Syntheses of Thioethers and Selenide Ethers from Anilines

Article abstract of DOI:10.1021/acs.joc.9b00322

In this study, a general procedure was proposed for synthesizing thioethers and selenide ethers from anilines under solvent-free and transition-metal-free conditions. Thioethers were formed when anilines reacted with thiols under blue light-emitting-diode (LED) irradiation at room temperature without a photocatalyst. When reactions were performed using anilines and diselenides, the corresponding selenide ethers were obtained with satisfactory to excellent yields. The reaction was performed under photocatalyst-free and solvent-free conditions without blue LEDs. The advantages of this system include convenient operations, mild reaction conditions, satisfactory functional group tolerance, and late-stage selenylation of drug molecules.

Full text of DOI:10.1021/acs.joc.9b00322

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Article
Syntheses of Thioethers and Selenide
Ethers from Anilines under Mild Conditions
Yi-Chen Shieh, Kai Du, R. Sidick Basha, Yung-Jing Xue, Bo-Hao Shih, Liang Li, and Chin-Fa Lee
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00322 • Publication Date (Web): 17 Apr 2019
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Syntheses of Thioethers and Selenide Ethers from Anilines
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Yi-Chen Shieh,† Kai Du,† R. Sidick Basha,† Yung-Jing Xue,† Bo-Hao Shih,† Liang
Li,† and Chin-Fa Lee*,†,‡,§
†Department of Chemistry, National Chung Hsing University, Taichung, Taiwan 402, R.O.C
‡Research Center for Sustainable Energy and Nanotechnology (RCSEN), Taiwan
§Innovation and Development Center of Sustainable Agriculture (IDCSA), Taiwan
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Abstract. In this study, a general procedure was proposed for synthesizing thioethers
and selenide ethers from anilines under solvent-free and transition-metal-free
conditions. Thioethers were formed when anilines reacted with thiols under blue light-
emitting-diode (LED) irradiation at room temperature without a photocatalyst. When
reactions were performed using anilines and diselenides, the corresponding selenide
ethers were obtained with satisfactory to excellent yields. The reaction was performed
under photocatalyst-free and solvent-free conditions without blue LEDs. The
advantages of this system include convenient operations, mild reaction conditions,
satisfactory functional group tolerance, and late-stage selenylation of drug molecules.
Keywords: Thioether; Selenide ether; Aniline; Thiol; Diselenide
Introduction
Thioethers are present in numerous bioactive molecules and are crucial in organic
synthesis and material chemistry.1-4 Therefore, the preparation of thioethers has
received considerable attention in previous decades.1-7 The cross-coupling of thiols with
aryl halides through a transition-metal-catalyzed reaction is a common approach for the
synthesis of thioethers.5-7 Anilines have low cost and are easily available when
compared with aryl halides. Anilines are considered starting materials for preparing
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thioethers when reacted with suitable thiol surrogates.8a-e Petrillo et al. reported the
SRN1 synthesis of thioether through an intermediate diazosulfides.8f-g Cuny et al.
recently reported the preparation of thioethers from anilines and thiols in the presence
of tert-butylnitrite through photoredox catalysis.9 However, an expensive ruthenium
catalyst and p-toluenesulfonic acid are required in this system (Scheme 1a). Jiang et al.
described the tert-butylnitrite-promoted copper-catalyzed synthesis of thioethers from
anilines and alkyl halides by using Na2S2O3 as a sulfur surrogate. However, this method
is limited to the formation of aryl-alkyl thioethers10 (Scheme 1b). Ranu et al. reported
C-S bond thioether formation assisted by stoichiometric iron nanoparticles from
anilines and organic disulfides in the presence of tert-butylnitrite.11 Cai et al. used half-
stoichiometric ascorbic acid as an organic acid for preparing thioethers12 (Scheme 1c,
eq. 1). Qin et al. has utilized the arenediazonium salts to access β-Arylethenesulfonyl
fluorides13a and diaryl disulfides.13b In this study, a general approach was used for the
synthesis of thioethers under catalyst-free, metal-free, solvent-free, and acid-free
conditions.
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Scheme 1. Strategies from anilines to thioethers and selenide ethers
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Results and Discussion
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Aniline, 1a and thiophenol, 2a were selected as substrates to optimize reaction
conditions. Several organo-photocatalysts were screened for C–S bond formation
(Table 1, entries 1–5), which provided the target with 43%–68% yields. A high yield
was observed for reactions performed in the absence of a photocatalyst (Table 1, entry
6). The product yield was reduced to 33% for reactions performed without blue light-
emitting diodes (LEDs) (Table 1, entry 7). When the amount of aniline was increased
from 0.5 to 0.6 mmol along with stoichiometric amount of t-BuONO with respect to
aniline, the product was afforded in 18% yield (Table 1, entry 8). An increase in yield
was obtained when the amount of t-BuONO was increased from 0.6 to 1.1 mmol (Table
1, entry 9). Finally, the product with 90% yield was obtained for the reaction conducted
with 0.6 mmol and 1.2 mmol of tert-butylnitrite (Table 1, entry 10). It is noteworthy
that we have not detected the intermediate diazosulfide in the reaction mixture (at varies
time intervals), as detected by Petrillo8f,g and Cuny.9 As a result, the assumption of
diazosulfide pathway is ruled out.
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Table 1. Reaction conditions optimizationa
Entry
1
Photocatalyst
Eosin Y
tBuONO (mmol)
Yield (%)
1.1
1.1
1.1
1.1
1.1
1.1
1.1
0.6
1.1
1.2
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90
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Eosin B
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Rose Bengal
Methylene blue
Acr Mes+ ClO4
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7b
8c,d
9c
10c,e
aReaction conditions: aniline, 1a (0.5 mmol), thiophenol, 2a (0.5 mmol), tBuONO (1.1 mmol) and photocatalyst (1
mol %) were reacted at room temperature for 2 h in blue LED. bNo Blue LEDs. c0.6 mmol of aniline was used. d0.6
t
e
t
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mmol of BuONO was used. 1.2 mmol of BuONO was used. Acr Mes+ ClO4 = 9-Mesityl-10-methylacridinium
perchlorate.
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Table 2 presents various anilines and thiophenols reactions conducted for the synthesis
of thioethers. Anilines with electron-donating (1b) or electron-withdrawing (1c, 1d, and
1e, 1f) groups were coupled with substituted thiophenols to obtain products with
satisfactory to excellent yields. Sterically hindered aniline (2-bromoaniline) and
thiophenols
(e.g.,
2,4,6-trimethylbenzenethiol,
2-methylthiophenol,
2-
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bromothiophenol, and 2-chlorothiophenol) can be used as starting materials for the
preparation of thioethers with satisfactory yields. Thioether 3b can be synthesized
through the reaction between p-anisidine and thiophenol or that between aniline and 4-
methoxythiophenol. A higher yield was observed for the reaction between aniline and
4-methoxythiophenol than that between p-anisidine and thiophenol, probably because
4-methoxythiophenol has stronger nucleophilicity than thiophenol. Similarly, 3d was
obtained with a higher yield from the reaction between 4-fluoroaniline and thiophenol
than that between aniline and 4-fluorothiophenol. Sterically hindered aniline is a more
reactive substrate in the system (63% for 3c) than hindered thiophenols (49% for 3c
and 33% for 3l). In case of low yielded reaction of 3l, the major side-product of
disulphide and biphenyl were formed. Functional groups, such as fluoro, chloro, and
bromo, are tolerated under reaction conditions. However, the aliphatic n-propyl amine
with thiophenol was failed to afford the desired thioether product.
It is to be noted that in the reaction of 3c or 3f, we have detected only minor traces of
reduced product, bromobenzene or nitrobenzene by GC-MS. whereas, in case of 3d, we
have not even detected fluorobenzene. These results clearly indicate there is no major
possible interaction of generated aryl radical with the hydrogen (from thiol). In addition,
on the reaction of 3d and 3e, bis(arylthio)arenes and the chain reaction side-products
were not detected as we compared with petrillo report. This observation ruled out the
hypothesis of SRN1, radical anion intermediates and its chain reaction process.8f
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Table 2. Scope of anilines with thiolsa
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aReaction conditions: aniline, 1 (0.6 mmol), thiophenol, 2 (0.5 mmol), tBuONO (1.2 mmol) were reacted at room
temperature for 2 h under blue LEDs.
To probe the scalability of the reaction, a gram scale reaction was performed between
1a and 2a in the presence of natural sunlight without stirring, and the desired product
3a was obtained in 75% yield (Scheme 2). The reaction rate will get increased as we
induce molecular interaction by stirring, under solvent-free gram scale natural sunlight
reaction and it may lead to by product issue. The main theme of the method in scheme
2 implies that, even in standby natural environment as only by using sunlight, the
reaction proceeded smoothly under environmentally benign mild condition.
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Scheme 2. Gram-scale synthesis of thioether
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Ranu et al. demonstrated the synthesis of selenide ethers from anilines and diaryl or
dialkyl diselenides.14,11 However, these reactions required the organo-photocatalyst or
stoichiometric equivalent of iron nanoparticles in presence of solvent (Scheme 1c, eq.
2). Therefore, an environmentally benign greener protocol is highly essential and
remains a challenge for selenide ether synthesis. The study was commenced by
selecting 4-chloroaniline 1e and diphenyl diselenide 4a as model substrates to optimize
reaction conditions (Table 3).
Table 3. Reaction conditions optimizationa
Entry
1
Photocatalyst
Light source
time
2 h
Yield (%)
Eosin Y
Blue LEDs
78
99
96
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2
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Blue LEDs
2 h
3b
4b
5c
6
Blue LEDs
2 h
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1 h
2 h
2 h
7
1 h
0.5 h
1 h
8
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10e
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1 h
96
aReaction conditions: 1e (0.5 mmol), 4a (0.5 mmol) and tBuONO (1.3 mmol) were reacted at room temperature for
1 h. b0.5 mmol of PhSeH was used instead of 4a. cReaction conducted with 0.25 mmol of 4a. dUnder atmosphere of
argon. eUnder atmosphere of air.
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Table 4. Scope of anilines with diselenidesa
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aReaction conditions: aniline, 1 (0.5 mmol), 4 (0.5 mmol), BuONO (1.3 mmol) were reacted at room temperature
for 1 h.
In the presence of a photocatalyst under blue LED irradiation, product 5a was obtained
with 78% yield. By contrasts, in the absence of a photocatalyst, the reaction afforded
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99% yield (Table 3, entries 1 and 2). On reaction with PhSeH, the product obtained
96% yield. However, in absence of light delivered 75% yield (Table 3, entries 3 and 4).
The reaction without the catalyst and light with 2:1 ratio of 1e and 4a resulted to 74%
yield. Whereas, the reaction with 1:1 ratio provided 99% yield (Table 3, entries 5 and
6). The reaction time was reduced to 1 h for furnishing the product with 99% yield
(Table 3, entry 7). A further reduction in the reaction time reduced the product yield
(Table 3, entry 8). The reactions performed in the presence of argon and in an open air
atmosphere delivered the product with 91% and 96% yields, respectively (Table 3,
entries 9 and 10). Meanwhile, Ranu et al has reported with no catalyst, in presence of
solvent under blue light irradiation, no product is formed.14 It is to be noted carefully
that conditions are different and thus predicting the role of the solvent is too intricate.
In addition, Ranu et al have proposed a mechanism as solvent plays a crucial role in
abstracting selenide ion, which is quiet unusual.14
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With the optimized reaction conditions in hand (Table 4), various halide-substituted
anilines were appropriately reacted with diphenyl diselenides to obtain the desired
products 5a-5g in 48%–99% yields. Moreover, 2-methoxyaniline and 4-methoxyaniline
were furnished products 5h and 5i in 53% and 73% yields, respectively. Aniline with
strong electron-withdrawing substituent provided the corresponding product 5j in 50%
yield. Sterically congested anilines survived, and the desired products 5k and 5l were
obtained in moderate yields. Furthermore, di(p-trifluoromethylphenyl) diselenide and
di(p-methylphenyl) diselenide smoothly reacted with various anilines bearing
functional groups, including chloro, methoxy, iodo, and methyl, providing the desired
products 5m-5t in 45%–99% yields. In case of aliphatic n-propyl amine with 4a, the
reaction failed to deliver the product.
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Scheme 3. Late-stage selenylation of drug molecules
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Sulfonamide15a-d families, such as sulfacetamide, sulfamethoxazole, and sulfameter, are
potent drug molecules and crucial in bioscience.15d On the basis of this biosignificant
application, the present protocol was employed in the late-stage selenylation of drug
molecules. Therefore, the desired selenide ether products (5u-5w) were obtained with
moderate to satisfactory yields (Scheme 3).
Control experiments were performed to understand the reaction mechanism. The
reaction was examined in the presence of TEMPO under standard reaction conditions.
A trace of product 3a was obtained. In addition, the aryl and thiyl radical adduct was
also detected by GC-MS. This result indicates that the reaction mechanism proceeds
through a radical pathway (Scheme 4a). On the other hand, we have investigated the
stability of diazonium ion (for 1a), with or without light in the presence of an excess of
tBuONO. In both cases, 1,2-diphenyldiazene, biphenyl, and 1,3-diphenyltriaz-1-ene
were detected by GC-MS. This result indicates that the diazonium salt is unstable. To
further study the participation of disulfide, a reaction between 1a and 6 was performed.
Therefore, the desired product 3a was obtained in 44% yield, suggesting that disulfide
might also be involved in this transformation. Similarly, we have performed the reaction
of 1 eq. of PhSSPh with respect to aniline 1a, the product 3a was obtained in only 5%
yield. This observation clearly indicates that an excess of disulfide diminishes the
reaction efficiency and it also ruled out the hypothesis of excess of PhSSPh as a reactant
could afford higher yield of the product 3a. In addition, it also reflects the importance
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of thiol in the present medium (Scheme 4b). Furthermore, the atmospheric conditions
influenced reaction yield (Scheme 4c). On the other hand, the reaction between 1e with
4a in the presence of TEMPO and butylated hydroxytoluene provided product 5a in
14% and 15% yields, respectively. This result indicates that the reaction mechanism is
involved through a radical pathway (Scheme 4d).
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Scheme 4. Control experiments
On the basis of the previous report16 and aforementioned results, a plausible mechanism
t
was proposed in Scheme 5. Aryl amine 1 initially interacts with BuONO to provide
aryl diazonium salt. In Path A, thiol 2 reacts with aryl diazonium salt generating aryl
and thiyl radicals, which subsequently react with each other to furnish the desired
thioether product 3. By contrast, in Path B, diselenide 4 reacts with aryl diazonium salt
to obtain aryl and selenyl radicals. The generated radicals react with each other to
provide selenide ether product 5. From the above studies of thio and selenide
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etherification, we suspect that in thioetherification reaction, for the generation of thiyl
radical from thiol on interaction with diazonium ions need high energy which is taken
maximum from light whereas, in selenide etherification reaction, the energy required
for the cleavage of Se-Se bond may be low and it is sufficient to get in the reaction
medium on interaction with diazonium ions and thus the reaction proceed without light
under ambient condition.
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Scheme 5. Plausible mechanism
Conclusion
In summary, one-pot straightforward procedure was developed in this study for the
synthesis of thioethers and selenide ethers from anilines under mild reaction conditions.
The present protocol has been accessed under catalyst-free, metal-free, solvent-free,
and acid-free conditions with satisfactory to excellent yields. The reaction was
compatible with and applicable for various substrates to construct C–S and C–Se bonds
from readily available starting materials. The high functional group tolerance of this
distinct method provides valuable functionalized thioethers and selenide ethers.
Moreover, it can be used in the late-stage functionalization of drug molecules. The
present protocol has simple operation and is highly effective, environmentally benign,
and convenient practical approach, which overcomes the hazardous utilization of toxic
metals and diazonium salts. The primary features of this facile protocol are generality,
ambient reaction conditions, high reaction efficiency, and prudent potent route to the
green synthesis of thioethers and selenide ethers.
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Experimental Section
General information:
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Merck silica gel 60 (230–400 mesh) were used to perform column chromatography. All
Melting points (M.P.) were observed by using a Büchi 535 apparatus. NMR spectra
were recorded in deuterochloroform and in deuterated DMSO with tetramethylsilane as
internal standard on a Varian Unity Inova-600 or a Varian Mercury-400 NMR
instrument and standard interpretations are given as s = singlet, d = doublet, t = triplet,
dd = double of doublet, m = multiplet and b = broad. Chemical shifts values are
represented in parts per million. Coupling constant (J) are given in hertz. All purchased
chemicals were used as received. GC-MS analyses were carried out on an Agilent
Technologies 5977A GC equipped with Agilent 7890B MS. HRMS were determined
by using Jeol JMS-HX 110 spectrometer with magnetic sector mass analyzer by the
services given at National Chung Hsing University.
The representative example of Table 1
Diphenyl sulfane (3a): A Schlenk tube equipped with a Teflon-coated magnetic stir bar
was charged with aniline (55.9 mg, 0.6 mmol) and thiophenol (55.1 mg, 0.5 mmol).
The tube was then evacuated and backfilled with nitrogen (this sequence was repeated
three times), and tert-butyl nitrite (1.2 mmol) was then added into the tube via syringe.
The reaction is irradiated by blue LED and stirring at room temperature for 2 h. After
reaction, the mixture was purified by column chromatography (SiO2, hexane) to yield
3a in 90% yield.
General procedures for Table 2 and Table 4
Condition A: A Schlenk tube equipped with a Teflon-coated magnetic stir bar was
charged with arylamine (0.6 mmol) and thiophenol (0.5 mmol). The tube was then
evacuated and backfilled with nitrogen (this sequence was repeated three times), and
tert-butyl nitrite (1.2 mmol, 124 mg) was then added into the tube via syringe. The
reaction is irradiated by blue LEDs and stirring at room temperature for 2 h. After
reaction, the mixture was purified by column chromatography (SiO2, hexane) to yield
thioethers.
Condition B: A Schlenk tube equipped with a Teflon-coated magnetic stir bar was
charged with arylamine (0.6 mmol) and thiol (0.5 mmol). The tube was then evacuated
and backfilled with nitrogen (this sequence was repeated three times), and tert-butyl
nitrite (1.2 mmol, 124 mg) was then added into the tube via syringe. The reaction is
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irradiated by blue LEDs and stirring at room temperature for 2 h. After reaction, the
mixture was purified by column chromatography (SiO2, hexane) to yield thioethers.
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Condition C: A Schlenk tube equipped with a Teflon-coated magnetic stir bar was
charged with arylamine (0.5 mmol) and diphenyl diselenide (0.5 mmol). The tube was
then evacuated and backfilled with nitrogen (this sequence was repeated three times),
and tert-butyl nitrite (1.3 mmol, 134 mg) was then added into the tube via syringe. The
reaction mixture was stirred at room temperature for 1 h. After completion of the
reaction, the mixture was extracted with ethyl acetate and washed with water and dried
over MgSO4 and filtered through a pad of Celite®. Then, the filtrate was concentrated
under reduced pressure and the obtained crude residue was purified by column
chromatography to yield selenide ethers.
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Diphenyl sulfane (3a):7h Following the condition A, using aniline (55.9 mg, 0.6 mmol),
thiophenol (55.1 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2 mmol), then purified by
column chromatography (SiO2, 10% ethyl acetate in hexanes) to provide 3a as the
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yellow oil (0.084 g, 90% yield). H NMR (400 MHz, CDCl3): δ 7.22-7.26 (m, 2H),
7.28-7.35 (m, 8H). 13C{1H} NMR (100 MHz, CDCl3): δ 126.9, 129.1, 130.8, 135.6.
(4-Methoxyphenyl)phenylsulfane (3b):7h Following the condition A, using p-anisidine
(73.9 mg, 0.6 mmol), thiophenol (55.1 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2
mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes)
to provide 3b as the yellow oil (0.061 g, 57% yield). Following the condition B, using
aniline (55.9 mg, 0.6 mmol), 4-Methoxythiophenol (70.1 mg, 0.5 mmol), tert-butyl
nitrite (124 mg, 1.2 mmol), then purified by column chromatography (SiO2, 10% ethyl
acetate in hexanes) to provide 3b as the yellow oil (0.103 g, 96% yield). 1H NMR (400
MHz, CDCl3): δ 3.76 (s, 3H), 6.85-6.87 (d, J = 8.8 Hz, 2H), 7.10-7.22 (m, 5H), 7.39 (d,
J = 8.4 Hz, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 55.2, 114.8, 124.0, 125.6, 127.9,
128.8, 135.3, 138.5, 159.7.
(2-Bromophenyl)phenylsulfane (3c):17a Following the condition A, using 2-
bromoaniline (103 mg, 0.6 mmol), thiophenol (55.1 mg, 0.5 mmol), tert-butyl nitrite
(124 mg, 1.2 mmol), then purified by column chromatography (SiO2, 10% ethyl acetate
in hexanes) to provide 3c as the yellow oil (0.083 g, 63% yield). Following the
condition B, using aniline (55.9 mg, 0.6 mmol), 2-bromothiophenol (94.5 mg, 0.5
mmol), tert-butyl nitrite (124 mg, 1.2 mmol), then purified by column chromatography
(SiO2, 10% ethyl acetate in hexanes) to provide 3c as the yellow oil (0.065 g, 49%
yield). 1H NMR (400 MHz, CDCl3): δ 6.90-6.93 (m, 1H), 6.99-7.02 (m, 1H), 7.10-7.14
(m, 1H) 7.34-7.39 (m, 3H), 7.43-7.45 (m, 2H), 7.53-7.55 (m, 1H). 13C{1H} NMR (100
MHz, CDCl3): δ 122.8, 127.1, 127.8, 128.4, 129.6, 132.7, 132.9, 133.5, 138.7.
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(4-Fluorophenyl)phenylsulfane (3d):7h Following the condition A, using 4-fluoroaniline
(66.7 mg, 0.6 mmol), thiophenol (55.1 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2
mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes)
to provide 3d as the yellow oil (0.086 g, 84% yield). Following the condition B, using
aniline (55.9 mg, 0.6 mmol), 4-fluorothiophenol (64.1 mg, 0.5 mmol), tert-butyl nitrite
(124 mg, 1.2 mmol), then purified by column chromatography (SiO2, 10% ethyl acetate
in hexanes) to provide 3d as the yellow oil (0.069 g, 68% yield). 1H NMR (400 MHz,
CDCl3): δ 6.99-7.03 (m, 2H), 7.20-7.22 (m, 1H), 7.24-7.27 (m, 4H) 7.35-7.38 (m, 2H).
13C{1H} NMR (150 MHz, CDCl3): δ 116.4 (d, J = 21.7 Hz), 126.7, 129.1, 129.9, 130.2
(d, J = 2.7 Hz), 134.0 (d, J = 8.1 Hz), 136.6, 162.3 (d, J = 246.3 Hz). 19F NMR (376
MHz, CDCl3): δ -115.4.
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(4-Chlorophenyl)phenylsulfane (3e):17b Following the condition A, using 4-
chloroaniline (76.5 mg, 0.6 mmol), thiophenol (55.1 mg, 0.5 mmol), tert-butyl nitrite
(124 mg, 1.2 mmol), then purified by column chromatography (SiO2, 10% ethyl acetate
in hexanes) to provide 3e as the yellow oil (0.057 g, 52% yield).Following the condition
B, using aniline (55.9 mg, 0.6 mmol), 4-chlorothiophenol (72.3 mg, 0.5 mmol), tert-
butyl nitrite (124 mg, 1.2 mmol), then purified by column chromatography (SiO2, 10%
ethyl acetate in hexanes) to provide 3e as the yellow oil (0.075 g, 68% yield). 1H NMR
(400 MHz, CDCl3): δ 7.26-7.30 (m, 5H), 7.31-7.37 (m, 4H). 13C{1H} NMR (100 MHz,
CDCl3): δ 127.5, 129.3, 129.4, 131.3, 132.0, 133.0, 134.7, 135.1.
(4-nitrophenyl)(phenyl)sulfane (3f):17c Following the condition A, using 4-nitroaniline
(82.9 mg, 0.6 mmol), thiophenol (55.1 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2
mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes)
to provide 3f as the yellow oil (0.074 g, 64% yield). 1H NMR (400 MHz, CDCl3): δ
7.17 (d, J = 8.4, 2H), 7.45-7.46 (m, 3H), 7.53-7.55 (m, 2H), 8.05 (d, J = 8.8 Hz, 2H).
13C{1H} NMR (100 MHz, CDCl3): δ 124.0, 126.6, 129.6, 130.0, 130.3, 134.7, 145.2,
148.5.
Phenyl(p-tolyl)sulfane (3g):7h Following the condition B, using aniline (55.9 mg, 0.6
mmol), 4-methylthiophenol (62 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2 mmol),
then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes) to
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provide 3g as the colorless oil (0.084 g, 84% yield). H NMR (400 MHz, CDCl3): δ
2.33 (s, 3H), 7.12 (d, J = 8.0 Hz, 2H), 7.16-7.26 (m, 5H), 7.29 (d, J = 7.6 Hz, 2H).
13C{1H} NMR (100 MHz, CDCl3): δ 21.1, 126.3, 129.0, 129.7, 130.0, 131.2, 132.2,
137.1, 137.5.
Mesitylphenylsulfane (3h):17d Following the condition B, using aniline (55.9 mg, 0.6
mmol), 2,4,6-trimethylbenzenethiol (76 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2
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mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes)
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to provide 3h as the yellow oil (0.067 g, 59% yield). H NMR (400 MHz, CDCl3): δ
2.36 (s, 3H), 2.44 (s, 6H), 6.96 (d, J = 7.6 Hz, 2H), 7.01-7.10 (m, 3H), 7.19-7.23 (m,
13
2H). C{1H} NMR (100 MHz, CDCl3): δ 21.11, 21.68, 124.4, 125.3, 126.9, 128.8,
129.3, 138.3, 139.2, 143.7.
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Phenyl(m-tolyl)sulfane (3i):7h Following the condition B, using aniline (55.9 mg, 0.6
mmol), 3-methylthiophenol (62 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2 mmol),
then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes) to
provide 3i as the colorless oil (0.064 g, 64% yield). 1H NMR (400 MHz, CDCl3): δ 2.33
(s, 3H), 7.03-7.09 (m, 1H), 7.16-7.20 (m, 4H), 7.22-7.36 (m, 4H). 13C{1H} NMR (100
MHz, CDCl3): δ 21.28, 126.8, 127.4, 128.3, 129.1, 130.7, 131.8, 135.2, 136.1, 139.0.
Phenyl(o-tolyl)sulfane (3j):7h Following the condition B, using aniline (55.9 mg, 0.6
mmol), 2-methylthiophenol (62 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2 mmol),
then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes) to
provide 3j as the colorless oil (0.041 g, 41% yield). 1H NMR (400 MHz, CDCl3): δ 2.35
(s, 3H), 7.08-7.22 (m, 8H), 7.28 (d, J = 7.6 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3):
δ 20.5, 126.2, 126.6, 127.8, 129.0, 129.5, 130.5, 132.9, 133.6, 136.0, 139.8.
(4-Bromophenyl)phenylsulfane (3k):17e Following the condition B, using aniline (55.9
mg, 0.6 mmol), 4-bromothiophenol (95 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2
mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes)
to provide 3k as the colorless oil (0.065 g, 49% yield). 1H NMR (400 MHz, CDCl3): δ
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7.23 (d, J = 8.4 Hz, 2H), 7.25-7.40 (m, 3H), 7.43-7.47 (m, 4H). C{1H} NMR (100
MHz, CDCl3): δ 120.8, 127.5, 129.4, 131.3, 131.5, 132.0, 132.2, 134.8, 135.4.
(2-Chlorophenyl)phenylsulfane (3l):7h Following the condition B, using aniline (55.9
mg, 0.6 mmol), 2-chlorothiophenol (72 mg, 0.5 mmol), tert-butyl nitrite (124 mg, 1.2
mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in hexanes)
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to provide 3l as the yellow oil (0.036 g, 33% yield). H NMR (400 MHz, CDCl3): δ
6.99-7.02 (m, 1H), 7.09-7.16 (m, 2H), 7.38-7.42 (m, 4H), 7.47-7.49 (m, 2H). 13C{1H}
NMR (100 MHz, CDCl3): δ 127.3, 128.4, 129.7, 129.8, 130.0, 132.6, 133.1, 133.4,
136.6.
(4-Chlorophenyl)(phenyl)selane (5a):17f Following the condition C, using 4-
chloroaniline (63.8 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl
nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2, hexanes)
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to provide 5a as the yellow oil (0.132 g, 99% yield). H NMR (400 MHz, CDCl3): δ
7.18 (d, J = 8.3 Hz, 2H), 7.23-7.25 (m, 3H), 7.33 (d, J = 8.4 Hz, 2H), 7.42-7.44 (m, 2H).
13C{1H} NMR (100 MHz, CDCl3): δ 127.6, 129.4, 129.5, 130.6, 133.1, 133.4, 134.0.
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(4-Fluorophenyl)(phenyl)selane (5b):17f Following the condition C, using 4-
fluoroaniline (55.6 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl
nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2, hexanes)
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to provide 5b as the yellow oil (0.070 g, 56% yield). H NMR (400 MHz, CDCl3): δ
6.92-7.23 (m, 2H), 7.24-7.25 (m, 3H), 7.38-7.45 (m, 2H), 7.46-7.48 (m, 2H). 13C{1H}
NMR (150 MHz, CDCl3): δ 116.5 (d, J = 21.3 Hz), 125.2 (d, J = 3.4 Hz), 127.2, 129.3,
131.6, 132.2, 135.7 (d, J = 7.9 Hz), 162.5 (d, J = 246.6 Hz).
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(2-Bromophenyl)(phenyl)selane (5c):17g Following the condition C, using 2-
bromoaniline (86.0 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl
nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2, hexanes)
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to provide 5c as the white solid (0.101 g, 65% yield). m.p. 50-51 C. H NMR (400
MHz, CDCl3): δ 6.87 (dd, J = 7.7, 1.8 Hz, 1H), 7.00-7.10 (m, 2H), 7.37-7.47 (m, 3H),
7.52 (dd, J = 7.6, 1.7 Hz, 1H), 7.68-7.63 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ
123.4, 127.3, 127.9, 128.5, 129.8, 129.9, 130.4, 132.8, 136.2, 136.32, 136.30, 136.4.
(3-Iodophenyl)(phenyl)selane (5d): Following the condition C, using 3-iodoaniline
(109.5 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl nitrite (134
mg, 1.3 mmol), then purified by column chromatography (SiO2, hexanes) to provide 5d
as the yellow oil (0.160 g, 89% yield). 1H NMR (400 MHz, CDCl3): δ 6.94 (t, J = 7.8
Hz, 1H), 7.30-7.25 (m, 3H), 7.34 (d, J = 7.8 Hz, 1H), 7.48 (dd, J = 6.4, 2.9 Hz, 2H),
7.54 (d, J = 7.9 Hz, 1H), 7.77 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 95.0, 127.9,
129.5, 129.9, 130.7, 131.4, 133.6, 133.7, 136.0, 140.3. HRMS (EI) calcd for C12H9ISe
[M]+ 359.8914, found 359.8917.
(4-Iodophenyl)(phenyl)selane (5e): Following the condition C, using 4-iodoaniline
(109.5 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl nitrite (134
mg, 1.3 mmol), then purified by column chromatography (SiO2, hexanes) to provide 5e
as the yellow solid (0.087 g, 48% yield). m.p. 56-58 °C. 1H NMR (400 MHz CDCl3): δ
7.14 (d, J = 8.2 Hz, 2H), 7.27-7.29 (m, 3H), 7.47 (dd, J= 6.5, 2.9 Hz, 2H), 7.55 (d, J =
13
8.2 Hz, 2H). C{1H} NMR (100 MHz, CDCl3): δ 92.7, 127.8, 129.5, 130.2, 131.5,
133.5, 134.2, 138.2. HRMS (EI) calcd for C12H9ISe [M]+ 359.8914, found 359.8909.
(3-Iodo-4-methylphenyl)(phenyl)selane (5f): Following the condition C, using 3-iodo-
4-methylaniline (116.5 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-
butyl nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2,
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hexanes) to provide 5f as the yellow oil (0.142 g, 76% yield). H NMR (400 MHz,
CDCl3): δ 2.38 (s, 3H), 7.10 (d, J = 7.8 Hz, 1H), 7.24-7.26 (m, 3H), 7.32 (dd, J = 7.8,
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1.7 Hz, 1H), 7.41-7.44 (m, 2H), 7.94 (d, J = 1.7 Hz, 1H). C{1H} NMR (100 MHz,
CDCl3): δ 27.7, 101.8, 127.4, 129.2, 129.3, 130.3, 130.9, 132.6, 133.1, 140.7, 142.7.
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HRMS (EI) calcd for C13H11ISe [M]+ 373.9071, found 373.9079.
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(2-Iodo-5-methylphenyl)(phenyl)selane (5g): Following the condition C, using 2-iodo-
5-methylaniline (116.5mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-
butyl nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2,
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hexanes) to provide 5g as the orange oil (0.149 g, 80% yield). H NMR (400 MHz,
CDCl3): δ 2.11 (s, 3H), 6.67 (dd, J = 8.0, 1.6 Hz, 1H), 6.77 (d, J = 1.5 Hz, 1H), 7.38-
7.31 (m, 3H), 7.55-7.59 (m, 2H), 7.60-7.64 (m, 1H). 13C{1H} NMR (100 MHz, CDCl3):
δ 20.9, 96.1, 128.5, 128.8, 129.7, 130.4, 131.4, 135.2, 138.8, 139.1, 139.7. HRMS (EI)
calcd for C13H11ISe [M]+ 373.9071, found 373.9076.
(2-Methoxyphenyl)(phenyl)selane (5h):17f Following the condition C, using o-anisidine
(61.6 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl nitrite (134
mg, 1.3 mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in
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hexanes) to provide 5h as the brown oil (0.070 g, 53% yield). H NMR (400 MHz,
CDCl3): δ 3.91 (s, 3H), 6.80-6.89 (m, 2H), 6.98 (dd, J = 7.7, 1.4 Hz, 1H), 7.20-7.23 (m,
2H), 7.34-7.37 (m, 2H), 7.61-7.63 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 55.78,
110.30, 121.54, 121.82, 127.63, 128.04, 128.14, 129.38, 130.68, 135.38, 156.50.
(4-Methoxyphenyl)(phenyl)selane (5i):17f Following the condition C, using p-anisidine
(61.6 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl nitrite (134
mg, 1.3 mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in
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hexanes) to provide 5i as the yellow oil (0.096 g, 73% yield). H NMR (400 MHz,
CDCl3): δ 3.78 (s, 3H), 6.83-6.85 (m, 2H), 7.17-7.20 (m, 3H), 7.30-7.33 (m, 2H), 7.49-
7.51 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 55.20, 115.04, 119.80, 126.36,
129.08, 130.76, 133.15, 136.48, 159.68.
(4-Nitrophenyl)(phenyl)selane (5j):17g Following the condition C, using 4-nitroaniline
(69.1 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-butyl nitrite (134
mg, 1.3 mmol), then purified by column chromatography (SiO2, 10% ethyl acetate in
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hexanes) to provide 5j as the yellow oil (0.070 g, 50% yield). H NMR (400 MHz,
CDCl3): δ 7.33-7.36 (m, 2H), 7.41-7.46 (m, 3H), 7.62-7.65 (m, 2H), 8.02-8.03 (m, 1H),
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8.03-8.04 (m, 1H). C{1H} NMR (100 MHz, CDCl3): δ 123.9, 127.1, 129.3, 129.6,
130.0, 135.8, 143.9, 146.1.
(2,6-Diisopropylphenyl)(phenyl)selane (5k): Following the condition C, using 2,6-
diisopropylaniline (88.6 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-
butyl nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2,
hexanes) to provide 5k as the light yellow oil (0.072 g, 45% yield). 1H NMR (400 MHz,
CDCl3): δ 1.13 (s, 6H), 1.15 (s, 6H), 3.76-3.79 (m, 2H), 7.03-7.09 (m, 3H), 7.10-7.15
(m, 2H), 7.24 (d, J = 7.7 Hz, 2H), 7.38-7.42 (m, 1H). 13C{1H} NMR (100 MHz, CDCl3):
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δ 24.3, 34.4, 123.9, 125.2, 128.3, 128.8, 129.0, 130.1, 134.8, 153.7. HRMS (EI) calcd
for C18H22Se [M]+ 318.0887, found 318.0897.
(2,6-Dimethylphenyl)(phenyl)selane (5l):11 Following the condition C, using 2,6-
dimethylaniline (60.6 mg, 0.5 mmol), diphenyl diselenide (156 mg, 0.5 mmol), tert-
butyl nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2, 10%
ethyl acetate in hexanes) to provide 5l as the orange oil (0.056 g, 43% yield). 1H NMR
(400 MHz, CDCl3): δ 2.48 (s, 6H), 7.07-7.12 (m, 4H), 7.13-7.17 (m, 3H), 7.19-7.25 (m,
1H). 13C{1H} NMR (100 MHz, CDCl3): δ 24.4, 125.5, 127.9, 128.6, 128.9, 129.1, 130.3,
133.1, 143.8.
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(4-Chlorophenyl)(4-(trifluoromethyl)phenyl)selane (5m): Following the condition C,
using 4-chloroaniline (63.8 mg, 0.5 mmol), bis(4-trifluoromethyl-phenyl) diselenide
(224 mg, 0.5 mmol), tert-butyl nitrite (134 mg, 1.3 mmol), then purified by column
chromatography (SiO2, hexanes) to provide 5m as the yellow solid (0.164 g, 98% yield).
m.p. 58-59 °C. 1H NMR (400 MHz, CDCl3): δ 7.30 (d, J = 7.7 Hz, 2H), 7.42 (d, J = 8.3
Hz, 2H), 7.46-7.48 (m, 4H). 13C{1H} NMR (150 MHz, CDCl3): δ 124.0 (q, J = 270.6
Hz), 126.0 (d, J = 3.1 Hz), 127.0, 129.1 (q, J = 32.5 Hz), 129.9, 131.2, 133.0, 134.9,
135.9, 137.1. 19F NMR (376 MHz, CDCl3): δ -64.153. HRMS (EI) calcd for
C13H8ClF3Se [M]+ 335.9432, found 335.9424.
(4-Chlorophenyl)(p-tolyl)selane (5n):17h Following the condition C, using 4-
chloroaniline (63.8 mg, 0.5 mmol), bis(4-methylphenyl) diselenide (170 mg, 0.5 mmol),
tert-butyl nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2,
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hexanes) to provide 5n as the yellow solid (0.126 g, 90% yield). m.p. 69-70 C. H
NMR (400 MHz, CDCl3): δ 2.33 (s, 3H), 7.10 (d, J = 7.9 Hz, 2H), 7.20-7.16 (m, 2H),
7.32-7.28 (m, 2H), 7.39 (d, J = 8.0 Hz, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 21.1,
126.3, 129.3, 130.3, 130.5, 133.0, 133.2, 134.0, 138.0.
(4-Methoxyphenyl)(4-(trifluoromethyl)phenyl)selane (5o): Following the condition C,
using p-anisidine (61.6 mg, 0.5 mmol), bis(4-trifluoromethylphenyl) diselenide (224
mg, 0.5 mmol), tert-butyl nitrite (134 mg, 1.3 mmol), then purified by column
chromatography (SiO2, 10% ethyl acetate in hexanes) to provide 5o as the yellow solid
(0.075 g, 45% yield). m.p. 88-90 °C. 1H NMR (400 MHz, CDCl3): δ 3.82 (s, 3H), 6.90
(d, J = 8.8 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 7.55 (d, J = 8.8
Hz, 2H). 13C{1H} NMR (150 MHz, CDCl3): δ 55.3, 115.4, 117.9, 124.1 (q, J = 270.3
Hz), 125.7 (d, J = 3.1 Hz), 128.1 (q, J = 32.4 Hz), 129.4, 137.7, 139.5, 160.4. 19F NMR
(376 MHz, CDCl3): δ -64.008. HRMS (EI) calcd for C14H11F3OSe [M]+ 331.9927,
found 331.9934.
(4-Methoxyphenyl)(p-tolyl)selane (5p):17i Following the condition C, using p-anisidine
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(61.6 mg, 0.5 mmol), bis(4-methylphenyl) diselenide (170 mg, 0.5 mmol), tert-butyl
nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2, 10% ethyl
acetate in hexanes) to provide 5p as the orange solid (0.085 g, 61% yield). m.p. 54-55
°C. 1H NMR (400 MHz, CDCl3): δ 2.28 (s, 3H), 3.78 (d, J = 2.4 Hz, 3H), 6.82 (d, J =
8.4 Hz, 2H), 7.03 (d, J = 8 Hz, 2H), 7.27 (d, J = 8 Hz, 2H), 7.44-7.46 (m, 2H). 13C{1H}
NMR (100 MHz, CDCl3): δ 21.0, 55.2, 115.0, 120.8, 128.9, 129.9, 131.8, 135.7, 136.6,
159.5.
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(3-Iodophenyl)(p-tolyl)selane (5q): Following the condition C, using 3-iodoaniline
(109.5 mg, 0.5 mmol), bis(4-methylphenyl) diselenide (170 mg, 0.5 mmol), tert-butyl
nitrite (134 mg, 1.3 mmol), then purified by column chromatography (SiO2, 10% ethyl
acetate in hexanes) to provide 5q as the yellow oil (0.185 g, 99% yield). 1H NMR (400
MHz, CDCl3): δ 2.33 (s, 3H), 6.90-6.93 (m, 1H), 7.11 (d, J = 7.6 Hz, 2H), 7.27-7.30
(m, 1H), 7.40-7.42 (m, 2H), 7.51 (dd, J = 8, 1.2 Hz, 1H), 7.71 (t, J = 1.6 Hz, 1H).
13C{1H} NMR (100 MHz, CDCl3): δ 21.18, 95.04, 125.59, 130.32, 130.44, 130.59,
134.37, 134.69, 135.49, 138.18, 139.41. HRMS (EI) calcd for C13H11ISe [M]+ 373.9071,
found 373.9075.
(3-Iodophenyl)(4-(trifluoromethyl)phenyl)selane (5r): Following the condition C,
using 3-iodoaniline (109.5 mg, 0.5 mmol), bis(4-trifluoromethyl-phenyl) diselenide
(224 mg, 0.5 mmol), tert-butyl nitrite (134 mg, 1.3 mmol), then purified by column
chromatography (SiO2, hexanes) to provide 5r as the yellow oil (0.196 g, 92% yield).
1H NMR (400 MHz, CDCl3): δ 7.03 (t, J = 7.8 Hz, 1H), 7.43-7.49 (m, 5H), 7.65 (d, J
= 7.9 Hz, 1H), 7.90 (t, J = 1.5 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 95.2, 123.9
(q, J = 270.7 Hz), 126.0 (d, J = 3.5 Hz), 129.2 (q, J = 32.3 Hz), 131.1, 131.6, 133.0,
133.3, 136.5, 137.3, 142.3. 19F NMR (376 MHz, CDCl3): δ -64.055. HRMS (EI) calcd
for C13H8F3ISe [M]+ 427.8788, found 427.8784.
(3-Iodo-4-methylphenyl)(4-(trifluoromethyl)phenyl) selane (5s): Following the
condition C, using 3-iodo-4-methylaniline (116.5 mg, 0.5 mmol), bis(4-
trifluoromethyl-phenyl) diselenide (224 mg, 0.5 mmol), tert-butyl nitrite (134 mg, 1.3
mmol), then purified by column chromatography (SiO2, hexanes) to provide 5s as the
yellow solid (0.190 g, 86% yield). m.p. 83-84 °C. 1H NMR (400 MHz, CDCl3): δ 2.44
(s, 3H), 7.20 (d, J = 7.8 Hz, 1H), 7.40-7.54 (m, 5H), 8.05 (d, J = 1.6 Hz, 1H). 13C{1H}
NMR (150 MHz, CDCl3): δ 27.9, 102.0, 124.0 (q, J = 270.4 Hz), 125.9 (d, J = 3.4 Hz),
126.8, 128.8 (q, J = 32.4 Hz), 130.7, 130.8, 134.8, 137.5, 142.2, 144.4. 19F NMR (376
MHz, CDCl3): δ -64.117. HRMS (EI) calcd for C14H10F3ISe [M]+ 441.8944, found
441.8950.
(3-Iodo-4-methylphenyl)(p-tolyl)selane (5t): Following the condition C, using 3-iodo-
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(SiO2, hexanes) to provide 5t as the yellow oil (0.151 g, 78% yield). H NMR (400
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MHz, CDCl3): δ 2.30 (s, 3H), 2.34 (s, 3H), 7.06 (dd, J = 7.6, 5.2 Hz, 3H), 7.25 (dd, J =
7.6, 1.6 Hz, 1H), 7.36 (d, J = 8 Hz, 2H), 7.87 (br, 1H). 13C{1H} NMR (100 MHz, CDCl3):
δ 21.1, 27.6, 101.8, 126.7, 130.2, 132.2, 133.5, 137.7, 140.1, 141.8. HRMS (EI) calcd
for C14H13ISe [M]+ 387.9227, found 387.9232.
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N-((4-(Phenylselanyl)phenyl)sulfonyl)acetamide (5u): Following the condition C,
using sulfacetamide (214 mg, 1 mmol), diphenyl diselenide (312 mg, 1 mmol), tert-
butyl nitrite (268 mg, 2.6 mmol), then purified by column chromatography (SiO2,
°
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hexanes) to provide 5u as the white solid (0.242 g, 68% yield). m.p. 143-145 C H
NMR (400 MHz, DMSO): δ 1.87 (s, 3H), 7.38-7.43 (m, 5H), 7.57 (dd, J = 7.6, 1.8 Hz,
2H), 7.74 (d, J = 8.6 Hz, 2H). 13C{1H} NMR (100 MHz, DMSO): δ 23.7, 127.6, 128.8,
129.6, 130.3, 130.6, 135.7, 137.7, 140.7, 169.2. HRMS (EI) calcd for C14H13NO3SSe
[M]+ 354.9781, found.354.9786.
N-(5-Methylisoxazol-3-yl)-4-(phenylselanyl)benzene sulfonamide (5v): Following the
condition C, using sulfamethoxazole (253 mg, 1 mmol), diphenyl diselenide (312 mg,
1 mmol), tert-butyl nitrite (268 mg, 2.6 mmol), then purified by column
chromatography (SiO2, hexanes) to provide 5v as the white solid (0.216 g, 55% yield).
m.p. 147-149 °C. 1H NMR (400 MHz, DMSO): δ 2.27 (s, 3H), 6.11 (s, 1H), 7.44 (dd, J
= 13.9, 7.0 Hz, 5H), 7.64-7.56 (m, 2H), 7.71 (d, J = 8.5 Hz, 2H), 11.45 (s, 1H). 13C{1H}
NMR (100 MHz, DMSO): δ 12.5, 95.8, 127.6, 128.0, 129.6, 130.6, 130.6, 135.6, 137.9,
140.3, 157.8, 170.8. HRMS (EI) calcd for C16H14N2O3SSe [M]+ 393.9890, found.
393.9892.
N-(5-Methoxypyrimidin-2-yl)-4-(phenylselanyl)benzene sulfonamide (5w): Following
the condition C, using sulfameter (280 mg, 1 mmol), diphenyl diselenide (312 mg, 1
mmol), tert-butyl nitrite (536 mg, 5.2 mmol), then purified by column chromatography
(SiO2, hexanes) to provide 5w as the white solid (0.126 g, 30% yield). m.p. 153-154 °C
1H NMR (400 MHz, DMSO): δ 3.78 (s, 3H), 7.43 (t, J = 7.5 Hz, 5H), 7.58 (dd, J = 7.4,
1.7 Hz, 2H), 7.82 (d, J = 8.4 Hz, 2H), 8.27 (s, 2H), 11.51 (s, 1H). 13C{1H} NMR (100
MHz, DMSO): δ 56.7, 127.9, 128.7, 129.4, 130.4, 130.5, 135.4, 139.1, 139.3, 145.1,
150.1, 151.2. HRMS (EI) calcd for C17H15N3O3SSe [M]+ 420.9999, found. 421.0006.
ASSOCIATED CONTENT
Supporting Information
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The Supporting Information is available free of charge on theACS Publications website.
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Light source details, NMR spectra for all compounds, and crystal structure
determination (PDF)
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CCDC no. 1874377 (5u) (CIF)
CCDC no. 1880857 (5w) (CIF)
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AUTHOR INFORMATION
Corresponding Author
*Email: cfalee@dragon.nchu.edu.tw
ORCID
Chin-Fa Lee: 0000-0003-0735-5691
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was financially supported by the Ministry of Science and Technology,
Taiwan (MOST 107-2113-M-005-019-MY3); National Chung Hsing University;
Research Center for Sustainable Energy and Nanotechnology (NCHU) and the
"Innovation and Development Center of Sustainable Agriculture" from The Featured
Areas Research Center Program within the framework of the Higher Education Sprout
Project by the Ministry of Education (MOE) in Taiwan.
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