Selenium dioxide promoted dinitrogen extrusion/direct selenation of arylhydrazines and anilines

Article abstract of DOI:10.1016/j.tet.2020.131105

A novel, efficient, economical strategy for the coupling and direct selenation of arylhydrazines to selenides using SeO₂ has been developed. Our method employs SeO₂ as the selenium source with hydrazines as coupling reactants to generate selenides via dinitrogen extrusion. This reagent also helped to generate ArSe substitued aniline derivatives via C–H functionalization reaction in good yields. The application of this method in gram scale was also carried out.

Full text of DOI:10.1016/j.tet.2020.131105

Journal Pre-proof
Selenium dioxide promoted dinitrogen extrusion/direct selenation of arylhydrazines
and anilines
Mohammad YaqoobBhat, Atul Kumar, Qazi Naveed Ahmed
PII:
S0040-4020(20)30226-X
https://doi.org/10.1016/j.tet.2020.131105
TET 131105
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 November 2019
Revised Date: 2 March 2020
Accepted Date: 5 March 2020
Please cite this article as: YaqoobBhat M, Kumar A, Naveed Ahmed Q, Selenium dioxide promoted
dinitrogen extrusion/direct selenation of arylhydrazines and anilines, Tetrahedron (2020), doi: https://
doi.org/10.1016/j.tet.2020.131105.
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Selenium
dioxide
Promoted
Dinitrogen
Leave this area blank for abstract info.
Extrusion/Direct Selenation of Arylhydrazines
and Anilines
Mohammad Yaqoob Bhat,Atul Kumar, Qazi Naveed Ahmed *

1
Author Name/Engineering Science and Technology, an International Journal
Tetrahedron
journal homepage: www.elsevier.com/locate/jestch
Selenium dioxide Promoted Dinitrogen Extrusion/Direct Selenation of Arylhydrazines
and Anilines.
Mohammad YaqoobBhat,a,bAtul Kumar,a,bQazi Naveed Ahmed*a,b
aMedicinal Chemistry Division, Indian Institute of Integrative Medicine (IIIM), 180001, Canal Road, Jammu, Jammu & Kashmir, India
bAcademy of Scientific and Innovative Research (AcSIR), Indian Institute of Integrative Medicine (IIIM), 180001, Canal Road, Jammu, Jammu & Kashmir, India
ABSTRACT
ARTICLE INFO
Article history:
Received
A novel, efficient, economical strategy for the coupling and direct selenation of arylhydrazines to selenides using
SeO2 has been developed. Our method employs SeO2 as the selenium source with hydrazines as coupling
reactants to generate selenides via dinitrogen extrusion. This reagent also helped to generate ArSesubstitued
aniline derivatives via C- H functionalization reaction in good yields. The application of this method in gram scale
was also carried out.
Received in revised form
Accepted
Available online
Keywords:
Dinitrogen Extrusion
Direct Selenation
Selenium dioxide
Arylhydrazines and Anilines
Selenation of β-Napthol
1. Introduction
Organoselenides, in particular the diaryl selenidesembracing
carbon-selenium-carbon connectivity engendered a prominent position
in material, biological, pharmaceutical science and are often found
active as medicinal hits displaying a broad range of bioactivities.1For
example,the diaryl selenide A could be used as human breast
cancercell growth inhibitor, B is useful as a thioredoxin reductase (TR)
and glutathione reductase (GR) inhibitorand C can serve as an
antitumor agent (Figure 1). Moreover, the 2-substituted 1-naphthol D
is a potent 5-lipoxygenase inhibitorwhile as the carboxylic acid E is a
retinoic acid receptor (RAR) agonist which is ~10 times more powerful
than its sulphur analogue. On the other hand, 4-substituted quinoline F
possesses antioxidant properties (Figure 1).1gBesides this, they have
also shown significant applications as catalysts and are useful
intermediates in organic reactions.2 As a result, a number of methods
have been esta-
Figure 2. Summary of this work
blished in the past towards the development of novel synthetic
protocols for organoselenides.3 Among the diverse customary
approaches, synthesis of organoselenides using aryldiazonium salts
have attracted much attention as a significant source of aryl radicals
Figure 1. Selected biologically active organoselenium compounds.

2
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and have been employed successfully for variety of aryl substitution
reactions.4-5Although, the visible light photocatalyzed C−Se bond
formation involving diazonium ion appeared useful, these conversions
were carried out using diselenides as an expensive and foul smelling
reagents in the presence ofdifferent additives for in-situ generation of
diazonium. In this regard, we envisage the possibility of presenting
selenium dioxide promoted dinitrogen extrusion assisted selenation
reaction with different hydrazines (Figure 2). These types of reactions
besides being the surrogate of diazocompouds, can also overcome
the limitations of using expensive reactantsor additives. Compared to
previously reported routes,6 our methods are probably more suitable
for larger scale syntheses since the selenium dioxide is cheap, stable,
odorless, readily available and convenient to handle. Further,
weextended the application to anilines as coupling reactants and
successfully generated different ArSesubstitued aniline derivatives
viaC-H functionalization. Previously, success in the area of C-H
activation has been accomplished using directing groups in the
presence of copper, palladium, ruthenium or rhodium catalysts
withdiselenides/selenylchlorides.7 Thereby, as an advantage, we also
presented a metal free methodin which bulky directing groups and
expensive selenium reagents with low atom/step-economyis avoided.
In general, both aspects of reactivities highlight the strength of
selenium dioxide to promote the coupling and direct selenation of both
aryl- hydrazines and anilines. All the reactions were performedwithout
any external additives or co-oxidants. The most imperative feature of
the synthesis can be the ease of SeO2 to promote dinitrogen extrusion
in hydrazines and C-H activation in anilines.In addition, these
strategies were successfully applied for the gram scale synthesis of
different selenides.
2. Results and discussion
We initiated our investigation by evaluating the selenation reaction
of phenylhydrazine1a (1 mmol) with SeO2 (0.5 mmol) in MeCN in
which the desired product 2a was obtained in 39% yield (Table 1,
entry 1). The temperature of the reaction and concentration of SeO2
appeared to play an important role, therefore, different optimization
reactions were performed as summarized in Table 1 (entry 2-11).
Good yields of the desired product 2a was observed when 1.5 mmol of
SeO2 was treated with phenylhydrazine1a (1 mmol) at 60oC in
MeCN(entry 5).
Reaction conditions: Phenylhydrazines1(1 mmol), and SeO2
(1.5 mmol) in 5 mL of MeCNat 60oC for 1h.
Scheme1.Scope of dinitrogen extrusion assisted selenationreaction.
The same reaction when tried with different solvents generated the
desired product in lower yields (entries 6-11). Increased temperature
in DMSO does not improve much yield of the desired product (entries
10-11).
Having identified optimized reaction conditions, various reactions with
divergent substrates and substituents were tested (Scheme 1). The
scope of SeO2 promoted dinitrogen extrusion reactions with different
hydrazines1 were demonstrated as listed in Scheme 1. Yields were
generally good for all the substrates being tested. However, it was
observed that the electronic environment of phenyl ring in hydrazines
affected the yields of products to some extent. On the basis of our
results, we observed that the substrates bearing electron withdrawing
groups like -CF3, -CN, -F (2b, 2c, 2fand 2j) afforded slightly lower
yields in comparison to unsubstituted substrates (2a) and those
containing electron donatinggroups like-Cl, -Br, -CH3 and OMe(2d, 2e,
2g, 2i, 2k, 2l and 2m).This observation can be attributed to more
migratory aptitude of aromatic rings that bear electron donating groups
in intermediate C (Scheme 6) as compared to electron withdrawing
groups. The hetero-coupling efficiency was also demonstrated by
reaction of different hydrazines as depicted in Scheme 2.Interestingly,
in all experiments the cross coupledproducts (3a-3c) were isolated in
good yields in comparison to the self coupled products. The hetero-
coupling reactions presented in Scheme 2clearly highlights the merit
of current reactions to generate unsymmetrical products in
predominant yields. These reactions also show the benefit of using
SeO2 as selenating reagent.
Table 1. Optimization of the reaction conditions.a
entry
1
SeO2 (mmol)
temp (oC)
solvent
yieldb(%)
39
0.5
1.0
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
rt
rt
MeCN
MeCN
2
44
MeCN
MeCN
MeCN
3
rt
57
4
45
60
60
60
60
60
80
100
69
5
81
6
DCM
72
7
Toluene
MeOH
DMSO
DMSO
DMSO
62
8
69
9
71
10
71
11
71
aPhenylhydrazine1a (1 mmol), SeO2 (1.5 mmol) in MeCN at
60oC for 1h.bIsolated yields.
Next, we extended the application of our concept by treating anilines 4
(1 mmol) with SeO2 (1.5 mmol) in MeCN at 80oC (for detailed

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Author Name/Engineering Science and Technology, an International Journal
5a-5n in good yields, due to strong ortho, para nature of aniline.
However, as expected in all these reactions, we didn’t isolated any
ortho-ortho coupled products due to steric and electronic reasons. In
addition, our reactionworked well withindoline
Scheme 2. Dinitrogen extrusion assisted hetero-couplingselenation
optimization see Supporting information). To our surprise we got para-
para Se inserted dianiline in major and ortho-para in minor
concentration. Different substituted anilines were tested and it was
found that substitution does not affect much on the yields of the
desired products (Scheme 3). However, the reactions with anilines
having electron donating group(s) at meta positionincrease the ortho
product slightly than unsubstituted and electron withdrawing groups at
meta position. With hydrogen atom at para position like aniline, 2-F, 3-
F, 3-Cl, 3-Br-2-Me, 2,3-diMe, 2,6-diMe, 2,5-diMe, 2-Cl, 2I, 2-Cl-5-I,2-
Scheme 4. Amine directed hetero-couplingselenation
and
diphenylamine
(5oand5p).
In
continuation,
many
OMe,2-Me-3-OMethe
predominantlyobtained.
para
coupledselenatedproduct
was
differentreactions were performed with different anilines 4 as per the
optimizedconditionsand cross coupled products6a-6ewere obtainedin
appreciable yields (Scheme 4). However, in all the cases, self coupled
products were also isolated in minor quantities.
Further, these strategies were successfully applied for the gram scale
synthesis of different selenides 2a, 5a, 5o and 5p in good yields
(Scheme 5).
Scheme 5. Gram scale synthesis of selenides.
Most likely, these reactions occur by the interaction of the SeO2 in two
different pathways as outlined in Scheme 6. In the preceding reaction
with hydrazines, we presume that the reaction of hydrazines
withSeO2initially generates intermediate A that undergoes dehydration
to form B.Addition of second mole of hydrazine to Bagain undergoes
dehydration to form intermediate C. Intermediate Con 1,3-sigmatropic
rearrangement followed by dinitrogen extrusion leads to the
generation of 2.Further, in case of anilines,SeO2 first undergoes a
disproportionation processto afforddianilinetriselenides as per
theWilshire’sassumption.8However;there exist possibilities ofthree
different triselinides out of which the para-para isformed in major
quantity followed by ortho-paratriselenation.Sincewe failed to isolate
Reaction conditions[a]: Anilines 4 (1 mmol), and SeO2 (1.5 mmol) in
5 mL of MeCN at 80oC for 3h.
Scheme 3. Scope of amine directed selenationreaction.a

4
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.
Scheme 6. Possible Reaction Pathway
In addition, the methodologywas successfully applied for the gram
scale synthesis of selinides and selenation of β-Napthol. Furthermore,
the ortho-ortho coupled product,therefore, the thirdcoupling possibility
is ignored. However, the para-paraand ortho-para intermediates later
on decompose to liberate metallicSe(0) leaving behind dianiline
selenides 5.9 In case of different anilinestested (Scheme 4),we failed to
isolate the ortho-ortho coupled product and thereby few
reactionswereconducted with para substituted anilines.As expected,
all thesereactions failed to produce the selenated products (Scheme
7).
applications across different C-nucleophiles are in progress.
4. Experimental Section.
1. General information
All chemicals were obtained from Sigma-Aldrich, Alfa Aesar and S.
D. Fine chemicals and used as received.The progress of the reactions
was monitored by thin-layer chromatography (TLC) on precoated
silica-gel plates using Merck Silica Gel 60 F254, Cat. No.
1.05554.0007 and visualized by short-wave ultraviolet light as well as
by treatment with I2. Column chromatography was performed by hand
using silica-gel (100–200 mesh, Silicycle).1H and 13C NMR spectra
were recorded on Brucker-Avance DPX FT-NMR 500 and 400 MHz
instruments. Chemical data for protons are reported in parts per million
(ppm) downfield from tetramethylsilane and are referenced to the
residual proton in the NMR solvent (CDCl3: 7.26 ppm). Carbon
nuclear magnetic resonance spectra (13C NMR solvent
CDCl3:77.0ppm) were recorded at 125 MHz or 100 MHz: chemical
data for carbons are reported in parts per million (ppm, δ scale) down
field from tetramethylsilane and are referenced to the carbon
resonance of the solvent. ESI-MS and HRMS spectra were recorded
on Agilent 1100 LC-Q-TOF and HRMS-6540-UHD machines
respectively.
Scheme 7. Control Experiment.
Since, β-napthol is
a good C-nucleophile, we premeditated to
accomplish selenation reaction under optimized conditions for the
synthesis of 7 in good yield (Scheme 8).
General procedure for the synthesis of 2a-2m:Phenylhydrazine (1
mmol), selenium dioxide (1.5mmol) was taken in 5mL of acetonitrile
and stirred at 60oC for 1h. Desired product was observed on TLC after
1 h. However, after column purification on silica gel (100-200 #) using
hexane as an eluent afforded the corresponding product 2a-2m in
good yield (60-87 %).
Scheme 8.Selenation of β-Napthol.
3. Conclusion
General procedure for the synthesis of 3a-3c: Phenylhydrazine
(1mmol) substituted phenylhydrazine (1 mmol) and selenium dioxide
o
(1.5 mmol) were taken in 5mL of acetonitrile and stirred at 60 C for
1h. Desired product was observed on TLC after 1 h. However, after
column purification on silica gel (100-200 #) using hexane as an eluent
afforded the corresponding product 3a-3c in good yield (47-52%).
General procedure for the synthesis of 5a-5p: A reaction vessel
was charged with aniline (1 mmol), selenium dioxide (1.5 mmol) in 5
mL of acetonitrile solvent. The reaction mixture was stirred at 80 oC for
2.5 h. After completion of the reaction, confirmed by thin layer
To conclude, an efficient, economical, metal free coupling and
direct selenation methods for the conversion of hydrazines/anilines to
selenides were developed. These procedures avoid handlingand
isolationof expensive reagents and protecting groups. Both the
methodologies tolerate a broad range of functionalities. This protocol
can also be employed for the synthesis of hetero-coupling reactions.

5
Author Name/Engineering Science and Technology, an International Journal
chromatography, the solvent was removed under reduced pressure.
The crude mixture was purified by column chromatography on silica
gel (100-200#) using hexane and ethyl acetate (7:3) as an eluent. It
afforded the corresponding product 5a-5p in good yields (62-86 %).
General procedure for the synthesis of 6a-6e: A reaction vessel
was charged with aniline (1 mmol), substituted aniline (1mmol) and
selenium dioxide (1.5 mmol) in 5 mL of acetonitrile solvent. The
Hz), 134.92 (dd, J = 15.2, 8.0 Hz), 116.49 (t, J = 21.0 Hz).HRMS
(TOF) m/z [M + H]+Calcd for C12H9F2Se 270.9832 found 270.9840. IR
(CHCl3 cm-1) v;2995, 2961, 2934, 2875, 1695, 1684, 1653, 1616,
1261, 1218.
,2i.Di-p-tolylselane
Yellow solid (180.39 mg, 84% yield); 1H NMR (400 MHz, CDCl3) δ
7.50 (d, J = 7.3 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 7.8 Hz,
4H), 2.32 (s, 6H ) 13C NMR (100 MHz, CDCl3) δ 133.03, 132.35,
130.10, 129.94, 29.73.HRMS (TOF) m/z [M + H]+Calcd for C14H15Se
263.0333 found 263.0336. IR (CHCl3 cm-1) v; 2919, 2951, 2849, 1623,
1613, 1595, 1568.
o
reaction mixture was stirred at 80 C for 2.5h. After completion of the
reaction, confirmed by thin layer chromatography, the solvent was
removed under reduced pressure. The crude mixture was purified by
column chromatography on silica gel (100-200#) using hexane and
ethyl acetate (7:3) as an eluent. It afforded the corresponding product
6a-6e in good yields (43-51 %).
2j.Dis(3-fluorophenyl)selane
Yellow solid (145.49 mg, 68% yield); 1H NMR (400 MHz, CDCl3) δ
7.97 (d, J = 6.9 Hz, 2H), 7.84 (d, J = 8.3 Hz, 2H), 7.52 – 7.45 (m, 2H),
7.31 – 7.25 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 163.75 (s), 161.76
(s), 131.24 (s), 129.93 (d, J = 5.0 Hz), 121.66 (d, J = 15.0 Hz), 119.97
(d, J = 16 Hz).HRMS (TOF) m/z [M + H]+Calcd for C12H9F2Se
270.9832 found 270.9830. IR (CHCl3 cm-1) v;3065, 2961, 2923, 2849,
1700, 1611, 1580, 1523, 1262, 1197.
5. Spectral Data
2a.Diphenylselane
Yellow liquid (174.75 mg, 81% yield; 1H NMR (400 MHz, CDCl3) δ 7.65
(dd, J = 6.1, 2.6 Hz, 4H), 7.43 – 7.39 (m, 4H). 13C NMR (100 MHz,
CDCl3) δ 133.23, 131.44, 129.61, 127.58.HRMS(TOF) m/z [M +
H]+Calcd for C12H11Se 235.0020 found 235.0016. IR (CHCl3 cm-1) v;
3070, 3056, 3016, 2997, 2922, 2850, 1650, 1575.
2k.Di-m-tolylselane
Yellow solid (173.28 mg, 81% yield); 1H NMR (400 MHz, CDCl3) δ
7.69 – 7.56 (m, 4H), 7.36 (d, J = 5.7 Hz, 4H), 2.42 (s, 6H). 13C NMR
2b.Bis(2-(trifluoromethyl)phenyl)selane
Yellow solid (134.18 mg, 64% yield); 1H NMR (400 MHz, CDCl3) δ
7.76 (d, J = 7.2 Hz, 4H), 7.43 – 7.37 (m, 4H). 13C NMR (100 MHz,
CDCl3) δ 136.62 (q), 132.52 (s), 131.83 (d, J = 24.0 Hz), 130.05 (s),
127.78 (s), 126.94 (m, J = 5.0 Hz), 123.73 (d, J = 218.0 HzHRMS
(TOF) m/z [M + H]+ Calcd for C14H9 F6Se 370.9768 found 370.9772. IR
(CHCl3 cm-1) v; 3200, 2952, 2918,2846,1695, 1659, 1642,1612, 1554,
1257, 1217.
(100 MHz, CDCl3)
δ 137.39, 135.26, 131.92, 131.84, 127.89,
21.2.HRMS (TOF) m/z [M + H]+Calcd for C14H15Se 263.0333 found
263.0337. IR (CHCl3 cm-1) v; 2919, 2951, 2849, 1623, 1613, 1595,
1568, 270, 261.
2l.Bis(3-methoxyphenyl)selane
Yellow solid (178.95 mg, 84% yield); 1H NMR (400 MHz, CDCl3) δ
7.38 (d, J = 4.9 Hz, 4H), 7.34 (d, J = 2.1 Hz, 2H), 7.10 – 7.04 (s, 2H),
3.84 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 159.14, 129.19, 127.02,
119.48, 116.94, 54.89.HRMS (TOF) m/z [M + H]+Calcd for C14H15O2Se
295.0232found 295.0233. IR (CHCl3 cm-1) v; 3070, 3056, 3016, 2997,
2922, 2850, 1650, 1575, 1095, 1055.
2c.Bis(4-(trifluoromethyl)phenyl)selane
Yellow solid (138.37 mg, 66% yield); 1H NMR (400 MHz, CDCl3) δ
7.64 – 7.47 (m, 8H). 13C NMR (100 MHz, CDCl3) δ 135.15 (q), 133.07
(s), 129.98 (m, J = 26.0 Hz), 126.33 (d, J = 3.4 Hz), 123.92 (d, J =
217.0 Hz).HRMS(TOF) m/z [M + H]+Calcd for C14H9 F6Se 370.9768
found 370.9770. IR(CHCl3 cm-1) v; 2956, 2923, 2849,1695, 1658,1652,
1641, 1261, 1216.
2m.Bis(3,4-dimethoxyphenyl)selane
Yellow solid (183.32 mg, 87% yield); 1H NMR (400 MHz, CDCl3) δ
7.41 (d, J = 7.9 Hz, 2H), 7.35 (s, 2H), 6.97 (d, J = 8.0 Hz, 2H), 3.94 (s,
6H), 3.92 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 151.67, 148.47,
128.92, 116.84, 110.55, 55.87, 55.82.HRMS (TOF) m/z [M + H]+Calcd
for C16H19O4Se 355.0443 found 355.0449. IR (CHCl3 cm-1) v; 3030,
3016, 3005, 2997, 2930, 2850, 1650, 1520, 1095, 1055. 1025.
3a. (4-Fluorophenyl)(phenyl)selane
2d.Bis(2-chlorophenyl)selane
Yellow solid (148.38 mg, 70% yield); 1H NMR (400 MHz, CDCl3) δ
7.49 – 7.45 (m, 2H), 7.29 – 7.23 (m, 4H), 7.19 – 7.13 (m, 2H). 13C
NMR (100 MHz, CDCl3) δ 136.46, 134.22, 130.35, 129.89, 129.12,
127.63.HRMS (TOF) m/z [M + H]+Calcd for C12H9Cl2Se 302.9241
found 302.9237. IR (CHCl3 cm-1) v; 2922, 2851, 2822, 1695, 1642,
1612, 1516, 893, 801.
Yellow solid (95.66 mg, 41% yield); 1H NMR (400 MHz, CDCl3) δ 7.49
(dd, J = 6.5, 3.0 Hz, 3H), 7.45 – 7.41 (m, 1H), 7.31 – 7.27 (m, 4H),
7.03 – 6.98 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 135.76 (d, J =
6.0Hz), 134.99 (d, J = 7.8 Hz), 132.97 (s), 132.22 (s), 131.15 (s),
129.38 (s), 127.31 (d, J = 13.0 Hz), 116.71 (d, J = 2.1 Hz).HRMS
(TOF) m/z [M + H]+Calcd forC12H10FSe 252.9926 found 252.9930. IR
(CHCl3 cm-1) v; 3146, 3058, 3016, 2998, 2959, 2923, 2852, 1635,
1581, 1485, 1476, 1437, 1291, 1180, 1261.
2e.Bis(4-chlorophenyl)selane
Yellow solid (152.61 mg, 72% yield); 1H NMR (400 MHz, CDCl3) δ
7.40 (d, J = 8.4 Hz, 4H), 7.28 (d, J = 8.8 Hz, 4H). 13C NMR (100 MHz,
CDCl3) δ 134.60, 132.60, 132.35, 129.43.HRMS(TOF) m/z [M +
H]+Calcd for C12H9Cl2Se 302.9241 found 302.9249. IR (CHCl3 cm-1) v;
2918, 2955, 2847, 1620, 1554, 1533,1516, 893, 866.
2f.4,4'-Selenodibenzonitrile
3b. (4-Chlorophenyl)(phenyl)selane
Yellow solid (127.66 mg, 60% yield);1H NMR (400 MHz, CDCl3) δ 7.69
(d, J = 7.2 Hz, 2H), 7.61 – 7.51 (m, 6H). 13C NMR (100 MHz, CDCl3) δ
133.28, 132.99, 132.75, 130.63, 118.25.HRMS (TOF) m/z [M +
H]+Calcd for C14H9N2Se 284.9925 found 284.9930. IR (CHCl3 cm-1) v;
3080, 3030, 2958, 2852, 2227, 1696, 1653, 1584, 1553, 1481.
2g.Bis(4-bromophenyl)selane
Yellow solid (106.70 mg, 43% yield); 1H NMR (400 MHz, CDCl3) δ
7.40 (dd, J = 6.5, 3.0 Hz, 2H), 7.33 – 7.29 (m, 2H), 7.24 – 7.21 (m,
2H), 7.20 – 7.15 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 135.79,
134.96, 133.01, 132.22, 131.15, 129.40, 127.33, 116.64.HRMS(TOF)
m/z [M + H]+Calcd forC12H10ClSe 268.9631 found 268.9637. IR (CHCl3
cm-1) v; 3063, 2952, 2919, 2849, 1662, 1652, 1640,1635, 1623, 1616,
771, 733.
Yellow solid (159.80 mg, 76% yield); lH NMR (400 MHz, CDCl3) δ 7.58
– 7.20 (m, 8H) 13C NMR (100 MHz, CDCl3) δ 134.60, 132.60, 132.35,
129.43.HRMS(TOF) m/z [M + H]+Calcd for C12H9Br2Se 390.8231
found 390.8235. IR (CHCl3 cm-1) v; 3070, 2919, 2959, 2847, 1684,
1534, 1516, 1512, 727, 707.
3c. (3-Chlorophenyl)(phenyl)selane
Yellow solid (101.74mg, 41% yield); 1H NMR (400 MHz, CDCl3) δ 7.40
(dd, J = 6.5, 3.0 Hz, 2H), 7.33 – 7.29 (m, 2H), 7.24 – 7.21 (m, 2H),
7.20 – 7.15 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 135.79, 134.96,
133.01, 132.22, 131.15, 129.40, 127.33, 116.64. HRMS (TOF) m/z [M
+ H]+Calcd for C12H10ClSe 268.9631 found 268.9637. IR (CHCl3 cm-1)
2h.Bis(4-fluorophenyl)selane
Yellow solid (138.76 mg, 65% yield); 1H NMR (400 MHz, CDCl3) δ
7.64 – 7.50 (m, 2H), 7.48 – 7.44 (m, 2H), 7.04 – 6.97 (m, 4H). 13C
NMR (100 MHz, CDCl3) δ 164.01 (d, J = 48.0 Hz), 161.55 (d, J = 47.6

6
<Journal Name>
v; 3063, 2952, 2919, 2849, 1662, 1652, 1640, 1635, 1623, 1616, 771,
733.
5a. 4,4'-Selenodianiline.
Black solid (193.77 mg, 68% yield); 1H NMR (400 MHz, CDCl3) δ 7.33
– 7.27 (m, 4H), 6.63 – 6.58 (m, 4H), 3.49 (s, 4H). 13C NMR (100 MHz,
CDCl3) δ 145.75, 135.10, 119.34, 116.04. HRMS (TOF) m/z [M +
H]+Calcd for C12H13N2Se 265.0238 found 265.0247.IR (CHCl3 cm-1) v ;
3451, 3339, 3021, 2970, 2955, 2928, 1684, 1675, 1669, 1623,
1550, 1533
5i. 4,4'-Selenobis(2,6-dimethylaniline)
Black solid (222.87 mg, 84% yield); 1H NMR (400 MHz, CDCl3) δ 7.14
(s, 4H), 3.58 (s, 4H), 2.16 (s, 12H). 13C NMR (100 MHz, CDCl3) δ
142.36, 133.34, 122.64, 118.91, 17.55. HRMS (TOF) m/z [M +
H]+Calcd for C16H21N2Se 321.0864 found 321.0859.IR (CHCl3 cm-1)
v;3451, 3359, 3021, 2970, 2928, 2855, 1684, 1675, 1669, 1653, 1623,
1533, 1472.
5j. 4,4'-Selenobis(5-chloro-2-iodoaniline)
Black solid (152.40 mg, 66% yield); 1H NMR (400 MHz, CDCl3) δ 7.59
(s, 2H), 6.86 (s, 2H), 4.40 – 4.01 (s, 4H). 13C NMR (100 MHz, CDCl3) δ
147.03, 143.86, 138.18, 119.43, 114.98, 82.35. HRMS (TOF) m/z [M +
H]+Calcd for C12H9Cl2I2N2Se 584.7392 found 584.7382.IR(CHCl3 cm-1)
v; 3365, 2920, 2847, 1695, 1659, 1642, 1612, 1565, 1554, 1533,
1453, 839, 770, 665, 502.
5b. 4, 4'-Selenobis (2-fluoroaniline)
Black solid (192.93 mg, 71% yield); 1H NMR (400 MHz, CDCl3) δ 7.29
– 7.00 (m, 2H), 6.81 – 6.61 (m, 4H), 3.65 (s, 4H) 13C NMR (100 MHz,
CDCl3) δ 162.78 (d, J = 240 .3 Hz), 148.73 (d, J = 10.7 Hz), 136.57 (d,
J = 7.7 Hz), 111.67 (d, J = 2.0 Hz), 104.12 (d, J = 23.4 Hz), 102.24 (d,
J = 27.3 Hz). HRMS (TOF) m/z [M + H]+Calcd for C12H11F2N2Se
301.0056 found 301.0051.IR (CHCl3 cm-1) v; 3355, 2918, 2847, 1695,
1659, 1642, 1554, 1534, 1516, 1489, 1279, 1175.
5k. 4,4'-Selenobis(2-iodoaniline)
Black solid (151.50 mg, 69% yield); 1H NMR (400 MHz, CDCl3) δ 7.71
(s, J = 1.6 Hz, 2H), 7.20 – 7.09 (m, 2H), 6.57 (d, J = 8.3 Hz, 2H), 4.19
– 3.35 (s, 4H). 13C NMR (100 MHz, CDCl3) δ 146.28, 142.58, 134.76,
120.20, 115.09, 84.21. HRMS (TOF) m/z [M +H]+Calcd for
C12H11I2N2Se 516.0029 found 516.0033.IR(CHCl3 cm-1) v; 3362, 2955,
2923, 2851, 1695, 1665, 1659, 1642, 1573, 1554, 1539, 1471, 666,
523.
5c.4,4'-Selenobis(3-fluoroaniline)
Black solid (181.68 mg, 67% yield); 1H NMR (400 MHz, CDCl3) δ 7.11
(d J = 8.0 Hz, 2H), 6.30 (m, J = 10.6, 9.2, 2.2 Hz, 4H), 3.70 (s, 4H) 13
C
NMR (100 MHz, CDCl3) δ 162.78 (d, J = 240 .3 Hz), 148.73 (d, J =
10.7 Hz), 136.57 (d, J = 7.7 Hz), 111.67 (d, J = 2.0 Hz), 104.12 (d, J =
23.4 Hz), 102.24 (d, J = 27.3 Hz). HRMS (TOF) m/z [M + H]+Calcd for
C12H11F2N2Se 301.0056 found 301.0054.IR (CHCl3 cm-1) v; 3373,
2922, 2847, 1622, 1603, 1487, 1466, 1318, 1236
5l. 4,4'-Selenobis(2,5-dimethylaniline)
Brown black solid (206.97 mg, 78% yield); H NMR (400 MHz, CDCl3)
δ 6.90 (s, 2H), 6.50 (s, 2H), 3.44 (s, 4H), 2.22 (s, 6H), 1.98 (s, 6H). 13
1
C
5d. 4,4'-Selenobis(3-chloroaniline)
NMR (100 MHz, CDCl3) δ 144.05, 138.61, 135.54, 120.96, 119.65,
116.82, 21.97, 16.80. HRMS (TOF) m/z [M + H]+Calcd for C16H21N2Se
321.0864 found 321.0860.IR (CHCl3 cm-1) v; 3372, 30006, 2956, 2858,
1621, 1565, 1489, 1457, 1395, 1371, 1291.
Black solid (173.02 mg, 66% yield); 1H NMR (400 MHz, CDCl3) δ 7.09
(s, J = 8.4 Hz, 2H), 6.80 (d, J = 2.4 Hz, 2H), 6.49 (dd, J = 8.4, 2.5 Hz,
2H), 3.76 (s, 4H). 13C NMR (100 MHz, CDCl3) δ 147.35, 137.45,
135.27, 117.96, 115.96, 114.29. HRMS (TOF) m/z [M + H]+Calcd for
C12H11Cl2N2Se 332.9465 found 332.9469.IR (CHCl3 cm-1) v; 3469,
3375, 3192, 3048, 3019, 2957, 2924, 2852, 1613, 1583, 1481, 845,
755.
5m. 4,4'-Selenobis(3-methoxy-2-methylaniline)
1
Brown black solid (172.63 mg, 67% yield); HNMR (400 MHz, CDCl3)
δ 6.64 (dd, J = 27.5, 10.0 Hz, 4H), 4.80 (s, 4H), 4.01 (s, 3H), 2.49 (s,
3H), 1.90 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 143.48, 139.05,
132.12, 119.75, 110.56, 60.43, 29.57, 12.98, 8.43. HRMS (TOF) m/z
[M + H]+Calcd for C16H21N2Se 353.0763 found 353.0761. IR (CHCl3
cm-1) v; 3372, 30006, 2956, 2858, 1621, 1565, 1489, 1457, 1395,
1371, 1291.
5e. 4,4'-Selenobis(3-bromo-2-methylaniline)
Black solid (164.67 mg, 68% yield); 1H NMR (400 MHz, MeOD) δ 6.72
(d, J = 8.3 Hz, 2H), 6.50 (d, J = 8.4 Hz, 2H), 3.21 (s, 4H), 2.21 (s,
6H).13C NMR (100 MHz, CDCl3) δ 150.08, 135.42, 133.60, 127.04,
125.57, 118.63, 21.22. HRMS (TOF) m/z [M +H]+Calcd for
C14H15Br2N2Se 448.8767 found 448.8774.IR (CHCl3 cm-1) v; 3375,
2922, 2851, 1695, 1659, 1621, 1555, 1486, 1461, 1379, 769, 669.
5f. 4,4'-Selenobis(2,3-dimethylaniline)
5n. 4,4'-Selenobis(2-methoxyaniline)
Brown black solid (203.45 mg, 77% yield); H NMR (400 MHz, CDCl3)
1
δ 7.15 – 7.02 (m, 1H), 6.97 (d, J = 6.5 Hz, 3H), 6.64 (dd, J = 12.2, 8.1
Hz, 2H), 3.92 (s, 4H), 3.83 (s, 6H). 13C NMR (100 MHz, CDCl3) δ
147.40, 146.89, 137.15, 135.60, 128.26, 127.69, 126.28, 119.22,
117.05, 115.57, 115.39, 114.60, 55.27.HRMS(TOF) m/z [M + H]+
Calcd for C16H21N2Se 325.0450 found 325.0447. IR (CHCl3 cm-1) v;
3372, 30006, 2956, 2858, 1621, 1565, 1489, 1457, 1395, 1371, 1291
5o. 5-Di(indolin-5-yl)selane
Black solid (201.67 mg, 76% yield); 1H NMR (400 MHz, CDCl3) δ 7.00
(d, J = 8.2 Hz, 2H), 6.49 (d, J = 8.2 Hz, 2H), 3.62 (s, 4H), 2.47 – 2.38
(s, 6H), 2.19 – 2.12 (s, 6H)..13C NMR (100 MHz, CDCl3) δ 144.12,
138.62, 131.53, 121.84, 121.35, 113.91, 19.43, 13.79.HRMS (TOF)
m/z [M + H]+Calcd for C16H21N2Se 321.0864 found 321.0867.IR (CHCl3
cm-1) v; 3373, 3229, 2960, 2921, 2859, 1653, 1617, 1576, 1505, 1464,
1415.
1
Black solid 167.72 mg, 63% yield); H NMR (400 MHz, CDCl3) δ 7.18
(s, 3H), 7.11 (d, J = 8.0 Hz, 3H), 6.46 (d, J = 8.0 Hz, 2H), 3.47 (t, J =
8.4 Hz, 4H), 2.91 (t, J = 8.4 Hz, 4H). 13C NMR (100 MHz, CDCl3) δ
150.87, 132.50, 131.09, 129.59, 120.05, 110.21, 47.24, 29.97. HRMS
(TOF) m/z [M + H]+Calcd forC16H17N2Se 317.0551 found 317.055IR
(CHCl3 cm-1) v; 3379, 2923, 2849, 1695, 1659, 1642, 1599, 1485,
1469, 1454, 1434, 1416, 1317, 1277.
5g. 4,4'-Selenobis(2-chloroaniline
Black solid (180.24 mg, 69% yield); 1H NMR (400 MHz, CDCl3) δ 7.32
(s, J = 1.6 Hz, 2H), 7.11 (dd, J = 8.2, 1.7 Hz, 2H), 6.58 (d, J = 8.3 Hz,
2H), 3.94 (s, 4H). 13C NMR (100 MHz, CDCl3) δ 142.62, 134.15,
133.09, 119.62, 119.35, 116.48. HRMS (TOF) m/z [M + H]+Calcd for
C12H11Cl2N2Se 332.9465 found 332.9468.IR (CHCl3 cm-1) v; 3461,
3371, 3219, 3054, 2971, 2925, 1620, 1588, 1556, 1470, 1412, 812,
757.
5p. 4,4'-Selenobis(N-phenylaniline)
Black solid (165.27 mg, 67% yield); 1H NMR (400 MHz, CDCl3) δ 7.41
(d, J = 8.6 Hz, 4H), 7.29 (dd, J = 13.0, 5.3 Hz, 4H), 7.09 (d, J = 7.8 Hz,
4H), 6.98 (t, J = 7.0 Hz, 6H), 5.73 (s, 2H).13C NMR (100 MHz, CDCl3)
δ 142.75 , 142.45 , 134.45 , 129.45 , 121.97 , 121.57 , 118.38 , 118.17
.HRMS (TOF) m/z [M + H]+Calcd for C24H21N2Se 417.0864 found
417.0874.IR (CHCl3 cm-1) v; 3393, 3052, 3025, 2960, 2921, 1585,
1503, 1486, 1441, 1390.
5h. 4,4'-Selenobis(2-bromoaniline)
Black solid (159.13 mg, 65% yield); 1H NMR (400 MHz, CDCl3) δ 7.57
(s, J = 0.9 Hz, 2H), 7.22 (dd, J = 8.3, 0.9 Hz, 2H), 6.64 (d, J = 8.2 Hz,
2H), 4.11 (s, 4H). 13C NMR (100 MHz, CDCl3) δ 143.80, 137.30,
133.81, 119.74, 116.41, 109.58. HRMS (TOF) m/z [M +H]+Calcd for
C12H11Br2N2Se 420.8449 found 420.8446.IR(CHCl3 cm-1) v; 3465,
3374, 3187, 3014, 3045, 2958, 2922, 2851, 1613, 1579, 1552, 1477,
756, 682
6a. 4,4'-Aminophenyl)selanyl)-3-fluoroaniline
Black solid (124.76 mg, 41% yield); 1H NMR (400 MHz, CDCl3) δ 7.34
(d, J = 7.9 Hz, 2H), 7.18 (d, J = 23.2, 7.8 Hz, 2H), 6.61 (d, J = 7.8 Hz,

7
Author Name/Engineering Science and Technology, an International Journal
1H), 6.45 – 6.32 (m, 2H), 3.73 (s, 4H). 13C NMR (100 MHz, CDCl3) δ
147.73 (s), 145.52 (s), 139.12 (s), 136.98 (s), 132.82 (d, J = 56.4 Hz),
130.42 (s), 129.98 (s), 118.82 (s), 116.26 (s), 115.03 (d, J = 5.0 Hz),
105.73 (d, J = 21.9 Hz), 101.49 (d, J = 28.0Hz).HRMS (TOF) m/z [M +
H]+Calcd for C12H12FN2Se 283.0144 found 283.0143.IR (CHCl3 cm-1) v;
3360, 3213, 2955, 2921, 2850, 1695, 1680, 1658, 1612, 1554, 1516,
1443, 1433, 1281, 1165.
(c) I. L. Martins, C. Charneira, V. Gandin, J. L. Ferreira da Silva, G. C.
Justino, J. P. Telo, A. J. S. C. Vieira, C. Marzano, A. M. M. Antunes, J.
Med. Chem. 58(2015) 4250;
(d) J. A. Woods, J. A. Hadfield, A. T. McGown, B. W. Fox, Bioorg. Med.
Chem. 1(1993) 333;
(e) L. Engman, D. Stern, H. Frisell, K. Vessman, M. Berglund, B. Ek, C-M.
Andersson, Bioorg. Med. Chem. 3(1995) 1255;
6b.44' -Amino-2-chlorophenyl)selanyl)-3-fluoroaniline
(f) T. Chatterjee, and B. C. Ranu, J. Org. Chem. 78(2013) 7145;
(g) R. N. Gaykar, A. Guin, S. Bhattacharjee, A. T. Biju, Org. Lett. 21, 23
(2019) 9613-9617.
Black solid (111.02 mg, 39% yield); 1H NMR (400 MHz, CDCl3) δ 7.52
– 7.42 (s, 1H), 6.92 (d, J = 16.0, 8.0 Hz, 1H), 6.41 – 6.22 (m, 4H), 3.93
(s, 4H). 13C NMR (100 MHz, CDCl3) δ 163.83 – 163.62 (m), 163.35 –
163.26 (m), 161.83 – 161.77 (m), 161.41 – 161.34 (m), 136.58 (d, J =
3.0 Hz), 135.92 (d, J = 3.0 Hz), 135.31 (s), 134.57 (s), 115.96 (s),
111.66 (s), 104.23 – 103.99 (m), 102.24 (d, J = 22.0 Hz). HRMS (TOF)
m/z [M + H]+Calcd for C12H11ClFN2Se 316.9755 found 316.9761.IR
(CHCl3 cm-1) v; 3373, 3219, 2955, 2921, 2851, 1695, 1687, 1622,
1602, 1487, 1469, 1437, 1314, 1235, 1044, 958, 840.
[2] (a)T. Ando, T. S. Kwon, A. Kitagawa, T. Tanemura, S. Kondo, H. Kunisada,
Y. Yuki, Macromol. Chem. Phys. 197(1996) 2803;
(b) P. K. Khanna, B. K. Das, Mater. Lett. 58 (2004) 1030;
(c) T. E. Frizon, D. S. Rampon, H. Gallardo, A. A. Merlo, P. H. Schneider, O. E.
D. Rodrigues, A. L. Braga, Liq. Cryst. 39(2012) 769;.
(d) A. Kumar, G. K. Rao, F. Saleem, A. K. Singh, Dalton Trans.41 (2012 )11949;
[3](a)K. Ren, M. Wang, and L. Wang, Org. Biomol. Chem.7(2009) 4858;
(b) I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov, P. V. Petrovskii, V.
N.Khrustalev, Chem. Lett. 39(2010) 720.
6c. 4-4'-Aminophenyl)selanyl)-2-fluoroaniline
(c) I. P. Beletskaya, V. P. Ananikov, Chem. Rev. 111(2011) 1596;
(d) H. Zhao, W. Hao, Z. Xi, M. Cai, New J. Chem. 35(2011) 2661;
(e) Y. Wang, W-X. Zhang, Z. Wang, Z. Xi, Angew. Chem., Int.Ed.50(2011)8122;
(f) V. G. Ricordi, C. S. Freitas, G. Perin, E. J. Lenardao, R. G. Jacob, L.
Savegnago, D. Alves, Green Chem.14 (2012)1030;
1
Black solid (130.8561 mg, 43% yield); H NMR (400 MHz, CDCl3) δ
7.54 (d, J = 7.6 Hz, 1H), 7.26 – 7.16 (m, 2H), 6.78 (d, J = 8.0 Hz, 1H),
6.71 (t, J = 7.5 Hz, 1H), 6.61 (d, J = 8.3 Hz, 2H), 4.35 (s, 2H), 3.69 (s,
2H).13C NMR (100 MHz, CDCl3) δ 147.77 (s), 145.77 (s), 136.98 (s),
133.18 (s), 130.02 (s), 118.82 (s), 118.29 – 115.19 (d), 116.17 (s),
114.99 (s).HRMS (TOF) m/z [M + H]+Calcd for C12H12FN2Se 283.0144
found 283.0140. IR (CHCl3 cm-1) v; 3360, 3213, 2955, 2921, 2850,
1695, 1680, 1658, 1612, 1554, 1516, 1443, 1433, 1281, 1165.
6d. 44'-Aminophenyl)selanyl)-2-bromoaniline
(g) D. Kundu, S. Ahammed, B. C. Ranu, Org. Lett. 16 (2014)1814 Lyle, F. R.
U.S. Patent 5 973 257, 1985; Chem. Abstr.65(1985)2870;
[4] D. Kundu, S. Ahammed, B. C. Ranu, Green Chem., 142012) 2024;
[5]
D. Kundu, S. Ahammed, B. C. Ranu,Org. Lett, 16(2014)1814;
Black solid (161.80 mg, 44% yield); 1H NMR (400 MHz, CDCl3) δ 7.26
(dd, J = 16.0, 8.3 Hz, 2H), 7.11 (dt, J = 21.8, 8.0 Hz, 1H), 6.54 (d, J =
8.1 Hz, 2H), 6.37 – 6.27 (m, 2H), 3.72 (s, 4H). 13C NMR (100 MHz,
CDCl3) δ 147.69, 145.75, 137.01, 136.44, 135.15, 133.06, 129.98,
[6] (a)M. Iwasaki, Y. Tsuchiya, K. Nakajima, Y. Nishihara, Org. Lett. 16(2014)
4920;
(b) M. Iwasaki, W. Kaneshika, Y.Tsuchiya, K. Nakajima, Y. Nishihara, J. Org.
Chem. 79 (2014) 11330;
(c) W. Jin, P. Zheng, W-T. Wong, G-L. Law, Asian J. Org. Chem. 4,(2015) 875;
118.69, 116.26, 114.88 HRMS (TOF) m/z [M
+
H]+Calcd for
(d) S. Vasquez-Ce ́ spedes, A. Ferry, L. Candish, F. Glorius, Angew. Chem., Int.
C12H12FN2Se 342.9344 found 342.9347. IR (CHCl3 cm-1) v; 3360,
3213, 2955, 2921, 2850, 1695, 1680, 1658, 1612, 1554, 1516, 1443,
1433, 1281, 1165.
Ed.54(2015) 5772;
(e) W. Jin, P. Zheng, G.-L. Law, W-T. J. Wong, Organomet. Chem. 812(2016)
66.
(f)R. Qiu, V. P. Reddy, T. Iwasaki, N. Kambe, J. Org. Chem.80 (2015)367;
(g)T.Taniguchi ,A.Murata ,M.Takeda ,T.Mizuno ,A.Nomoto ,A.Agawa
Eur.J.Org.chem. 33 (2017) 4928;
6e.44'-Amino-2-fluorophenyl)selanyl)-2-iodoaniline
Black solid (150.70 mg, 41% yield); 1H NMR (400 MHz, CDCl3) δ 7.62
– 7.52 (m, 1H), 7.02 (t, J = 8.0 Hz, 1H), 6.53 – 6.33 (m, 4H), 4.32 (s,
4H). 13C NMR (100 MHz, CDCl3) δ 163.83 – 163.62 (m), 163.35 –
163.26 (m), 161.83 – 161.77 (m), 161.41 – 161.34 (m), 136.58 (d, J =
3.0 Hz), 135.92 (d, J = 3.0 Hz), 135.31 (s), 134.57 (s), 115.96 (s),
111.66 (s), 104.23 – 103.99 (m), 102.24 (d, J = 22.0 Hz).HRMS (TOF)
m/z [M + H]+Calcd for C12H12FN2Se 408.9111 found 408.9110 IR
(CHCl3 cm-1) v; 3360, 3213, 2955, 2921, 2850, 1695, 1680, 1658,
1612, 1554, 1516, 1443, 1433, 1281, 1165
(h)A.J. Sahania , A. S. Burangeb, , S. D. Thakurb , R. V. Jayarama.
Mol.Cat.476 (2019),110534;
[7](a) P. Sehnal, R. J. K. Taylor, I. J. S. Fairlamb, Chem. Rev. 110(2010) 824;
(b)P. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem. Rev.11 (2012) 5879;
(c) K. M. Engle, T-S. Mei, M. Wasa, J.-Q. Yu, Acc. Chem. Res. 45 (2012)788;
(d) A. N. Vedernikov, Acc. Chem. Res. 45 (2012)803.
(e) D. C. Powers, T. Ritter, Acc. Chem. Res. 45 (2012) 840;
(f) J. F. Hartwig, Acc. Chem. Res.45(2012), 864;
(g) J. Liu, G. Chen, Z. Tan, Adv. Synth. Catal. 358(2016) 1174;
(h) W. Liu, L. Ackermann, ACS Catal. 6(2016) 3743;
7. 1,1'-Selenobis(naphthalen-2-ol)
Brown solid (167.29mg, 66% yield); 1H NMR (400 MHz, CDCl3) δ 7.98
(d, J = 8.3 Hz, 2H), 7.90 (d, J = 6.9 Hz, 2H), 7.36 (dd, J = 25.9, 6.7 Hz,
6H), 7.17 (d, J = 6.8 Hz, 2H), 5.08 (s, 2H). 13C NMR (100 MHz, CDCl3)
δ 152.78, 134.43, 129.17, 128.94, 127.71, 125.82, 124.42, 122.33,
117.89, 114.63. HRMS (TOF) m/z [M - H]+Calcd for C20H13O2Se
365.0086 found 365.0077.IR(CHCl3 cm-1) v; 3487, 3058, 3013, 2956;
2923, 2853, 1695, 1658, 1642, 1619, 1596, 1554, 1515, 1462, 1433,
1383.
[ 8] J. F. K. Wilshire, Aust. J. Chem.20, (1967) 359;
[9] B.Y.DakovaN.J.Evers,L.R.Christimas, N.R Guillman.Bull.Soc.Chim.Belg.
96 (1987
[10]A.J.Sahani, A.S. Burange, S.D.Thakur, R.V.Jayaram, Molecular catalysis476
(2019) 110534.
Acknowledgments
M. Y. B and A. Kumar thanks CSIR and UGC for the award of JRF and
SRF respectively. We also thank the analytical department of IIIM.
Finally, I am grateful to the CSIR network project (BSC-0108) for
funding to this work. IIIM communication no. CSIR-IIIM/IPR/00113.
References
[1](a)G. Mugesh, W-W. du Mont, H. Sies, Chem. Rev. 101 (2001) 2125;
(b) C. W. Nogueira, G. Zeni, J. B. T. Rocha, Chem. Rev.104 (2004) 6255;

8
<Journal Name>

The present work highlights the following important findings:
1. A novel, efficient, economical strategy for the direct selenation of
arylamines and hydrazines to selenides using SeO2 was successfully
developed.
2. Our reaction revealed a good functional group tolerance and proceeded well
with variation in the electronic nature of Anilines and Phenylhydrazines.
3. This reagent is compatible with hydrazines and helps to promotes unusual
dinitrogen extrusion assisted selenation reaction in good yields.
4. The application of our work is the gram scale synthesis and extension to
napthol.
β-
5. Mechanistically, first SeO2 undergoes a disproportionation process to afford
dianilinetriselenides as per Wilshire’s assumption. However, there exist
three different possibilities of trisilinides out of which the para-para is
formed in maximum quantity followed by para-ortho triselenation.
6. Application of this approach towards Selenation of β-Napthol
7. Further studies related to the application of this system against different C-
nucleophiles is in progress