Reaction of ketone hydrazones with TeCl4: Isolation and reactions of novel divinyl telluride

Article abstract of DOI:10.1039/d0ob00782j

The reaction of acetophenone hydrazones with TeCl4 in the presence of DBU gave a mixture of divinyl ditellurides and divinyl tellurides, which easily reacted with Cu powder in refluxing toluene to afford divinyl tellurides in good yields. The reaction of divinyl tellurides with bromine (1.2 eq.) gave the corresponding tellurium dibromide rather than the addition of the double bond whereas 3 molar amount of bromine gave excess brominated and oxidized products. The reaction of divinyl tellurides with 2-(trimethylsilyl)phenyl triflate in the presence of CsF gave (E)-2-alkenyldiaryl tellurides in good yields.

Full text of DOI:10.1039/d0ob00782j

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DOI: 10.1039/D0OB00782J
ARTICLE
Reaction of ketone hydrazones with TeCl4: Isolation and reactions
of novel divinyl telluride
Kentaro Okuma,* Yuxuan Qu, Aoi Suetome, and Noriyoshi Nagahora
Received 00th January 20xx,
Accepted 00th January 20xx
Reaction of acetophenone hydrazones with TeCl4 in the presence of DBU gave a mixture of divinyl ditellurides and divinyl
tellurides, which easily reacted with Cu powder in refluxing toluene to afford divinyl tellurides in good yields. Reaction of
divinyl telluride with bromine (1.2 eq) gave the corresponding tellurium dibromide rather than the addition of the double
bond whereas 3 molar amount of bromine gave excess brominated and oxidized products. Reaction of divinyl tellurides
with 2-(trimethylsilyl)phenyl triflate in the presence of CsF gave (E)-2-alkenyldiaryl tellurides in good yields.
DOI: 10.1039/x0xx00000x
R'Te
+
R
NaBH4
Introduction
+ R'TeTeR'
R
Mack
H
R
TeR'
Organic tellurium compounds have been the focus of intensive
study and a number of literature appeared for their valuable
synthetic intermediates.1 Tellurophenes are well known for their
use of organic materials due to their fluorescence activity.2
major
minor
H
+ Te + KOH
+ SnCl2
Te
H2O
Vinyl tellurides constitute important organic tellurium compounds
that is often employed in organic synthesis.3 Hydrotelluration of
alkynes to give vinyl tellurides is a well-known method for the
formation of 2-substituted vinyl tellurides. Preparation of simple
divinyl telluride was reported by Potapov et al.,4 whereas 1-aryl
substituted divinyl tellurides were not synthesized until our recent
communication,5 which constitutes a convenient synthesis of 2,5-
diaryltellurophenes by the reaction of acetophenone hydrazones
with tellurium tetrachloride in the presence of DBU, intermediates of
which would be divinyl ditellurides along with small amount of divinyl
tellurides. We have also reported that reaction of camphor
hydrazone with TeCl4 gave the corresponding ditelluride.6 During
mechanistic investigation of these reactions, we have found a
convenient synthesis of divinyl tellurides. Herein, we would like to
show the isolation of divinyl tellurides and novel formation of
tellurium dibromides by the reaction with bromine and 2-
alkenyldiaryl tellurides by the reaction with benzyne (Figure 1).
autoclave
110-120 o
Trofimov et al.
C
Ar
1) DBU
CH2
Ar
H2C
Ar
CH2
Ar
H2C
Ar
NNH2
Br2
2) Cu
H3C
Te
1
Te
Br
Br
TeCl4
+
3
5
H
Ar
H
Ar
Te
H
H
11
This work
Figure 1. Previous results and this work
Results and discussion
Initially, the reaction of p-methylacetophenone hydrazone (1a)
with TeCl4 was selected for screening the reaction conditions. We
evaluated the influence of temperature, solvent, and molar
amounts of TeCl4 and bases. Treatment of 1a with TeCl4 (1 eq) and
Et3N (3 eq) in refluxing DMF resulted in the formation of 2,5-di-p-
tolyltellurophene 2a and bis(1-p-tolyl)vinyl telluride (3a) in 32% and
12% yields, respectively (Table 1, entry 1). Other results were
shown in Table 1.
a. Department of Chemistry, Fukuoka University, Jonan-ku, Fukuoka 814-0180,
Japan.
.† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [1H and 13C NMR spectra and
X-ray crystallographic data]. See DOI: 10.1039/x0xx00000x
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Page 2 of 8
ARTICLE
Journal Name
a
Table 1. Reaction of 1a with TeCl4 in the presence of Basea
Table 2. Reaction of acetophenone hydrazones 1 with TeCl4
View Article Online
DOI: 10.1039/D0OB00782J
H3C
R
H2C
CH2
CH3
H3C
Te
N
N
Base
Te
H3C
+
NH2
H3C
+
NH2
R
R
R
3
1
1a
TeCl4
DBU
Cu
3
CHCl3
rt
toluene
reflux
CH2
TeCl4
2a
Te
+
Te
H2C
H2C
CH2
4
R
Te
+
Entry
1
R
CH3
H
3
Yield/%
65
H3C
CH3
1
2
3
4
5
6
7
1a
1b
1c
1d
1e
1f
3a
3b
3c
3d
3e
3f
3a
62
Cu
3a
Cl
67
H3C
toluene
reflux
CH2
Br
55
Te
+
NO2
Ph
61
Te
H2C
51
CH3
4a
1g
o-CH3
3g
54
Solvent Temp 2ab
3ab,c
(%)
12
36
48
18
52
53
55
65
52
a)Reactions performed in the presence of 1 (5.0 mmol), DBU (6 eq) TeCl4
Entry
TeCl4
Base
(eq)
(oC)
reflux
rt
(%)
32
5
(2 eq), and chloroform at rt.
(eq)
1.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1
2
3
4
5
6
7
8
9
Et3N
Et3N
DBU
DBU
DBU
DBU
DBU
DBU
DBU
3.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
DMF
DMF
DMF
Introduction of various electron-donating and electron-withdrawing
groups into the p-positions was fully tolerated (Entries 1-6), whereas
o-Me gave 3g in 54% yield (Entry 7). Generally, para-substituted
acetophenone hydrazones gave better yields of these products.
Thus, we have developed a convenient synthesis of bis(1-aryl)vinyl
tellurides 3.
rt
5
toluene reflux
28
0
CH2Cl2
CH2Cl2
CHCl3
CHCl3
CHCl3
reflux
rt
0
reflux
rt
0
We have already reported that the reaction of camphor hydrazone
with TeCl4 afforded the corresponding divinyl ditelluride via
tellurocamphor intermediate.6 Analogously, the reaction might
proceed as follows; Hydrazones 1 reacted with TeCl4 to afford the
corresponding telluroacetophenones, which easily enolyzed to give
enetellurols. Under these conditions, enetellurols oxidized to give
the corresponding divinyl ditellurides 4. Ditellurides are relatively
unstable, which gradually changed to more stable divinyl tellurides 3
(Scheme 1).
0
0
0
a) Reactions performed in the presence of 1a (5.0 mmol), base (3 eq or 6
eq), TeCl4 (1 or 2 eq), and solvent at rt or reflux. b) Yields are given for isolated
2a and 3a. c) There is no smell problem for compound 3a due to low volatility.
Although compound 3a could not be obtained effectively in DMF
solution at several reaction temperatures (rt to reflux) by using Et3N
or DBU as a base (Entries 1-3), we then tried the reaction in several
solvents under moderate reaction temperature. When the reaction
was carried out in dichloromethane solution at room temperature, a
mixture of vinyl telluride (3a) and vinyl ditelluride (4a) was obtained
in 4:3 ratio (60% by NMR). However, isolation of vinyl telluride 3a
was very difficult for their similar polarity. Since ditellurides are
known to react with Cu powder to give the corresponding telluride7,
we have added Cu powder to the mixture and refluxed for 3h. Vinyl
telluride 3a was isolated in 53% yield (Entry 6). When chloroform
was used as a solvent, 3a was obtained in 65% yield (Entry 8). With
the optimal conditions in hand (CHCl3, rt, 5h), we have investigated
the scope and generality of this synthesis. The results were shown in
Table 2.
Ar
Ar
Te
NNH2
H3C
CH2
CH2
DBU
H3C
+
1
Ar
Ar
Te
Te
TeCl4
4
Ar
TeH
H2C
CH2
Ar
CH2
Ar
Te
3
Scheme 1. Formation mechanism of 3.
2 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
NO2
Reaction of vinyl telluride with bromine
NO2
O2N
O2N
View Article Online
Br
Te
Br
Br Br
DOI: 10.1039/D0OB00782J
Tellurophenes and tellurides easily react with bromine to afford the
corresponding tellurium dibromides, which show interesting
photoelectronic properties.1, 2 Thus, we have tried the reaction with
bromine whether the corresponding tellurium dibromide would be
formed. Treatment of bis-1-(4-methylphenyl)vinyl telluride 3a with
1.2 molar amount of bromine afforded tellurium dibromide 5a. Bis-
1-(4-bromophenl)vinyl telluride 3d and bis-1-(4-nitrophenl)vinyl
telluride 3e also reacted with bromine to give stable tellurium
dibromide 5d and 5e, respectively (Scheme 2).
Br2
Te
Br
CH2
CH2
H2C
H2C
Br
5e
O2N
H2O
HBr
Te
NO2
Br
H2C
Br2
O
H
R
R
R
R
NO2
H2C
Br
O2N
NO2
C
Br
Br
Br
+ Br2
Te
Te
Br
H2C
CH2Cl2
rt, 1 h
Te
CH2
CH2
H2C
H2C
Br
Br
CH2Br
Br
CH2
3a R= CH3
3d R= Br
3e R= NO2
O
5a R=CH3 95%
5d R= Br 52%
5e R= NO2 62%
Br
CH2
Br
Br
8
Br2
NO2
Scheme 2. Synthesis of tellurium dibromide 5
6b
O2N
Br
Te
O2N
Br
O2N
{O}
Since there is no report on the reaction with excess amount of
bromine to vinyl tellurides, we then tried the reaction of tellurides 3
with excess amount of bromine whether the corresponding bromine
adduct would be formed. Treatment of 3a with 3.2 molar amount of
Te
Br
+
TeO2
Br
Br
Br
H2C
CH2
CH2
Br
Br
Br
8
bromine afforded
methylbenzene and (E)-1-(1,2-dibromovinyl)-4-methylbenzene
(13:1) in 35% yield along with 2-bromo-p-methylphenylethanone 6a
(28%). Similarly, when 3 molar amount of bromine was reacted with corresponding tellurium dibromides 5. Further bromination to
a
mixture of (Z)-1-(1,2-dibromovinyl)-4-
Scheme 4. Reaction mechanism
7
Thus, vinyl tellurides 3 were easily brominated to give the
3e, 1-nitro-4-(1,1,2-tribromoethyl)benzene
8 and 2-bromo-p-
double bond is relatively difficult and elimination proceeded to give
7 or 8. Difference in the reactivity between tellurides 3a and 3e
would be the difference in the stability between 5a and 5e.
Dibromide 5e is stable in chloroform solution at rt for 2 days,
whereas 5a is easily oxidized to give p-methylacetophenone after
standing at rt in chloroform for 2 days (Scheme 5).
nitrophenylethanone 6b were obtained in 65% and 5% yields,
respectively (Scheme 3). The structure of tribromide 8 was
determined by 1H and 13C NMR along with X-ray single
crystallographic analysis.8
CH3
CH3
H3C
H3C
CH3
3 Br2
H3C
Br
Br
Te
Te
+
O
O
CH2Cl2
H
+ HBr
CH2
H2C
Br
H3C
+ TeO2
BrH2C
CHCl3
rt, 2 days
CH3
3a
Br
7 35%
CH2
H2C
6a 28%
5a
NO2
NO2
O2N
+
O2N
3 Br2
Scheme 5. Oxidation of dibromide 5a
X-Ray crystallographic analysis
Te
CH2Cl2
O
Br
CH2Br
Br
H2C
CH2
BrH2C
5%
8
6b
65%
3e
Attempts to grow single crystals of dibromides were only successful
in the case of 5e. The ORTEP view of 5e is presented in Figure 2.8 In
view of the steric demand of the active lone pair, the primary
geometry of the tellurium atom may be describes as distorted
trigonal bypyramidal. The distortion is apparent from the reduced
bond angles Br(1)-Te(1)-Br(2) (171.2o) and C(1)-Te-C(1)* (111.1o) as
against 180o and120o, respectively, for idealized trigonal bipyramidal
Scheme 3. Reaction of tellurides 3 with excess amount of
bromine
The reaction might proceed as follows: initially formed
dibromide 5e brominated to afford bromonium ion, which
further attacked by bromide and eliminated to give tribromide
8. Bromonium ion further reacted with water to give 2-
bromoacetophenone 6b (Scheme 4).
geometry.
There are relatively few examples of X-ray
crystallographic structures of telluride-halogen adducts, which show
trigonal bypyramidal geometry around tellurium atom.9 This is the
first example of X-ray crystallographic structure of vinyl telluride-
bromine adduct.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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ARTICLE
Journal Name
corresponding 11 in moderate yields (Entries 4-6, 8, and 9).
View Article Online
However, nitro derivative 3e did not afford dDiaOryI:l1t0e.l1l0u3r9id/De0dOuBe0t0o7l8o2wJ
reactivity (Entry 7).
C1*
Table 3. Reaction of vinyl telluride 3 with triflate in the presence
of water
C1
R
R
TMS
OTf
H
Te
CsF
H
9
CH3CN
50oC,
15 h
Figure 2. X-ray crystallographic analysis of Compound 5e. (50%
probability) Selcted bond lengths and bond angles Te(1)-C(1)
2.133A, Te(1)-C(1)* 2.133, Te(1)-Br(1) 2.669, Te(1)-Br(1)* 2.133, C(1)-
Te(1)-C(1)* 111.1o, C(1)*-Te(1)-Br(1) 88.40o, C(1)-Te-Br(1) 86.63o.
C(1)*-Te(1)-Br(1)* 86.63o. C(1)-Te(1)-Br(1) 88.40o.
R
R
10
+
H
H
Te
3a
+ H2O
+
Te
H
H
R
R
11
Reaction of vinyl telluride 3 with 2-trimethylsilylphenyl triflate 9a
It is well known that alkyl sulfides react with benzyne to afford the
corresponding phenyl sulfides.10 Vinyl sulfides having electron-
withdrawing group are known to react with benzyne followed by the
addition of water to give 2-alkenylphenyl aryl sulfides in good
yields.11（Figure 3） Although these methods provide a variety of
functionalized aromatic sulfides, it is very difficult to synthesize
functionalized aromatic tellurides.
Entry
Telluri
de 3
R
9
Eq.
Water
( eq)
Products
Yield
/ %
10
11
1
2
3
4
5
6
7
8
9
3a
3a
3a
3b
3c
3d
3e
3f
p-CH3
p-CH3
p-CH3
H
p-Cl
p-Br
p-NO2
p-Ph
o-CH3
1.2
3
3
3
3
3
3
3
3
0
0
3
3
3
3
3
3
3
10a
5
11a
11a
11a
11b
11c
11d
11e
11f
8
10a 12
21
70
60
60
63
0
0
0
0
0
0
0
0
N2
S
S
46
51
Cl
+
3g
11g
ClCH2CH2Cl
reflux
CO2H
Cl
Nakayama et al.
The reaction might proceed as follows: [3+2] cycloaddition gave
tellurolium ylide a, which reacted with water to give telluronium ion
b. Hydrogen abstraction of b afforded the mono vinyl telluride
10a, which further reacted with another molar of benzyne and water
to give final telluride 11a (Scheme 6). To confirm the role of water,
D2O was added to the reaction. The corresponding deuterated
telluride 11a (60% D) was obtained in 55% yield.
S
TMS
KF
S
F
+
THF
OTf
Fan et al.
CO2Me
TMS
CsF, H2O
CO2Me
+
CH3CN
80oC, 14 h
OTf
Studer et al.
Figure 3.
SAr
SAr
H
O
H
Te
Tol
Te
Since divinyl tellurides 3 were obtained in one-pot operation from
acetophenone hydrazones 1, we then tried the reaction of these
compounds with benzyne prepared from 2-(trimethylsilyl)phenyl
triflate 9. Treatment of triflate 9 (1.2 eq) with divinyl telluride 3a in
the presence of CsF at 50oC for 24 h resulted in the formation of 2-
Tol
Tol
Tol
a
3a
H
HO
phenylethenylphenyl
aryl
telluride
10
and
bis(2-
H2O
11a
Te
Te
phenylethenyl)phenyl telluride 11a and in 5% and 8% yields,
respectively. Telluride 3a was recovered in 45 % (Table 3, Entry 1).
When 3 molar amount of triflate 9 was used to the reaction,
compounds 10 and 11a were obtained in 12 and 35% yields along
with starting 3a (20%) (Entry 2). These results clearly showed that
water must be required for completion of the reaction. Treatment
of 3 molar amount of triflate 9 with divinyl telluride 3a and 3 eq water
in the presence of CsF at 50oC resulted in the formation of the desired
trans-diaryl telluride 11a in 70% yield (Entry 3). Under these
conditions, other tellurides 3 also reacted with triflate 9 to afford the
Tol
Tol
Tol
Tol
b
10a
Scheme 6. Formation mechanism of 11 from telluride 3
Conclusions
we have successfully synthesized divinyl tellurides 3 by the
reaction of acetophenone hydrazones
1
with TeCl4.
4 | J. Name., 2012, 00, 1-3
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Consequently, we completed the synthesis of divinyl tellurides
ARTICLE
o
Bis-1-(p-nitrophenyl)vinyl telluride 3e: yellow solid, mp 123-124 C.
View Article Online
via a different route from the previously reported ones. The 1H NMR (CDCl3)  = 6.03 (s, 2H, =CH), 6.36 (sD, O2HI:,1=0.C1H03),9/7D.407O(Bd0,047H82,JJ
= 9 Hz, Ar), 8.09 (d, 4H, J = 9 Hz, Ar). 13C NMR (CDCl3)  = 123.6, 126.0,
128.7 (=CH2), 131.3, 147.3, 148.8. Anal. Calcd for C16H12N2O4Te: C,
45.34; H, 2.85; N, 6.61. Found: C, 45.46; H, 2.85; N, 6.44.
reaction of these tellurides with bromine gave the
corresponding tellurium dibromides 5, which further reacted
with additional bromine to give tribromoethylbenzene. The
reaction with aryne prepared from triflate 9 afforded the
corresponding insertion products 11.
Bis-1-([1,1'-biphenyl]-4-yl)vinyl telluride 3f: orange solid, mp 147-149
1
oC. H NMR (CDCl3)  = 5.90 (s, 2H, =CH), 6.36 (s, 2H, =CH), 7.33 (t,
2H, J = 7 Hz, Ar), 7.42 (t, 4H, J = 7 Hz, Ar), 7.48 (d, 4H, J = 8 Hz, Ar),
7.50 (d, 4H, J = 8 Hz, Ar), 7.56 (d, 4H, J = 8 Hz, Ar). 13C NMR (CDCl3)
 = 126.9, 127.0, 127.4 (=CH2), 127.6, 128.3, 128.4, 128.8, 140.6,
140.7, 141.6. Anal. Calcd for C28H22Te: C, 52.23; H, 3.13. Found C,
51.96; H, 3.21.
Bis-1-(o-tolyl)vinyl telluride 3g: reddish orange oil. ¹H-NMR (CDCl3)
 = 2.22 (s, 6H, CH3), 5.94 (d, J = 1 Hz, 2H, = CH), 6.05 d, J = 1 Hz, 2H,
=CH), 7.03-7.17 (m, 8H, Ar). 13C NMR (CDCl3)  = 20.3, 125.5, 127.1,
127.6, 128.9, 129.5, 133.3, 134.8, 143.7. HRMS (EI): Calcd for
C18H18Te: m/z = 364.0471 (M+). Found: m/z = 364.0473 (M+)
Experimental
General: All chemicals were obtained from commercial suppliers and
were used without further purification. Analytical TLC was carried
out on precoated plates (Merck silica gel 60, F254) and flash column
chromatography was performed with silica gel (Merck, 70-230
mesh). NMR spectra (1H at 400 MHz; 13C at 101 MHz) were recorded
in CDCl3 and chemical shifts are expressed in ppm relative to internal
TMS for 1H- and 13C-NMR. Melting points are uncorrected.
Reaction of acetophenone hydrazone with TeCl4
Reaction of bis(1-p-nitrophenyl)vinyl telluride with bromine
To a solution of telluride 3a (145 mg, 0.4 mmol) in dichloromethane
(6 mL) was added Br2 (4.4 ml, 0.44 mmol, 0.1 M in dichloromethane)
at rt. After being stirred for 2h, the reaction mixture was evaporated
to give pale yellow oily crystals, which was chromatographed over
silica gel by elution with hexane:dichloromethane (1:1) to afford
tellurium dibromide 5a (198 mg, 0.38 mmol).
Bis-1-(p-methylphenyl)vinyltellurium dibromide 5a: Pale yellow
solid: mp 69-70 oC. 1H NMR (CDCl3)  = 2.40 (s, 6H, CH3), 6.24 (d, 2H,
J = 3 Hz, =CH), 6.37 (d, 2H, J = 3 Hz, =CH), 7.23 (d, 4H, J = 8 Hz, Ar),
7.36 (d, 4H, J = 8 Hz, Ar). 13C NMR (CDCl3)  = 21.4 (CH3), 128.4, 129.3,
129.4 (=CH2), 134.0, 140.1, 147.7. Anal. Calcd for C18H18Br2Te: C;
41.44; H, 3.48. Found: C, 41.36; H, 3.58.
Bis-1-(p-bromophenyl)vinyltellurium dibromide 5d: yellow solid, mp
123-125oC. 1H NMR (400 MHz, CDCl3  = 6.30 (d, 2H, J = 3 Hz, =CH),
6.39 (d, 2H, J = 3 Hz, =CH), 7.32 (d, 4H, J= 9 Hz, Ar), 7.56 (d, 4H, J = 9
Hz, Ar). 13C NMR (CDCl3)  = 124.5, 130.2, 130.6, 132.0, 135.7,
146.0. Anal. Calcd for C16H12Br4Te: C, 29.50; H, 1.86. Found: C,
29.86; H, 1.84.
To a solution of TeCl4 (2.69 g, 10.0 mmol) and DBU (4.57 g, 30.0
mmol) in chloroform (30 mL) was added p-methylacetophenone
hydrazone (0.741 g, 5.0 mmol) in chloroform (20 mL) at rt over 1 h.
After being stirred for 0.5 h, the reaction mixture was filtered and
poured into water which was extracted with dichloromethane (10
mL) for three times. The combined extract was dried over sodium
sulfate, filtered and evaporated to give a mixture of bis(1-p-
tolyl)vinyl ditelluride 2a and bis(1-p-tolyl)vinyl telluride 3a (0.95g,
70% by 1H NMR). To a suspension of the mixture (0.95 g) in toluene
(20 mL) was added Cu powder (0.63 g, 10 mmol) and refluxed for 12
h. After filtering the suspension, the filtrate was evaporated to give
orange oil, which was chromatographed over silica gel by elution
with hexane:dichloromethtane (1:1) to afford divinyl telluride 3a
(0.58 g, 1.6 mmol).
1
Bis-1-(p-tolyl)vinyl telluride 3a: orange oil. H NMR (CDCl3)  = 2.32
(s, 6H, CH3), 5.79 (s, 2H, =CH), 6.30(s, 2H, =CH), 7.07 (d, 4H, J = 8 Hz,
Ar), 7.36 (d, 4H, J = 8 Hz, Ar). 13C NMR (CDCl3)  = 21.1 (CH3), 126.7,
127.7, 128.7 (=CH2) ,128.9, 137.8, 139.8. HRMS (EI): Calcd for
C18H18Te: m/z = 364.0471 (M+). Found: m/z = 364.0467 (M+)
1
Bis-1-(phenyl)vinyl telluride 3b: reddish orange oil. H NMR (CDCl3)
Bis-1-(p-nitrophenyl)vinyltellurium dibromide 5e: Orange solid. mp
o
1
 = 5.84 (s, 2H, =CH), 6.30 (s, 2H, =CH), 7.22-7.27 (m, 6H, Ar), 7.41-
7.46 (m, 4H, Ar). 13C NMR (CDCl3)  = 127.4, 127.7, 127.8 (=CH2),
128.2, 128.8, 142.6. HRMS (EI): Calcd for C16H14Te: m/z = 336.0158
(M+). Found: m/z = 336.0151 (M+).
Bis-1-(p-chlorophenyl)vinyl telluride 3c: orange oil. 1H NMR (CDCl3)
 = 5.83 (s, 2H, =CH), 6.23 (s, 2H, =CH), 7.19 (d, 4H, J = 8Hz, Ar), 7.29
(d, 4H, J = 8 Hz, Ar). 13C NMR (CDCl3)  = 127.4, 128.1, 128.3 (=CH2),
129.1, 133.7z, 141.0. HRMS (EI): Calcd for C16H12Cl2Te: m/z =
403.9378 (M+). Found: m/z = 403.9370 (M+)
154-156 C. H NMR (CDCl3)  = 6.52 (d, 2H, J = 3 Hz, =CH), 6.56 (d,
2H, J = 3 Hz, =CH), 7.62 (d, 4H, J = 9 Hz, Ar), 8.31 (d, 4H, J = 8 Hz, Ar).
13C NMR (CDCl3)  = 124.0, 129.8, 132.4 (=CH2), 142.7, 144.3, 148.7.
Anal. Calcd for C18H18Br2N2O4Te: C, 32.92; H, 2.07; N, 4.80. Found: C,
32.76; H, 2.25; N, 3.52.
Reaction of bis(1-p-tolyl)vinyl telluride 3a with 3 molar amount of
bromine
To a solution of telluride 3a (108 mg, 0.3 mmol) in dichloromethane
Bis-1-(p-bromophenyl)vinyl telluride 3d: orange sold, mp 154-156 oC
(dec). 1H NMR (CDCl3)  = 5.84 (s, 2H, =CH), 6.23 (s, 2H, =CH), 7.22 (d,
4H, J = 8Hz, Ar), 7.35 (d, 4H, J = 8 Hz, Ar). 13C NMR (CDCl3)  = 122.0,
127.5, 128.3 (=CH2), 129.5, 131.3, 141.6. HRMS (EI): Calcd for
C16H12Br2Te: m/z = 493.8348 (M+) Found: m/z = 493.8344 (M+)
(8 mL) was added bromine (2 ml, 1.0 mmol, 0.5
dichloromethane) at room temperature. After being stirred for 2 h,
the solution was evaporated to give orange oil, which was
M in
chromatographed
hexane:dichloromethtane
over
silica
(1:1)
gel
to
by
afford
elution
with
2-bromo-p-
methylphenylethanone 6a (36 mg, 0.17 mmol) and (E)- and (Z)-1,2-
dibromo-p-methylstyrene 7 (1:13) (58 mg, 0.21 mmol).
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Organic & Biomolecular Chemistry
Page 6 of 8
ARTICLE
Journal Name
2-bromo-p-methylphenylethanone 6a: pale yellow oily solid, mp 46- Reaction of bis(1-p-methylphenyl)vinyl telluride withV2ie-w Article Online
49oC (lit.12 mp 51-52oC). 1H NMR (CDCl3)  = 2.43 (s, 3H, CH3), 4.42 (s,
2H, CH2), 7.28 (d, 2H, J = 8 Hz, Ar), 7.88 (d, 2H, J = 8 Hz, Ar). 13C NMR
(CDCl3) δ = 21.7 (CH3), 30.8 (CH2), 129.1, 129.5, 131.6, 144.9 (Ar),
190.9 (C=O).
DOI: 10.1039/D0OB00782J
trimethylsilylphenyl triflate (3 eq) and water in the presence of
CsF
To a suspension of vinyl telluride 3a (72 mg, 0.20 mmol), water (7.2
L, 0.40 mmol) and CsF (273 mg, 1.8 mmol) in CH3CN (1 mL) was
(Z)-1,2-dibromo-p-methylstyrene 7: pale orange oil.13 1H NMR added a solution of 2-trimethylsilylphenyl triflate 9 (180 mg, 0.60
o
mmol) in CH3CN (3 mL). After being stirred for 12 h at 50 C, the
reaction mixture was poured into water and extracted with
dichloromethane (6 mL x 3). The combined extract was dried over
Na2SO4, filtered, and evaporated to give a pale brown oil, which was
(CDCl3)  = 2.35 (s, 3H, CH3), 7.00 (s, 1H, =CH), 7.15 (d, 2H, J = 8 Hz,
Ar), 7.39 (d, 2H, J = 8 Hz, Ar). 13C NMR (CDCl3) δ = 21.2 (CH3), 107.9
(=CH), 127.2, 129.2, 131.2, 135.7, 139.6.
chromatographed
hexane:dichloromethane
over
silica
(3:1)
gel
to
by
give
elution
with
Reaction of bis(1-p-nitrophenyl)vinyl telluride 3e with 3 molar
amount of bromine
bis(2-((E)-4-
methylstyryl)phenyl) telluride 11a (67 mg, 0.13 mmol).
To a solution of telluride 3e (127 mg, 0.3 mmol) in dichloromethane
1
Bis(2-((E)-4-methylstyryl)phenyl) telluride 11a: orange oil. H NMR
(CDCl3) δ = 2.34 (s, 6H, CH3), 6.90 (d, 2H, J = 16 Hz, =CH), 7.00 (t,2H, J
= 8 Hz, Ar), 7.11 (d, 4H, J = 8 Hz, Ar), 7.27 (t, 2H, J = 8 Hz, Ar), 7.35 (d,
4H, J = 8 Hz, Ar), 7.39 (d, 2H, J = 16 Hz, =CH), 7.60-7.67 (m, 4H, Ar).
13C NMR (CDCl3) δ = 21.4, 119.2, 125.9, 126.8, 128.4, 128.8, 129.5,
131.0, 131.4, 134.5, 137.9, 139.5, 142.2. HRMS m/z Calcd for
C30H26Te: 516.1097 (M+), Found: 516.1084 (M+).
(8 mL) was added bromine (2 ml, 1.0 mmol, 0.5
M in
dichloromethane) at rt. After being stirred for 2h, the reaction
mixture was evaporated to give a pale yellow oil, which was
chromatographed
hexane:dichloromethane
over
silica
(1:1)
gel
to
by
afford
elution
with
2-bromo-p-
nitrophenylethanone 6b (7 mg, 0.03 mmol) and 1-nitro-4-(1,1,2-
tribromoethyl)benzene 8 (151 mg, 0.39 mmol).
2-bromo-p-nitrophenylethanone 6b: pale orange solid: mp 97-99 oC Bis(2-((E)-styryl)phenyl) telluride 11b: orange oil. ¹H NMR (CDCl3)  =
(lit.14 mp 99-100 oC). 1H NMR (CDCl3) = 4.46 (s, 2H, CH2), 8.16 (d, 2H,
J = 9 Hz, Ar), 8.35 (d, 2H, J = 9 Hz, Ar). 13C NMR (CDCl3)  = 30.0 (CH2),
124.0, 130.1, 138.4, 150.8 (Ar), 189.9 (C=O).
1-Nitro-4-(1,1,2-tribromoethyl)benzene 8: colorless solid, mp 68-69
oC. 1H NMR (CDCl3)  = 4.64 (s, 2H, CH2), 7.94 (d, 2H, J = 9 Hz, Ar), 8.24
(d, 2H, J = 9 Hz, Ar). 13C NMR (CDCl3)  = 44.7 (CH2), 61.2 (q-C), 123.5,
128.6, 147.3, 148.1 (Ar). Anal. Calcd for C8H6Br3NO2: C, 25.85; H,
1.63; N, 3.77. Found: C, 25.49; H, 1.80; N, 3.52.
6.82(d, 2H, J = 16 Hz, =CH), 6.89 (t, 2H, J = 8 Hz, Ar), 7.10-7.24 (m, 8H,
Ar), 7.31-7.39 (m, 6H, Ar), 7.49-7.60 (m, 4H, Ar). 13C NMR (CDCl3)  =
119.1, 125.9, 126.8, 127.9, 128.5, 128.7, 128.8, 131.4, 131.9, 137.2,
139.5, 142.0. HRMS m/z Calcd for C28H22Te: 488.0784 (M+), Found:
488.0783 (M+).
Bis(2-((E)-4-chlorostyryl)phenyl) telluride 11c: pale yellow oil. ¹H
NMR (CDCl3)  = 6.85 (d, 2H, J = 16 Hz, =CH), 7.05 (t, 2H, J = 8 Hz, Ar),
7.27 (d, 4H, J = 8 Hz, Ar), 7.30-7.35 (m, 6H, Ar), 7.38 (d, 2H, J = 16 Hz,
=CH), 7.62 (d, 2H, J = 8 Hz, Ar), 7.67 (d, 2H, J = 8 Hz, Ar). 13C NMR
(CDCl3)  = 119.1, 125.9, 127.9, 128.7, 128.8, 128.9, 130.0, 132.5,
133.5, 135.6, 139.5, 141.7. HRMS m/z Calcd for C28H20Cl2Te:
556.0004 (M+), Found: 556.0023 (M+).
Bis(2-((E)-4-bromostyryl)phenyl) telluride 11d: pale yellow solid
(MeOH then hexane). mp 70-75 oC. 1H NMR (CDCl3)  = 6.83 (d, 2H, J
= 14 Hz, =CH), 7.04 (t, 2H, J = 8 Hz, Ar), 7.24-7.32 (m, 6H, Ar), 7.40-
7.44 (m, 6H, Ar), 7.61 (d, 2H, J = 8 Hz, Ar), 7.66 (d, 2H, J = 8 Hz, Ar).
13C NMR (CDCl3)  = 119.1, 121.6,125.9, 128.1, 128.6, 128.8, 129.9,
131.7, 132.6, 136.0, 139.4, 141.6. Anal. Calcd for C28H20BrTe: Calc. C,
52.23; H, 3.13. Found C, 51.96; H, 3.21.
Reaction of bis(1-p-methylphenyl)vinyl telluride with 2-
trimethylsilylphenyl triflate (1.2 eq) in the presence of CsF
To a suspension of vinyl telluride 3a (72 mg, 0.20 mmol) and CsF (182
mg, 1.2 mmol) in CH3CN (1 mL) was added a solution of 2-
trimethylsilylphenyl triflate 9 (135 mg, 0.44 mmol) in CH3CN (3 mL).
After being stirred for 24 h at 50 oC, the reaction mixture was poured
into water and extracted with dichloromethane (6 mL x 3). The
combined extract was dried over Na2SO4, filtered, and evaporated to
give a pale brown oil, which was chromatographed over silica gel by
elution with hexane:dichloromethane (3:1) to give 1-(p-
methylphenyl)vinyl-2-((E)-4-methylstyryl)phenyl) telluride 10a (4.5
mg, 0.01 mmol) and bis(2-((E)-4-methylstyryl)phenyl) telluride 11a (8
mg, 0.016 mmol).
Bis(2-((E)-4-phenylstyryl)phenyl) telluride 11f: pale yellow solid
(MeOH then hexane), mp 228-230 oC. 1H NMR (CDCl3)  = 6.98 (d, 2H,
J = 14 Hz, =CH), 7.03 (t, 2H, J = 8 Hz, Ar), 7.30-7.34 (m, 4H, Ar), 7.42
(t, 4H, J = 8 Hz, Ar), 7.49-7.56 (m, 14H, Ar), 7.65-7.74 (m, 4H, Ar). 13C
NMR (CDCl3)  = 119.2, 125.8, 126.9, 127.2, 127.3, 127.3, 128.5,
128.8, 128.9, 130.8, 132.1, 136.2, 139.6, 140.6, 140.6, 142.0. Anal.
1-(p-methylphenyl)vinyl-2-((E)-4-methylstyryl)phenyl) telluride 10a:
orange oil. 1H NMR (400 MHz, CDCl3): δ 2.31 (s, 3H, CH3), 2.36 (s, 3H,
CH3), 5.54 (s, 1H, =CHH), 6.28 (s, 1H, =CHH), 6.92 (d, 1H, J = 16 Hz,
=CH), 7.02-7.10 (m, 3H, Ar), 7.16 (d, 2H, J = 8 Hz, Ar), 7.32 (t, 1H, J =
8 Hz, Ar), 7.37-7.43 (m, 4H, Ar), 7.46 (d, 1H, J = 16 Hz, =CH), 7.66 (d,
1H, J = 8 Hz, Ar), 7.86 (d, 1H, J = 8 Hz, Ar). 13C NMR (CDCl3)  =
21.1(CH3), 21.3(CH3), 118.8, 125.0, 125.5, 126.7, 127.5, 128.2, 128.9,
129.1, 129.1, 129.4, 131.0, 121.5, 134.5, 137.8, 138.0, 139.9, 140.5,
.
Calcd for C40H30Te H2O: Calc. C, 73.20; H, 4.91. Found C, 72.75; H,
5.07.
Bis(2-((E)-2-methylstyryl)phenyl) telluride 11g: orange oil. ¹H NMR
(CDCl3)  = 2.37 (s, 6H, CH3), 7.01 (t, 2H, J = 8 Hz, Ar), 7.16-7.09 (m,
8H, Ar), 7.33-7.25 (m, 4H, Ar), 7.48-7.43 (m, 2H, Ar), 7.66-7.59 (m, 4H,
Ar). 13C NMR (CDCl3)  = 20.0, 119.1, 125.9, 126.2, 126.3, 127.8,
128.5, 128.8, 129.4, 130.4, 133.2, 135.9, 136.2, 139.3, 142.5. HRMS
m/z Calcd for C30H26Te (M+): 516.1097, Found: 516.1103 (M+).
142.3.
HRMS m/z Calcd for C24H22Te: 440.0784 (M+),
Found:440.0774 (M+).
6 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
Conflicts of interest
View Article Online
DOI: 10.1039/D0OB00782J
There are no conflicts to declare.
Notes and references
1
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1991388. 1-nitro-4-(1,1,2-tribromoethyl)benzene 8: CCDC-
1991386. These data can be obtained free of charge from The
Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
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This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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Organic & Biomolecular Chemistry
Page 8 of 8
View Article Online
DOI: 10.1039/D0OB00782J
Graphical Abstract
Reaction of acetophenone hydrazones with TeCl4 in the presence of DBU followed by the addition of
Cu powder gave divinyl tellurides. Reaction of divinyl tellurides with bromine or benzyne afforded
the corresponding tellurium dibromides or (E)-2-alkenyl tellurides in good yields.
Ar
1) DBU
2) Cu
CH2
Ar
H2C
Ar
CH2
Ar
H2C
Ar
NNH2
Br2
H3C
Te
Te
Br
Br
TeCl4
+
H
Ar
H
H
Ar
Te
H