde
and
(chloromethyl)benzaldehyde (4e) : The precursors were a
max 1684, 1651, 1631, 1618, 1465, 1448, 1362, 1310, 1216, 1178, mixture
of 1-(chloromethyl)-ortho-vinylbenzene and 1-
Ortho
-
2
9
ν
-
1 1
1
127, 1085 cm . HNMR (250 MHz, CDCl
3
)
δ
(ppm); 4.24 (s, 2H,
overlapped), 4.25 (s, 2H, overlapped), 5.11-5.17 (m, 2H), 5.58-
(chloromethyl)-para-vinylbenzene, so the products were also
obtained a mixture of ortho-(chloromethyl)benzaldehyde and
para-(chloromethyl)benzaldehyde. Colorless liquid, Yield: 88%,
IR (KBr) νmax 2865, 2843, 2771, 2738, 1707, 1692, 1612, 1596,
1509, 1488 cm . HNMR (300 MHz, CDCl
4.57 (s, 2H), 4.44-7.50 (m, 3H), 7.59 (d, 1H, J = 7.5 Hz), 7.75-7.83
1
3
5
.67 (m, 2H), 6.52-6.63 (m, 2H), 7.12-7.26 (m, 8H). CNMR (100
MHz, CDCl ), (ppm); 40.44, 40.45, 40.60, 40.61, 60.09, 60.10,
25.44, 126.39, 126.89, 128.44, 128.78, 129.23, 134.97, 135.71,
3
δ
-
1 1
1
1
4
5
3
) δ (ppm); 4.56 (s, 2H),
36.90, 137.90, 214.70, 214.72. Anal. Calcd for C10
9.07, H 3.71. Found: C 48.95, H 3.86.
-(4-Chlorophenyl)-1,3-oxathiolane-2-thione (3e) : Yellow
9 2
H ClOS : C
1
3
3
(m, 4H), 9.94 (s, 1H), 9.95 (s, 1H). CNMR (75 MHz, CDCl ), δ
(ppm); 45.26, 45.28, 129.13, 129.48, 129.54, 129.80, 130.13,
134.47, 136.13, 136.76, 138.60, 143.84, 191.70, 191.82. Anal.
27
viscose liquid, Yield: 77%. IR (KBr) νmax 1684, 1642, 1433, 1308,
-1 1
1
145, 1088 cm . HNMR (250 MHz, CDCl
3
)
δ
(ppm); 3.98 (dd, 1H,
Calcd for C
8 7
H ClO: C 62.16, H 4.56. Found: C 62.31, H 4.63.
2
3a
J = 12.1, 5.7 Hz), 4.138 (dd, 1H, J = 12.0, 10.5 Hz), 5.60 (dd, 1H,
J = 10.5, 5.7 Hz), 7.40 (d, 2H, J = 7.7 Hz), 7.55 (d, 2H, J = 7.7 Hz).
4-Chlorobenzaldehyde (4f) : White solid, Yield: 85%, M.P =
o
1
46-48 C. HNMR (300 MHz, CDCl
6.9, 1.8 Hz), 7.84 (dd, 2H, J = 6.9, 1.8 Hz), 10.00 (s, 1H). CNMR
(75 MHz, CDCl ), (ppm); 129.45, 130.90, 134.69, 140.96,
190.87. Anal. Calcd for C H ClO: C 59.81, H 3.59. Found: C 58.74,
3
) δ (ppm); 7.53 (dd, 2H, J =
1
3
13
3
CNMR (75 MHz, CDCl ), δ (ppm); 49.99, 44.43, 128.49, 130.10,
1
3
5
33.52, 138.90, 227.24. Anal. Calcd for C
9
H
7
ClOS
2
: C 46.85, H
3
δ
.06. Found: C 47.03, H 3.17.
-(4-Bromophenyl)-1,3-oxathiolane-2-thione (3f)
7
5
2
7
: Yellow
(ppm); IR
H 3.66.
4-Bromobenzaldehyde (4g) : White solid, Yield: 87%, M.P =
1
23a
viscous liquid, Yield: 80%. HNMR (250 MHz, CDCl
3
)
δ
-1
o
1
(KBr) νmax 1697, 1651, 1486, 1394, 1289, 1129 cm . 4.01 (dd, 1H,
56-58 C. HNMR (300 MHz, CDCl
Hz), 7.77 (d, 2H, J = 8.4 Hz), 10.00 (s, 1H). CNMR (75 MHz,
CDCl ), (ppm); 129.81, 130.99, 132.45, 135.03, 191.13. Anal.
Calcd for C H BrO: C 45.44, H 2.72. Found: C 45.61, H 2.68.
3
) δ (ppm); 6.72 (d, 2H, J = 8.4
1
3
J = 12.0, 6.0 Hz), 4.16 (dd, 1H, J = 12.0, 10.5 Hz), 5.63 (dd, 1H,
J = 10.5, 6.0 Hz), 7.39 (d, 2H, J = 8.2 Hz), 7.65 (d, 2H, J = 8.2 Hz).
3
δ
1
3
3
CNMR (75 MHz, CDCl ), δ (ppm); 50.00, 64.52, 121.33, 130.02,
7
5
3
0
1
2
31.98, 138,95, 227.33. Anal. Calcd for C
.56. Found: C 38.96, H 2.49.
9
H
7
BrOS
2
: C 39.28, H
4-Fluorobenzaldehyde (4h) : Pale yellow liquid, Yield: 82%,
1
HNMR (300 MHz, CDCl3)
7.91 (dd, 2H, J = 8.4, 5.4 Hz), 9.97 (s, 1H). CNMR (75 MHz,
CDCl ), (ppm); 116.33 (d, J = 22.3 Hz), 132.22 (d, J = 9.6 Hz),
32.95 (d, J = 2.0 Hz), 166.50 (d, J = 255.0 Hz), 190.49. Anal.
Calcd for C H FO: C 67.74, H 4.06. Found: C 67.88, H 4.13.
δ (ppm); 7.21 (dd, 2H, J = 8.7, 8.1 Hz),
26b
13
(
Trans)-4,5-diphenyl-1,3-oxathiolane-2-thione (3g) : Yellow
o
o
solid, Yield: 93%, M.P = 126-128 C (127-129 C). IR (KBr) νmax
3
δ
-
1
1
1
691, 1638, 1444, 1322, 1195, 1047 cm . HNMR (400 MHz,
CDCl (ppm); 4.27 (d, 1H, J = 5.6 Hz), 4.81 (d, 1H, J = 5.6 Hz),
.04-7.07 (m, 2H), 7.08-7.11 (m, 3H), 7.16-7.19 (m, 2H),
1
3
) δ
7
5
2
3a
7
7
8
1
4-Nitrobenzaldehyde (4i) : Yellow solid, Yield: 69%, 104-106
1
13
o
.19.7.22 (m, 3H). CNMR (100 MHz, CDCl
8.33, 127.74, 128.23, 128.50, 128.60, 128.72, 128.80, 138.00,
41.00, 227.01. Anal. Calcd for C15 : C 66.14, H 4.44.
3
),
δ
(ppm); 57.89,
3
C. HNMR (300 MHz, CDCl ) δ (ppm); 8.10 (d, 2H, J = 8.7 Hz),
1
3
8.41 (d, 2H, J = 8.7 Hz), 10.18 (s, 1H). CNMR (75 MHz, CDCl ),
δ
3
H12OS
2
(ppm); 124.31, 130.49, 140.03, 151.12, 190.29. Anal. Calcd for
NO : C 55.64, H 3.34. Found: C 55.53, H 3.28.
Found: C 66.30, H 4.33.
,5'-(1,4-Phenylene)bis(1,3-oxathiolane-2-thione) (3h): Yellow
C
7
H
5
3
5
31
1
Isonicotinaldehyde (4j) : Yellow liquid, Yield: 64%, HNMR
o
solid, Yield: 83%, M.P = 133-135 C. IR (KBr) νmax 1613, 1575,
(300 MHz, CDCl
(dd, 2H, J = 4.5, 1.2 Hz), 10.04. CNMR (75 MHz, CDCl
(ppm); 122.08, 141.33, 151.19, 191.51. Anal. Calcd for C H
5
3
) δ (ppm); 7.66 (dd, 2H, J = 4.5, 1.8 Hz), 8.84
-
1 1
1
3
5
469, 1422, 1342, 1123 cm . HNMR (300 MHz, CDCl )
.97 (dd, 2H, J = 12.0, 5.7 Hz), 4.13 (dd, 2H, J = 12.0, 10.5 Hz),
3
δ
(ppm);
13
3
),
δ
NO:
6
13
.77 (dd, 2H, J = 10.5, 5.7 Hz), 7.38 (s, 4H). CNMR (75 MHz,
), (ppm); 49,96, 65.59, 125.12, 135.86, 217.39. Anal.
Calcd for C12 : C 45.84, H 3.21. Found: C 45.96, H 3.10.
,5'-(1,3-Phenylene)bis(1,3-oxathiolane-2-thione) (3i): Yellow
C 67.28, H 4.71, N 13.08. Found: C 66.98, H 4.86, N 13.22.
32
CDCl
3
δ
Terephthalaldehyde (4k) : White solid, Yield: 83%, M.P = 116-
H
10
O
2
S
4
o
1
1
18 C. HNMR (300 MHz, CDCl
3
)
δ
(ppm); 8.05 (s, 4H), 10.13 (s,
(ppm); 130.12, 139.98, 191.52.
8 6 2
H O : C 71.64, H 4.51. Found: C 71.59, H 4.62.
5
13
2
3
H). CNMR (75 MHz, CDCl ), δ
o
solid, Yield: 76%, M.P = 128-130 C. IR (KBr) νmax 1620, 1543,
Anal. Calcd for C
Isophthalaldehyde (4l) : White solid, Yield: 77%, M.P = 89-91
-1 1
1
3
5
1
451, 1418, 1342, 1201 cm . HNMR (300 MHz, CDCl
.98 (dd, 2H, J = 12.0, 5.7 Hz), 4.12 (dd, 2H, J = 12.0, 10.5 Hz),
.59 (dd, 2H, J = 10.5, 5.7 Hz), 7.48 (t, 1H, J = 8.4 Hz), 7.56 (s,
3
)
δ
(ppm);
33
o
1
C. HNMR (300 MHz, CDCl
.10 (dd, 2H, J = 7.5, 1.5 Hz), 8.32 (s, 1H), 10.05 (s, 2H). CNMR
75 MHz, CDCl ), (ppm); 129.20, 131.01, 134.64, 136.98,
98.10. Anal. Calcd for C : C 71.64, H 4.51. Found: C 71.80,
3
) δ (ppm); 7.67 (t, 1H, J = 7.8 Hz),
13
8
13
3
H), 7.68 (dd, 2H, J = 8.7, 0.7 Hz). CNMR (75 MHz, CDCl ), δ
(
1
3
δ
(
ppm); 49.84, 64.50, 127.41, 128.34, 128.87, 135.32, 226.99.
Anal. Calcd for C12 : C 45.84, H 3.21. Found: C 46.07, H
.29.
8 6 2
H O
10 2 4
H O S
H 4.69.
3
23a
Benzaldehyde (4a) and (4b) : Colorless liquid, Yield 4a: 95%,
Yield 4b: 88%, IR (KBr) νmax 1756, 1620, 1543, 1451, 1418, 1342,
Keywords: cyclic dithiocarbonate
nanoparticles • photo-induced catalyst • photo-difunctionalization
photo-oxidative cleavage
• aryl aldehyde • CdS
-1 1
1
Hz), 7.54 (t, 1H, J = 6.9 Hz), 7.89 (t, 2H, J = 7.8 Hz), 10.03 (s, 1H).
201 cm . HNMR (300 MHz, CDCl
3
) δ (ppm); 7.54 (t, 2H, J = 7.8
•
1
3
3
CNMR (75 MHz, CDCl ), δ (ppm); 128.99, 129.74, 134.47,
136.37, 192.42. Anal. Calcd for C
C 78.94, H 5.88.
Acetophenone (4c)
8
H
8
O: C 79.23, H 5.70. Found:
[
2
1] (a) R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science. 2001, 293,
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19e
1
: Colorless liquid, Yield: 93%, HNMR
[
(
7
300 MHz, CDCl
.57 (t, 1H, J = 7.5 Hz), 7.96 (d, 2H, J = 7.5 Hz). CNMR (75 MHz,
CDCl ), (ppm); 26.63, 128.29, 128.56, 133.11, 137.07, 198.16.
Anal. Calcd for C O: C 79.97, H 6.71. Found: C 80.14, H 6.59.
-Methoxybenzaldehyde (4d) : Colorless liquid, Yield: 90%,
3
) δ (ppm); 2.61 (s, 3H), 7.64 (t, 2H, J = 7.5 Hz),
13
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3
δ
8
H
8
19e
4
1
HNMR (300 MHz, CDCl
3
) δ (ppm); 3.88 (s, 3H), 7.00 (dd, 2H, J
13
=
7.2, 1.5 Hz), 7.84 (dd, 2H, J = 7.3, 1.5 Hz), 9.88 (s, 1H). CNMR
7
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European Journal of Organic Chemistry
10.1002/ejoc.202000448
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European Journal of Organic Chemistry
10.1002/ejoc.202000448
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Key Topic
Photo-oxidative Cleavage
Table of Contents
Nanosized cadmium sulfide as an efficient visible light-
induced reusable nano-catalyst was designed for the photo-
difunctionalization and photo-oxidative cleavage of the C–C
double bond of styrene in mild conditions.
This article is protected by copyright. All rights reserved.
9