Diaroyl tellurides: Synthesis, structure and NBO analysis of (2-MeOC 6H4CO)2Te - comparison with its sulfur and selenium isologues. The first observation of [MgBr][R(C=Te)O] salts

Article abstract of DOI:10.3390/molecules14072555

A series of aromatic diacyl tellurides were prepared in moderate to good yields by the reactions of sodium or potassium arenecarbotelluroates with acyl chlorides in acetonitrile. X-ray structure analyses and theoretical calculations of 2-methoxybenzoic an

Full text of DOI:10.3390/molecules14072555

Molecules 2009, 14, 2555-2572; doi:10.3390/molecules14072555
OPEN ACCESS
molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Diaroyl Tellurides: Synthesis, Structure and NBO Analysis of
(2-MeOC6H4CO)2Te – Comparison with Its Sulfur and Selenium
Isologues. The First Observation of [MgBr][R(C=Te)O] Salts
Osamu Niyomura 1, Shoho Nakaiida 1, Ryo Yamada 1, Shinzi Kato 2,*, Masaru Ishida 1, Masahiro
Ebihara 1, Fumio Ando 2 and Jugo Koketsu 2
1
Department of Chemistry, School of Engineering, Gifu University, Gifu, Japan
2
Department of Applied Chemistry, College of Engineering, Chubu University, Kasugai, Japan
* Author to whom correspondence should be addressed; E-mail: kshinzi@nifty.com;
Tel./Fax: +81-52-222-2442
Received: 3 June 2009; in revised form: 7 July 2009/ Accepted: 9 July 2009 /
Published: 13 July 2009
Abstract: A series of aromatic diacyl tellurides were prepared in moderate to good yields
by the reactions of sodium or potassium arenecarbotelluroates with acyl chlorides in
acetonitrile. X-ray structure analyses and theoretical calculations of 2-methoxybenzoic
anhydride and bis(2-methoxybenzoyl) sulfide, selenide and telluride were carried out. The
two 2-MeOC6H4CO moieties of bis(2-methoxybenzoyl) telluride are nearly planar and the
two methoxy oxygen atoms intramolecularly coordinate to the central tellurium atom from
both side of C(11)-Te(11)-C(22) plane. In contrast, the oxygen and sulfur isologues (2-
MeOC6H4CO)2E (E = O, S), show that one of the two methoxy oxygen atoms contacts
with the oxygen atom of the carbonyl group connected to the same benzene ring. The
structure of di(2-methoxybenzoyl) selenide which was obtained by MO calculation
resembles that of tellurium isologues rather than the corresponding oxygen and sulfur
isologues. The reactions of di(aroyl) tellurides with Grignard reagents lead to the
formation of tellurocarboxylato magnesium complexes [MgBr][R(C=Te)O].
Keywords: diacyl telluride; diacyl selenide; diacyl sulfides; Grignard reagent; magnesium
carbotelluroate

Molecules 2009, 14
2556
Introduction
In contrast to diacyl sulfides and selenides, the isolation of diacyl tellurides is very difficult due to
their instability toward oxygen and thermal conditions. The first isolation of diacyl telluride was
reported in 1978 by Bergman and Engman, who isolated phthaloyl telluride [1]. In 1985, du Mont and
his coworkers successfully isolated two aliphatic diacyl tellurides [(RCO)2Te: R = Me, t-Bu] by using
(Me3Si)2Te as a tellurium source [2] and reported a molecular structural analysis of di(adamanthoyl)
tellurides [3]. In 1986 we also reported the isolation of two aromatic diacyl tellurides from the reaction
of sodium carbotelluroate with acyl chlorides [4]. In this paper, we report an improved synthesis and
some reactions of diaroyl tellurides, and NBO (natural bond orbital) analysis of (2-MeOC6H4)2E
(E= O, S, Se, Te).
Results and Discussion
Synthesis
The reactions of sodium telluride with two molar equivalents of acyl chlorides in ether, benzene and
tetrahydrofuran etc. gave di(acyl) tellurides 4 in yields below 50% [5], due to the difficulty of
separating by-products such as diacyl ditelluride, acid anhydride and black tellurium. We then found
that the use of acetonitrile as a solvent led to good yields of 4. For example, two molar equivalents of
4-methylbenzoyl chloride in acetonitrile were added dropwise at 0 ºC to a suspension of freshly
prepared sodium telluride in the same solvent, and the mixture was stirred for 2 h. The precipitates and
excess of sodium telluride were filtered out and the solvent was removed under reduced pressure to
give bis(4-methylbenzoyl) telluride (4e) in 54% yield.
Scheme 1. Synthesis of diacyl tellurides 4a-k.

Molecules 2009, 14
2557
Under similar conditions, the reactions of other sodium or potassium arenecarbotelluroates with the
corresponding aroyl chlorides led to the expected diacyl tellurides 4d, 4f−4k in isolated yields of
39−84% (Scheme 1). In contrast, the preparation of aliphatic compounds 4a−4c resulted in low yields
of 21−34%, most likely due to their instability.
Compounds 4 are pale yellow to yellow liquids or crystals that readily dissolve in common aprotic
solvents such dichloromethane and chloroform. They are susceptible to degradation by oxygen,
although the aromatic compounds appear to be much more stable in this respect than the aliphatic
ones. For example, while 4-methylbenzoyl derivative 4e can be stored without an appreciable change
for 3 hours under exposure to air at 15 °C, and it is stable for at least a week under oxygen-free
conditions at 0 °C. Upon exposure to air under similar conditions, aliphatic diacyl tellurides 4a-4c
quickly decomposed to give the corresponding acid anhydrides with the liberation of black tellurium.
Molecular structures of bis(2-methoxybenzoyl) chalcogenides
Figure 1 shows the ORTEP drawing of (2-MeOC6H4)2Te (4f) along with those of the corresponding
oxygen and sulfur isologues (2-MeOC6H4CO)2O (5) and (2-MeOC6H4CO)2S (6). The final atomic
positional parameters are shown in Table 1. Selected bond distances and angles are listed in Table 2.
Figure 1. ORTEP drawings of (a) bis(2-methoxybenzoyl) telluride (4f), (b) 2-methoxy-
benzoic anhydride (5) and (c) bis(2-methoxybenzoyl) sulfide (6). The thermal ellipsoid
plots represent 50% probability.

Molecules 2009, 14
2558
Table 1. Crystal date and data collection of bis(2-methoxybenzoyl) telluride (4f) [8], 2-
methoxybenzoic anhydride (5) [8], and bis(2-methoxybenzoyl) sulfide (6) [8].
4f
5
6
compounds
empirical formula
formula weight
color
C16H14O4Te
397.88
C16H14O5
C16H14O4S
303.34
pale yellow, prismatic
triclinic
286.28
yellow, prismatic
triclinic
a= 8.380(2)
b= 13.330(2)
c= 7.891(2)
98.17(2)
116.91(1)
73.84(1)
4104(2)
P-1 (#2)
2
colorless, prismatic
monoclinic
a= 7.408(1)
b= 19.206(2)
c= 10.278(2)
crystal system
unit-cell dimentions
(a = Å), (b = Å), (c = Å)
a= 9.294(9)
b= 11.2361(9)
c= 7.2789(7)
106.332(7)
102.798(8)
85.825(7)
711.32(11)
P-1 (#2)
2
α (deg)
β (deg)
104.70(1)
γ (deg)
volume of unit cell (Å3)
space group
Z value
1414.4(3)
P21/c (#14)
4
Dcalc (g/cm3)
crystal size (mm)
μ (Mo-Kα) (cm-1)
temp (°C)
1.750
1.750
1.412
0.29 x 0.14 x 0.34
19.83
0.374 x 0.29 x 0.26
1.00
0.34 x 0.34 x 0.23
2.40
-80.0
23.0
-80.0
0.71069
55.0
0.71069
55.0
0.71069
λ
MoΚα(Å)
2θmax (°)
55.0
3697
3489
3475
no. of measured reflections
no. of observations (I > 3σ(I))
no. of variables
3459
1454
2634
192
190
191
residuals: R,a Rw
0.031, 0.0943
1.257
0.070, 0.242
1.029
0.035, 0.0932
1.027
b
goodness of fit indicator
aR=
bRw=
Σ
[
(lFO
l
−
l
FCl)/
ΣlFOl.
-1
Σ
(lFO
l
−
l
FCl)2/
Σ
w
l
FOl2]1/2, w=
[
σ2(FO)+p2(FO)2
/
4
]
.
Table 2. Selected bond distances (A), angles (o) and torsion angles (o) of bis(2-methoxy-
benzoyl) telluride (4f), 2-methoxybenzoic anhyride (5) and bis(2-methoxybenzoyl)
sulfide (6).
Compound (4f)
Angles
Bond lengths
67.1(2)
131.7(1)
105.8(2)
Te(11)−C(11) 2.185(4) Te(11)···O(12) 2.826(4) C(11)–Te(11)−C(21) 93.6(1)
C(21)−Te(21)−O(22)
O(12)–Te(11)−O(22)
C(13)−O(12)–Te(11)
O(11)−C(11)–Te(11)
O(21)−C(21)−Te(22)
C(11)−Te(11)−O(12)
Te(11)−C(21) 2.192(4) Te(11)···O(22) 2.846(4)
C(11)−O(11) 1.203(5) O(11)···O(21) 2.925(2)
C(21)−O(21) 1.204(5)
120.9(2)
120.5(2)
67.7(4)
O(23)−O(22)−Te(11) 104.8(2)
161.6(4)
C(23)–C(22)−C(21)−O(21)
Torsion angles
O(11)−C(11)–Te(11)–C(21)
O(21)−C(21)–Te(11)–C(11)
O(12)−Te(11)-C(11)–C(12)
O(12)−Te(11)-C(21)–C(22)
23.3(6) O(22)−Te(11)-C(11)−O(11)
24.1(7) O(12)−Te(11)-C(21)-O(21)
25.5(6)
21.8(6)
9.9(4)
11.8(4)
C(13)–C(12)–C(11)−O(11) 158.5(4)
O(11)−C(11)---C(21)−O(21)
42.7(3)
Compound (5)
Angles
Bond lengths
O(11)−C(11) 1.386(5) O(13)···O(11) 2.691(4) C(11)−O(11)−C(21) 118.2(4) O(13)−O(21)−O(22) 149.0(2)
O(11)−C(11)−O(12)
O(11)−C(21)−O(21)
119.5(5)
116.1(5)
O(13)−O(11)−C(21) 126.8(2)
O(13)−O(11)−O(21)
O(11)−C(21) 1.406(6) O(21)···O(22) 2.651(4)
C(11)−O(12) 1.190(6) O(13)···O(21) 3.404(2)
C(21)−O(22) 1.183(6) O(12)···O(21) 3.565(2)
83.2(2)
Torsion angles
O(22)−C(23)−O(22)-C(21)
2.7(2) O(21)−C(21)−C22)–C(23)
6.5(1)
O(21)−C(21)−O(11)–C(11) 20.3(2)
O(12)−C(11)---C(21)−O(22) 97.1(2)
O(12)−C(11)−O(11)−C21) 132.9(3) C(12)−C(13)---C(22)–C(23) 83.9(1)
Compound (6)
Bond lengths
Angles
S(11)−C(11) 1.812(2) S(11)···O(22) 2.719(4)
S(11)−C(21) 1.805(2) S(11)···O(12) 4.089(4)
C(11)−O(11) 1.201(2) O(11)···O(21) 2.761(2)
C(21)−O(21) 1.198(2) O(12)···O(11) 2.932(2)
C(11)−S(11)−C(21) 107.1(1) O(22)−S(11)−C(11) 173.5(2)
O(11)−C(11)−S(11)
O(21)−C(21)−S(11)
120.3(2)
126.0(2)
O(12)−O(11)−O(21) 143.5(2)
C(21)−S(11)−O(22)
75.3(2)
Torsion angles
O(11)−C(11)---C21)−O(21) 30.6(3)
89.4(1)
S(11)−C(21)−C(22)-C(27) 24.8(2)
O(22)−C(27)−C(22)–C(21)
O(11)−C(21)−S(11)–C(21)
2.6(2)
9.4(3)
C(17)−C(12)---C22)−C(27)
O(11)−C(11)−C12)−C(17) 56.5(3)

Molecules 2009, 14
2559
The two 2-MeOC6H4CO moieties of 4f are nearly planar [torsion angles: C(21)-C(22)-C(23)-O(22)
= –5.3°; C(11)-C(12)-C(13)-O(12) = –5.1°], with the two carbonyl groups in the same direction and
connected to the central tellurium atom. The interplanar angle involving two carbonyl groups
O(11)C(11)---C(21)O(21) is 42.6°, which is significantly larger than that of di(1-adamantoyl) telluride
(9.6°) [3]. The distance (2.925 Å) between the two carbonyl oxygen atoms [O(11)---O(21)] is
somewhat shorter than the sum of the van der Waals radii of both atoms (3.04 Å) [6], which suggests
weak intramolecular interaction. The two methoxy groups occupy the position opposite the carbonyl
groups. The distances between the methoxy oxygen and central tellurium atoms [O(22)---Te(11) and
O(21)---Te(11) (2.826 Å and 2.846 Å, respectively) are significantly shorter than the sum of the van
der Waals radii of both atoms (3.58 Å) [6], which suggests intramolecular nonbonding orbital
interactions [7].
For comparison, we carried out an X-ray structure analysis of 2-methoxybenzoic anhydride and
thioanhydride, 5 and 6. One benzene ring [C(12)–C(13)] and the carboxyl group [O(11), C(21), O(21)]
in 5 or the thiocarboxyl group [S(11), C(21), O(21)] in 6 are not coplanar. In both compounds 5 and 6,
the distances between one of the two methoxy oxygen atoms and one of the two carbonyl oxygen
atoms are short: 2.651 Å [O(21)---O(22) ] in 5 and 2.932 Å [O(11)---O(12) ] in 6, respectively. The
distances between the central oxygen and the methoxy oxygen atoms [O(11)---O(13)] in 5 and
between the central sulfur and the methoxy oxygen [S(11)---O(22)] in 6 are 2.691 Å and 2.719 Å,
respectively. These values are shorter than the sum (3.04 Å) [6] of the van der Waals radii of both
atoms, which suggests O---O intramolecular nonbonding interaction. On the other hand, the two
carbonyl groups in thioanhydride 6 are in the same direction, with an interplanar angle [O(11)–C(11)–
C(21)–O(21) of 30.5(1)° and the distance between the two carbonyl oxygen atoms [O(11)---O(21)] is
only 2.761(2) Å, which suggests an O---O intramolecular nonbonding interaction. The alignment of
O(22)–S(11)–C(11) is nearly linear: 173.4 (7)° [7,9].
We were unable to obtain single-crystals of the selenium isologue 7 even after several attempts.
Therefore, the structure of 7 was optimized by using the structure parameters of bis(2-
methoxybenzoyl) diselenide [10]. As shown in Figure 2, the structure of 7 resembles that of tellurium
isologue 4f rather than the corresponding sulfur isologue 6, although the 2-MeOC6H4 and C=O groups
in the 2-MeOC6H4CO moiety are not planar [torsion angles: O(4)–C(2)–C(6)–C(8) = 29.5°]. Thus, the
two carbonyl groups are in the same direction with torsion angles [O(4)-C(2)---C(3)-O(5)] of 63.1°.
The distance between the two carbonyl oxygen atoms [O(4)---O(5)] (2.877 Å) is somewhat shorter
than the sum of the van der Waals radii of the oxygen atoms (3.04 Å) [6]. The two methoxy oxygen
atoms contact to the central selenium atom and both distances, O(18)---Se(1) and O(19)---Se(1), are
short [2.973 Å], indicating intramolecular nonbonding interactions, as in 4f.
The C-E-C and O=C---C=O interplanar angles in the -CO-E-CO- moieties of (2-MeOC6H4CO)2E
(E = O, S, Se, Te) are shown in Table 3. Both the C-E-C angles and O=C---C=O interplanar angles are
narrow, in the order E = O > S > Se > Te. Narrowing of the C-Te-C angle reduces the intramolecular
repulsion of the carbonyl oxygen atoms.

Molecules 2009, 14
Figure 2. The optimized structure of (2-MeOC6H4CO)2Te (7) calculated at the
2560
RHF/LANL-2dz level. Distances are in angstrom (Å) and angles (°). Torsion angles: O4-
C2-C3-O5 = 63.5°; C2-Se1-O18-C8 = 24.2° in degrees (for the other distances and
angles: see Table 3).
O4
O5
94.7
C7
C9
C6
C8
C2
C3
3
7
9
.
2
Se1
O18
O19
Table 3. C=O---O=C distances and < C-E-C and interplanar angles (φO=C---C=O) in (2-
MeOC6H4CO)2E (E= O, S, Se, Te).
O
C
O
C
R
E
R
O---O
∠C-E-C
φO=C---C=O
E
3.565
2.762
2.854
2.925
118.2
103.2
94.7
97.1
89.7
63.1
42.7
O
S
Se
Te
93.7
Packing
The unit cells and intermolecular short contacts of compounds 4f, 5 and 6 are shown in Figures
3−5, respectively. Compounds 4f and 6 exist as two molecules in a unit cell, while compound 5 exists
as four molecules [Figure 3, (a); Figure 4, (a); Figure 5, (a)]. Structures 4f-A and 4f-B, 5-A, 5-A’, 5-B
and 5-B’, and 6-A and 6-B are enantiomorphic. Their 3-D packing structures are formed by weak
hydrogen-bond interactions between the carbonyl oxygen and the aromatic ring or methoxy methyl
protons and CH-(π) interactions between the methoxy methyl hydrogen and benzene-ring carbon
atoms [Figure 3, (b); Figure 4, (b); Figure 5, (b)] [11].

Molecules 2009, 14
Figure 3. (a) Packing and (b) intermolecular short contacts of (2-MeOC6H4CO)2Te (4f),
2561
view down to c-axis. Green, red, yellow and gray balls are tellurium, oxygen, sulfur and
carbon atoms, respectively. For (a), hydrogen atoms are omitted for clarity and molecules
4f-A and 4f-B are enantiomorphic with each other. For (b), red and light blue dotted lines
show intermolecular short contacts.
(a)
(b)
H
O"
4f-A
O
C
O
C
H"
Te
O
O
a
C""
H""
Te
O
4f-B
H
O
O'
H"
H
O
O
O
O'
O
H"'
C"'
O
b
Te
O'
O'
H"'
c
0
O
O"'
H'
Figure 4. (a) Packing and (b) intermolecular short contacts of (2-MeOC6H4CO)2O (5)
view down to a-axis. Red, gray and white balls are oxygen, carbon and hydrogen atoms,
respectively. For (a), hydrogen atoms are omitted for clarity and molecules 5-A, 5-A', 5-B
and 5-B' are enantiomorphic with each other. For (b), red dotted lines show intermolecular
short contacts.
(a)
(b)
O""
O
c
H'
5-A
H""
O
5-A'
H
O
O
5-B'
O
H
5-B
O"'
H"
b
0
H"'
O"

Molecules 2009, 14
Figure 5. (a) Packings and (b) intermolecular short contacts of (2-MeOC6H4CO)2S (6)
2562
view down to a-axis. Yellow, red, gray and white balls are sulfur, oxygen, carbon and
hydrogen atoms, respectively. For (a), hydrogen atoms are omitted for clarity and
molecules 6-A and 6-B are enantiomorphic with each other. For (b), red dotted lines show
intermolecular short contacts.
Ab initio calculations
To elucidate the nature of the nonbonding attractions, ab initio geometry optimizations were
performed at the B3LYP/6-311G(2d,p) level for compounds 5 and sulfur 6 and at the RHF/LANL2DZ
level+p for compounds 4f and 7 with the Gaussian 03 program [12,13] using their X-ray geometries
[10,14]. The Beck-style three-parameter density functional theory [15] with the Lee/Yang/Parr [16]
gradient-corrected correlation function was used in our calculation. Effective core potentials (ECP)
with an appropriate valence basis set [LANL2DZ+polarization functions (d) and diffusion functions
(sp)] were used for Te, Se, S and O, and the 04-31G* basis set was used for C and H [17]. At all levels
and with all of the basis sets used, two conformational energy minima were seen for (2-
MeOC6H4CO)2E [E = O (5), S (6), Se (7), Te (4f)], which are conformers with RCO groups [syn- (Cs
symmetry) and anti-conformer (C2 symmetry)] (Figure 5). The structure parameters of the optimized
geometries of these compounds are consistent with the absence of intermolecular interactions in crystal
structures with these XRD values (detail data: ESI-Table 1).
To understand the orbital interactions of the -C(O)EC(O)- (E = O, S, Se, Te) moiety, the NBO
analysis of (2-MeOC6H4CO)2E [E = O (5), S (6), Se (7), Te (4f)] was performed using the X-ray
geometries of 5 and 6 (Table 4). For the -C(O)EC(O)- moiety, orbital interactions are observed for the
lone-pair electrons, which indicates delocalization of the lone-pair electrons on the carbonyl oxygen to
the π* of a chalcogen atom (E) – carbon bond and on the central atom (E) to the π* orbital of the
carbonyl groups. In addition, for 4f, there are nonbonding intramolecular interactions nO2→σ*Te-C2 and
nO4→σ*Te-C1, which indicates a large stabilization compared to other derivatives without an ortho-
methoxy substituent.

Molecules 2009, 14
Table 4. NBO analysis of (2-MeOC6H4CO)2E [E = O (5), S (6), Se (7), Te (4f)].
2563
O3
O1
O3
C2
O1
C1
O2
O4
C2
O2
C3
O4
E
E
(2-MeOC6H4CO)2E
(2-MeOC6H4CO)2E
cis
trans
ΔEa [kcal mol-1]b
ΔEa [kcal mol-1]c
nO2 σ*E-C2
nO4 π*O3-C2
nO1 σ*E-C2
nO3 σ*E-C1
nO4 σ*E-C2
nO5 σ*E-C3
nE π*C1-O2
nE π*C2-O3
nO2 σ*E-C2
nO4 σ*E-C3
nE π*C2-O1
nE π*C3-3
E
O
S
No.
5
No. E
40.7
40.7
36.0
36.0
3.2
3.2
0.9
5.0
Se
Te
22.2
22.2
20.6
19.0
21.9
39.6
28.2
28.4
7
42.0
41.5
45.3
45.5
-
1.4
1.9
1.9
b
4f
6
aStabilization energy associated with delocalization. Calculation level: RHF3-21G for compounds 5 and 6.
cCalculation level: RHF/LANL2dz(p.d) for compounds 7 and 4f.
Reactions diacyl tellurides with Grignard reagents
Compound 4f readily reacts with sodium methoxide and piperidine at 0 °C to yield the
corresponding sodium (1, R = 2-MeOC6H4) and piperidinium salts (8) [C5H10N+ (2-MeOC6H4COTe)-],
respectively [4b]. It is well known that the treatment of aromatic acid anhydrides such as benzoic
anhydride with RMgBr (R = aryl), followed by hydrolysis, gives the corresponding carboxylic acid
and triarylmethanol [18]. Previously, we had observed that bis(4-methylbenzoyl) sulfide and selenide
readily react with 4-methylphenylmagnesium bromide, and subsequent HCl-acidolysis gives tris(4-
methylphenyl)carbinol, along with the corresponding thio- [19] and selenocarboxylic acid salts [20a,
20b]. As expected, bis(2-methoxybenzoyl) telluride (4f) reacted with arylmagnesium bromides at 0 ºC
to afford the corresponding ketone and triarylmethanol 11 in moderate yields (Scheme 2, Table 5).
However, the reaction with t-butylmagnesium bromide under similar conditions gave bis(2-
methoxybenzoyl) ditelluride (12) [10], along with 2-methoxybenzoic acid.
Interestingly, when a tetrahydrofuran solution of phenylmagnesium bromide was added, the orange-
13
colored solution of 4f immediately changed to dark green. The electron and C-NMR spectra of this
dark green solution showed a characteristic absorption maximum at λmax 732 nm and a new signal at δ
232 ppm, respectively. In addition, treatment of the dark green solution with excess of iodomethane
led to Te-methyl 2-methoxybenzenecarbotelluroate (9). Several attempts to isolate the dark green
compound with an absorption maximum at λmax 732 nm were unsuccessful. As for the cause of this
change, du Mont and his coworkers have reported that the n-π* transitions of the C=Te group of O-
trimethylsilyl ethanecarbotelluroate appear at 732 nm [2a]. We have also found that O-triorganylsilyl
arenecarbotelluroates [20a] and aromatic carbotelluroic OH-acid (ArCTeOH) in polar solvents [20b]
show a similar dark green to deep blue coloration and that their n-π* transitions of the C=Te group
and tellurocarbonyl carbon chemical shifts appear in the ranges of 600−750 nm and δ 230−250 ppm,
respectively [20].

Molecules 2009, 14
Scheme 2. Reactions of bis(2-methoxybenzoyl) telluride (4f) with Grignard reagents.
2564
O
O
O
R'MgBr
excess MeI
2 h
+
+
RR'2COH
RCOR'
R
Te
R
R
TeMe
in THF, Ar
0 °C, 5 min
10
11
9
4f
(R = 2-MeOC6H4)
Table 5. Reactions of (2-MeOC6H4CO)2 Te (4f) with Grignard reagents.
(RCO)2Te
Entry R
Products
Yield
[%]
R'MgBr
R'
2-MeOC6H4(i-Pr)2COH (11a)
(2-MeOC6H4COTe)2 (12)
2-MeOC6H4(Ph)2COH (11b)
(2-CH3OC6H4)3COH (11c)
24
69
52
24
2-MeOC6H4 (4f)
i-Pr
1
2
3
4
5
6
t -Bu
Ph
2-CH3OC6H4
4-CH3C6H4
4-CH3C6H4
2-MeOC6H4(4-MeC6H4)2COH (11d) 20
2-MeOC6H4(4-MeC6H4)2COH (11d) 56
Scheme 3. A possible mechanism for the reactions of (2-MeOC6H4CO)2 Te (4f) with
Grignard reagents.
(MgBr)+
O-
O
O
O
+
R'MgBr
OMgBr
in THF, Ar
0 °C, 5 min
R
Te
R
R
Te
R
R'
4
A
Te
1) R'MgBr
+
RCOR'
RR'2COH
R
2) HCl/H2O
11
10
13
(dark green
to deep blue)
MeI
R' = t-Bu (?)
(RCOTe)2
RCOTeMe
9
12
Presumably, the absorption maximum at 732 nm observed in the reaction of bis(2-methoxybenzoyl)
telluride with Grignard reagent may be attributable to the n-π* transitions of the C=Te group,
indicating the formation of a complex 13, in which the oxygen atom of the carbotelluroato moiety is
connected to the central magnesium ion. (Scheme 3) At present stage, it is unclear whether or not the

Molecules 2009, 14
2565
ditelluride 12 (R = 2-MeOC6H4) forms via 13, since no color change to dark green or deep sky blue
was observed when t-BuMgBr was added.
Conclusions
The use of acetonitrile as a solvent was found to be effective for the synthesis of aromatic diacyl
tellurides from the reaction of acyl chlorides with sodium and potassium tellurides. X-ray crystal
structure analyses and theoretical calculations for 2-methoxybenzoic anhydride (5) and bis(2-
methoxybenzoyl) sulfide (6), selenide 7 and telluride 4f revealed that the two 2-MeOC6H4CO moieties
of 4f are nearly planar, where the two carbonyl oxygen atoms are in the same direction, and the two
methoxy oxygen atoms intramolecularly coordinate to the central tellurium atom from both sides of the
C(11)–Te(11)–C(22) plane. For the corresponding acid anhydride 5 and diacyl sulfide 6, one of the
two methoxy oxygen atoms is in contact with the central oxygen or sulfur atom and the other methoxy
oxygen atom is in contact the oxygen atom of a carbonyl group connected to the same benzene ring.
The structure of bis(2-methoxybenzoyl) selenide (7) obtained by theoretical calculations resembles
that of tellurium isologue 4f, rather than the corresponding oxygen and sulfur isologues 5 or 6. Thus,
the two carbonyl oxygen atoms are in the same direction and the two methoxy oxygen atoms
intramolecularly contact the central selenium atom from both sides of the C(11)–Se(11)–C(22) plane.
Natural bond orbital (NBO) analysis of the telluride 4f and selenide 7 revealed that two types of orbital
interactions, nO2→σ*E-C2/nO4→σ*E-C1 and nO2→σ*E-C1/nO4→σ*E-C2, are important and the former
particularly play a predominant role. The reactions of diaroyl tellurides with Grignard reagents led to
the formation of the corresponding carbotelluroato magnesium complexes in which the oxygen atoms
of carbotelluroato ligands are connected to the magnesium ion.
Experimental
General
The melting points were measured by a Yanagimoto micromelting point apparatus and uncorrected.
The IR spectra were measured on a PERKIN ELMER FT-IR 1640 and a JASCO grating IR
1
spectrophotometer IR-G. The H-NMR spectra were recorded on JEOL JNM-GX 270 (270 MHz) or
JNM-α400 (399.7 MHz) instruments, respectively, with tetramethylsilane as an internal standard. The
13C-NMR spectra were obtained from a JEOL JMN-GX 270 (67.9 MHz). The 125Te NMR spectra for
aromatic diacyl tellurides 4d−4k were obtained from a JEOL JNM-GX-270 (85.9 MHz) with Ph2Te as
an external standard: their chemical shifts were determined relative to Me2Te with δ (Ph2Te) = 420
ppm relative to Me2Te. The 125Te-NMR spectra for aliphatic diacyl tellurides 4a-4c were obtained on
a JEOL JNM-α400 (126.0 MHz) instrument with dimethyl telluride as an external standard. The
electron spectra were obtained with Hitachi 124 and 310 spectrometers. The mass spectra were
recorded on Shimadzu GCMS QP1000 (A) (EI/CI, model) mass spectrometers. The high resolution
mass spectra (HRMS) were recorded on Shimadzu GCMS 9020DF high resolution mass spectrometer.

Molecules 2009, 14
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Materials
Sodium [20c] and potassium carbotelluroates 1 and 2 [4b,20d] were prepared according to the
literature. Diethyl ether and hexane were refluxed and distilled from sodium metal using
benzophenone as indicator before use. Dichloromethane and acetonitrile were distilled over
phosphorus pentoxide. All manipulations were carried out under argon.
X-ray Measurements [20-24]
The measurements were carried out on a Rigaku AFC7R four-circle diffract meter with graphite-
monochromated Mo-K radiation (= 0.71069 Å). All of the structures were solved and refined using the
teXsan crystallographic software package on an IRIS Indigo computer. X-ray quality crystals of 4f, 5
and 6 were obtained by recrystallization from ether/petroleum ether. The crystal of 4f was cut from the
grown needles and coated with an epoxy resin and mounted on a glass fiber. The cell dimensions were
determined from a least-squares refinement of the setting diffract-meter angles for 25 automatically
centered reflections. The crystals of 5 and 6 were obtained by recrystallization from a mixed solvent of
ether/hexane. Lorentz and polarization corrections were applied to the data, and empirical absorption
corrections (ψ-scans [21]) were also applied. The structures were solved by direct methods using
SIR97 [22] and refined by using SHELXL97 [23]. Scattering factors for neutral atoms were from
Cromer and Waber [24] and anomalous dispersion [25] was used. The final full-matrix least-squares
cycle included nonhydrogen atoms with anisotropic thermal parameters. H atoms were placed in
idealized positions and treated as riding atoms with C–H distances in the range 0.93–0.98 Å.
Preparation of (2-MeOC6H4CO)2S (5) [26] and (2-MeOC6H4CO)2O (6) [27]
These compounds were synthesized following the indicated literature procedures and recrystallized
from benzene/petroleum ether. Compound 5: M.p. 66–69 °C; IR (KBr) [cm-1]: 1,732 [C=O], 1,662
[C=O]; 1H-NMR (399.7 MHz, CDCl3): δ = 3.21 (s, 3H) [CH3O], 6.96 (d, J = 7.9 Hz, 2H) [arom], 7.00
(t, J = 7.9 Hz, 2H) [arom], 7.48 (t, J = 7.9 Hz, 2H) [arom], 7.71 (d, J = 7.9 Hz, 2H) [arom]; 13C-NMR
(67.9 MHz, CDCl3): δ = 55.8 [CH3O], 112.0, 120.4, 127.4, 130.2, 134.2, 157.8 [arom], 192.1 [C=O].
1
Compound 6: M.p. 73-74 °C. IR (KBr) [cm-1]: 1,733 [C=O], 1,700 [C=O]; H-NMR (399.7 MHz,
CDCl3): δ = 3.85 (s, 6H) [CH3O], 7.00 (d, J = 8.0 Hz, 2H, [arom]), 7.03 (t, J = 8.0 Hz, 2H, [arom]),
7.55 (t, J = 8.0 Hz, 2H, [arom]), 8.01 (d, J = 8.0 Hz, 2H, [arom]); 13C-NMR (67.9 MHz, CDCl3): δ =
55.9 [CH3O], 112.1, 118.1, 120.3, 133.0, 135.2 [arom], 161.9 [C=O].
Syntheses of di(acyl) tellurides 4a-k
The preparation of bis(4-methylbenzoyl) telluride (4e) is described in detail as a typical procedure.
Except were indicated, potassium carbotelluroates 2 were used for the preparation of compounds 4.
The IR spectra of the latter were consistent with those of the corresponding authentic samples,
respectively, which were prepared by the reaction of the corresponding piperidinium or potassium salts
with acyl chlorides.

Molecules 2009, 14
2567
Diacetyl telluride (4a) [2a]. Acetyl chloride (2.01 g, 10.3 mmol) was added to a suspension of freshly
prepared sodium methanecarbotelluroate (0.808 g, 10.3 mmol) in acetonitrile (15 mL) and the mixture
was stirred at 0 °C for 30 min. The resulting precipitates were filtered out. Removal of the solvent
under reduced pressure and vacuum distillation of the residue gave 1.426 g (65 %) of crude diacetyl
telluride (4a) as yellow liquid. Vacuum distillation of the resulting residue gave 0.37 g (21 %) of 4a as
a pale yellow liquid. B.p. 88–90 °C/25 torr; IR (CsI, neat) [cm-1]: 3,410, 3,000, 2,900, 1,821, 1,755
1
[C=O], 1,710 [C=O], 1,410, 1,350, 1,230, 1,070, 550; H-NMR (270 MHz, CDCl3): δ = 2.68 (s,
[CH3]); 13C-NMR (67.8 MHz, CDCl3): δ = 42.6 [CH3], 196.6 [C=O]; 125Te-NMR (85.9 MHz, CDCl3):
δ = 1035.5; MS (CI, 70 eV), m/e = 218 [M+ +1], 216, 214; HRMS (EI, 20 eV) calcd. for C4H6O2Te:
m/z = 215.9430; Found: 215.9447.
Bis(2,2-dimethylpropanoyl) telluride (4b). Yield: 34%; Pale yellow liquid; b.p. 72–74°C/0.2 torr; IR
(CsI, neat) [cm-1]: 2,980, 1,745 [C=O], 1,695 [C=O], 1,470, 1,450, 1,390, 1,360, 1,220, 1,025, 1,000,
1
13
865, 765, 580; H-NMR (270 MHz, CDCl3): 1.15 (s, 18H) [CH3]; C-NMR (67.8 MHz, CDCl3): δ =
26.10 (CH3), 53.7 [CCO], 206.1 [C=O]; 125Te-NMR (85.9 MHz, CDCl3): δ = 1013.7; MS (CI, 70 eV):
m/z = 301 [M+ +1], 299, 297, 85 [C4H9CO]; HRMS (EI, 20 eV) calcd. for C10H18O2Te: m/z =
300.03689; Found: 300.03695.
Dihexanoyl telluride (4c). Yield: 24%; Pale yellow liquid; b.p. 75–78°C/0.15 torr; IR (CsI, neat)
1
[cm-1]: 2,950, 2,900, 1,750 [C=O], 1,700 [C=O], 1,470, 1,120 m 1,040, 720; H-NMR (270 MHz,
CDCl3): δ = 0.90 (t, J = 7.3 Hz, 3H) [CH3], 1.33 (m, 4H) [CH2], 1.67 (m, 2H) [CH2], 2.85 (t, J = 7.3
Hz, 2H) [CH2]; 13C-NMR (67.8 MHz, CDCl3): δ = 13.8 [CH3], 22.4, 24.4, 31.0 [CH2], 56.0 [CH2CO],
200.5 [C=O]; 125Te-NMR (85.9 MHz, CDCl3): δ = 1111.7; MS (CI, 70 eV): m/z = 329 [M+ +1], 327,
325, 99 (C5H11CO); HRMS (EI, 20 eV) calcd. for C12H22O2Te: m/z = 328.06842; Found: 328.06826.
Dibenzoyl telluride (4d). 78%. Orange yellow microfine crystals (recrystallization solvents:
dichloromethane/petroleum ether). M.p. 70–71°C (dec.); IR (KBr) [cm-1]: 3,020, 3,010, 1,710 [C=O],
1,675 [C=O], 1,590, 1,575, 1,485, 1,440, 1,300, 1,235, 1,160, 1,070, 1,055, 1,000, 940, 845, 760, 695,
675, 665, 630, 600, 585; 1H-NMR (270 MHz, CDCl3): δ = 7.438.18 (m, 10 H) [arom]; 13C-NMR (67.8
MHz, CDCl3): δ = 128.2, 129.0, 134.4, 141.6 [arom], 192.1 [C=O]; 125Te-NMR (85.9 MHz, CDCl3):
δ = 1054.7.
Preparation of bis(4-methylbenzoyl) telluride (4e): From sodium 4-methylbenzenecarbotelluroate. 4-
Methylbenzoyl chloride (0.357 g, 2.32 mmol) in acetonitrile (5 ml) was added to a suspension of
sodium 4-methylbenzenecarbotelluroate (1, R = 4-CH3C6H4) (0.680 g, 2.52 mmol) in ether (20 mL)
and the mixture was stirred at 0 °C for 2 h. The solvents were evaporated under reduced pressure and
ether (50 mL) was added. The precipitates (NaCl and excess of the sodium salt) were filtered out.
Removal of the ether under reduced pressure and recrystallization of the residue from
dichloromethane/petroleum ether gave 0.497 g (54%) of bis(4-methylbenzoyl) telluride (4e) as orange
yellow micro crystals. M.p. 83–86 °C (dec.); IR (KBr) [cm-1]: 3,020, 2,928, 1,741 [C=O], 1,706
[C=O], 1,690 [C=O], 1,599, 1,548, 1,404, 1,308, 1,198, 1,165, 1,122, 1,039, 1,016, 973, 869, 853, 825,
814, 772, 709, 604, 593, 463; 1H-NMR (270 MHz, CDCl3): δ = 2.38 (s, 3H) [CH3], 7.24 (d, J = 8.2 Hz,

Molecules 2009, 14
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13
2H) [arom], 7.69 (d, J = 8.2 Hz, 2H) [arom]; C-NMR (67.8 MHz, CDCl3): δ = 21.7 (CH3), 128.5,
129.6, 139.3, 145.5 [arom], 191.6 [C=O]; 125Te-NMR (85.9 MHz, CDCl3): δ = 1038.9.
From potassium 4-methylbenznecarbotelluroate. Similar to the sodium salt, the reaction of 4-
methylbenzoyl chloride (0.300 g, 1.95 mmol) with potassium 4-methylbenzenecarbotelluroate (2, R =
4-CH3C6H4) (0.561 g, 1.95 mmol) gave 0.520 g (73%) of 4e.
Bis(2-methoxybenzoyl) telluride (4f): From sodium 2-methoxybenzenecarbotelluroate. Similarly to the
synthesis of 4e, the reaction of 2-methoxybenzoyl chloride (0.42 g, 2.46 mmol) with freshly prepared
sodium 2-methoxybenzene-carbotelluroate (0.749 g, 2.62 mmol) in acetonitrile (5 mL), followed by
recrystallization from chloroform/petroleum ether gave 0.708 g (72%) of 4f as yellow needles. M.p. 88
°C (dec.); IR (KBr) [cm-1]: 3,100, 3,000, 2,950, 2,850, 1,742 [C=O?], 1,675 [C=O], 1,625 [C=O],
1,590, 1,575, 1,480, 1,460, 1,445, 1,425, 1,305, 1,240, 1,175, 1,155, 1,100, 1,045, 1,010, 1,000, 840,
1
780, 745, 640, 590, 520, 490; H-NMR (270 MHz, CDCl3): δ = 3.95 (s, 3H) [CH3O], 6.98-7.62 (m,
8H) [arom]; 13C-NMR (67.8 MHz, CDCl3): δ = 55.4 [CH3O], 111.0, 121.0, 128.6, 132.0, 134.1, 158.6
[arom], 192.1 [C=O]; 125Te-NMR (85.9 MHz, CDCl3): δ = 1279.3; UV/Vis. (CH2Cl2) [nm]: 255, 313,
355 sh, 400 sh, 460; MS (CI, 70 eV): m/z = 367 [M+ +1], 395, 393.
From potassium 2-methoxybenznecarbotelluroate. 82%. Yellow needles (recrystallization solvents:
dichloromethane/petroleum ether). M.p. 88 °C (dec.).
Bis(4-methoxybenzoyl) telluride (4g). 29%. Yellow needles (recrystallization solvents:
dichloromethane/petroleum ether); m.p. 95–98°C (dec.); IR (KBr) [cm-1]: 3,026, 2,985, 2,925, 2,830,
1,716 [C=O], 1,702 [C=O], 1,595, 1,570. 1,505, 1,420, 1,290, 1,170, 1,155, 1,120, 1,095, 1,020, 915,
835, 810, 760, 675, 618, 598, 531, 490, 470; 1H-NMR (270 MHz, CDCl3): δ = 3.82 (s, 3H) [CH3], 6.87
13
(d, J = 9.8 Hz, 2H) [arom], 7.80 (d, J = 8.8 Hz, 2H) [arom]; C-NMR (67.8 MHz, CDCl3): δ = 55.7
[CH3], 114.4, 131.0, 132.3, 164.5 [arom], 181.6 [C=O]; 125Te-NMR (85.9 MHz, CDCl3): δ = 1070.9.
Bis(2-chlorobenzoyl) telluride (4h). M.p. 70 °C (dec.); Yellow needles (recrystallization solvents:
dichloromethane/petroleum ether/ether). IR (KBr) [cm-1]: 3,010, 1,750 [C=O], 1,650 [C=O], 1,590,
1
1,465, 1,435, 1,250, 1,180, 1,100, 1,040, 960, 950, 865, 770, 745, 720, 685, 633, 590; H-NMR (270
MHz, CDCl3): δ = 7.17–7.31 (m, 8H) [arom]; 13C-NMR (67.8 MHz, CDCl3): δ = 126.8, 128.9, 130.6,
132.6, 140.9, 159.8 [arom], 192.1 [C=O]; 125Te-NMR (85.9 MHz, CDCl3): δ = 1294.7.
Bis(4-chlorobenzoyl) telluride (4i). 68%; Orange yellow micro-crystals; m.p. 75–78 °C ? (dec).; IR
1
(KBr) [cm-1]: 3,028, 1,725 (C=O), 1,700 (C=O), 1,470, 1,120 m 1,040, 720; H-NMR (270 MHz,
13
CDCl3): δ = 7.47 (d, J = 8.5 Hz, 2H) [arom], 7.74 (d, J = 8.5 Hz, 2H) [arom]; C-NMR (67.8 MHz,
CDCl3): δ = 129.5, 129.6, 139.9, 141.2 [arom], 190.4 [C=O]; 125Te-NMR (85.9 MHz, CDCl3):
δ = 1488.9.
Bis(3-chloro-2,6-dimethoxybenzoyl) telluride (4j). 39%; M.p. 89-91 °C (dec.) (recrystallization
solvents: dichloromethane/petroleum ether); IR (KBr) [cm-1]: 3,025, 2,950, 2,850, 1,715 (C=O), 1,685
(C=O), 1,575, 1,560, 1,540, 1,465, 1,455, 1,430, 1,395, 1,365, 1,285, 1,270, 1,230, 1,170, 1,140,
1
1,080, 1,005, 1,000, 915, 895, 880, 800, 775, 725, 705, 680, 665, 640, 625, 575, 540, 490; H-NMR

Molecules 2009, 14
2569
13
(270 MHz, CDCl3): δ = 3.81 (s, 6H) [CH3O], 3.86 (s, 6H) [CH3O], 6.62−7.36 (m, 4H) [arom]; C-
NMR (67.8 MHz, CDCl3): δ = 56.1 [CH3O], 62.6 [CH3O], 108.9, 119.9, 129.8, 132.5, 151.4, 154.8
[arom], 192.1 [C=O]; 125Te-NMR (85.9 MHz, CDCl3): δ = 1248.5; UV/Vis. (CH2Cl2) [nm]: 252,
285, 455.
Di(1-naphthoyl) telluride (4k). 84%. Orange yellow needles. M.p. 104 °C (dec.) (recrystallization
solvents: dichloromethane/petroleum ether); IR (neat, CsI) [cm-1]: 3,075, 1,710 [C=O], 1,665 [C=O],
1,590, 1,575, 1,500, 1,210, 1,205, 1,195, 1,155, 1,040, 880, 870, 865, 800, 790, 765, 730, 715, 640,
1
13
625, 585, 555, 480; H-NMR (270 MHz, CDCl3): δ = 7.51–8.69 (m, 20H) [arom]; C-NMR (67.8
MHz, CDCl3): δ = 124.6, 125.1, 127.1, 127.4, 128.3, 128.9, 130.9, 132.1, 134.0, 139.5 [arom], 196.1
[C=O]; 125Te-NMR [85.9 MHz, CDCl3]: δ = 1176.4.
Reactions of compounds 4 with Grignard reagents
With 4-methylphenylmagnesium bromide: A solution of 4-methylphenylmagnesium bromide (0.396 N,
5 mL) in tetrahydrofuran was added to di(2-methoxybenzoyl) telluride (4f, 0.393 g, 1.0 mmol) in the
same solvent (20 mL) at 0 °C and the mixture was stirred at the same temperature for 2 h. The orange
yellow color [λmax (CH2Cl2): 255, 313, 350 sh; λmax (THF): 260, 315, 356 sh] quickly changed to dark
13
green [UV-Vis (THF): λmax 392 sh, 732 nm; C-NMR (67.8 MHz, THF-d8): δ = 232 [C=Te]. Water
(30 mL) was added and stirred at 20 °C for 12 h until the green color changed to red orange [Caution:
very unpleasant smell (He2Te ?)]. Dichloromethane (100 mL) was added and the organic layer washed
with water (30 mL x 3), followed by drying with anhydrous sodium sulfate. Removal of the solvent
under reduced pressure and preparative thin layer chromatography of the residue (eluent:
dichloromethane/hexane = 3:1) gave 1,1-bis(4-methylphenyl)-1-(2-methoxyphenyl)-methanol (11d)
(Rf = 0.08) as colorless micro-crystals. Yield: 0.235 g (84%); m.p. 123-125 °C; IR (KBr) [cm-1]:
3,450, 3,050, 2,975, 2,925, 2,850, 1,590, 1,575, 1,505, 1,480, 1,455, 1,425, 1,405, 1,350, 1,275, 1,235,
1
1,175, 1,150, 1,115, 1,015, 1,010, 915, 900, 815, 770, 750, 735, 650, 595, 575, 560, 495; H-NMR
(270 MHz, CDCl3): δ = 2.32 (s, 6H) [CH3], 3.73 (s, 3H) [CH3O], 5.26 (s, 1H) [OH]; 6.6−7.3 (m, 12H)
[arom]; MS (EI, 20 eV) : m/z = 318 [M+], 301 [M –OH], 300 [M -H2O], 287 [M -CH3O].
With 1-methylethylmagnesium bromide: Compound 4f (0,383 g, 1.0 mmol) and 1-methylethyl-
magnesium bromide (0.57 N, 5 mL) were stirred in THF (15 mL) at 0 °C for 1 h. Water (20 mL) was
added and stirred at 22 °C for 12 h. The reaction mixture was extracted with dichloromethane (2 x 50
mL), followed by drying over anhydrous sodium sulfate (ca. 5 g) for 1 h. The solvents were evaporated
under reduced pressure. Thin layer chromatography (Rf = 0.16) of the resulting residue using a mixed
solvent of dichloromethane/hexane (1:2) gave 1-(2-methoxyphenyl)-1-(1-methylethyl)methanol (11a)
(Rf : 0.16); Yield: 0.072 g (24%) as a colorless oil; IR (KBr) [cm-1] 3,400 (br), 2,850, 2,925, 2,825,
1
1,485, 1,455, 1,430, 1,235, 1,020, 745; H-NMR (270 MHz, CDCl3): δ = 0.80 (d, 3H, J = 8.1 Hz)
[CH3], 1.0 (d, 3H, J = 6.6 Hz) [CH3], 2.0 (sept, 1H, J = 10.1 Hz) [CH], 2.5 9 (br, 1H,) [OH], 3.80 (s,
3H) [CH3], 4.50 (d, 1H, J = 8.1 Hz) [CH], 6.83−7.23 (m, 4H) [arom; MS (CI, 70 eV): m/z = 180 [M+],
+
162 [M-OH], 137 [2-MeOC6H4(OH)CH+], 107 [2-MeOC6H4 ].

Molecules 2009, 14
2570
With 1,1-dimethylethylmagnesium bromide: The reaction of 4f (0.800 g, 2.01 mmol) with 1,1-
dimethylethylmagnesium bromide (0.603 N, 10 mL), followed by washing of the reaction mixture with
water (50 mL) and evaporation of the THF under reduced pressure, gave bis(2-methoxybenzoyl)
ditelluride (12) as red crystals. Yield: 0.363 g (69%); 128−130 °C (dec); (lit. m.p. 130−131°C, dec.
1
[4b]); IR (KBr) [cm-1] 1620 (C=O); H-NMR (270 MHz, CDCl3): δ = 3.15 (s, 6H, CH3O). The IR
spectrum of 12 was identical to that of an authentic sample prepared by the oxidation of piperidinium
2-methoxybenzenecarbotelluroate with iodine [4b].
With 2-methoxyphenylmagnesium bromide: Compound 4f (0.402 g, 1.01 mmol) and 2-methoxy-
phenylmagnesium bromide (0.304 N, 10 mL) were stirred in THF (20 mL) at 0 °C for 1 h, followed by
treatment of the reaction mixture with water (50 mL) and by thin layer chromatographic separation as
mentioned above to give 1,1,1-tris(2-methoxyphenyl)methanol (11c) as colorless crystals. Yield: 0.591
g (24%) as colorless crystals; m.p. 184−185 °C; IR (KBr) [cm-1]: 3,560. 3,530, 2,975, 2,875, 2,850,
1,597, 1,580, 1,487, 1,465, 1,455, 1,430, 1,405, 1,285, 1,245, 1,230, 1,180, 1,160, 1,115, 1,105, 1,020,
1,000, 910, 900, 790, 755, 730, 625, 565; 1H-NMR (270 MHz, CDCl3): δ = 3.46 (s, 6H) [CH3], 3.73 (s,
3H) [CH3O], 5.26 (s, 1H) [OH], 6.6−7.3 (m, 12H) [arom]; MS (CI, 70 eV) (m/z = 318 (M+), 301
(M -OH), 300 (M -H2O), 287 (M -CH3O).
Acknowledgements
This work was supported by the Grant-in-Aids for Scientific Research (B) and on Priority Areas
provided by the Ministry of Education, Science, Sport and Culture, Japan. S.K. thanks Dr. Takahiro
Kanda for his experimental support of Gifu University and Associate Professor Mao Minoura of
Kitasato University for the graphical support.
References and Notes
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Data Availability: the electronic supplementary information: ESI-Table 1 is available from the
corresponding author.
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