One-pot synthesis of aryl butyl tellurides from tellurium tetrachloride and activated aromatics through a solventless step

Article abstract of DOI:10.1016/j.jorganchem.2004.08.041

A solventless preparation of aryl tellurium trichlorides from activated aromatic compounds avoiding the use of hazardous solvents as carbon tetrachloride and chloroform is described. The trichlorides were reduced and alkylated leading to aryl butyl tellurides in a one-pot procedure. Transmetallation of these tellurides with n-butyllithium followed by reaction with benzaldehyde gave the corresponding benzhydrols in good yields.

Full text of DOI:10.1016/j.jorganchem.2004.08.041

Journal of Organometallic Chemistry 689 (2004) 3631–3636
www.elsevier.com/locate/jorganchem
Note
One-pot synthesis of aryl butyl tellurides from tellurium
tetrachloride and activated aromatics through a solventless step
´
Rodrigo L. O. R. Cunha, Alvaro T. Omori, Priscila Castelani,
*
Fabiano T. Toledo, Joa˜o V. Comasseto
´ ´
Departamento de Quımica Fundamental, Instituto de Quımica, Universidade de Sa˜o Paulo,
Av. Prof. Lineu Prestes, 748, 05508-900 Sa˜o Paulo – SP, Brazil
Received 11 August 2004; accepted 30 August 2004
Available online 25 September 2004
Abstract
A solventless preparation of aryl tellurium trichlorides from activated aromatic compounds avoiding the use of hazardous
solvents as carbon tetrachloride and chloroform is described. The trichlorides were reduced and alkylated leading to aryl butyl
tellurides in a one-pot procedure. Transmetallation of these tellurides with n-butyllithium followed by reaction with benzaldehyde
gave the corresponding benzhydrols in good yields.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Tellurium trichlorides; Arylic tellurides; One-pot synthesis; Transmetallation; Aryllithiums
1. Introduction
nyllithium. Recently we found that aromatic tellurides
can directly generate aryl cyanocuprates through reac-
tion with easily prepared dilithium diorgano cyanocu-
prates [6]. However, the aromatic derivatives of
tellurium, which were the focus of the pioneering works
in this area [7], have been neglected and most of them
are still prepared by methodologies developed more
than fifty years ago, employing hazardous solvents such
as benzene, dioxane, carbon tetrachloride and chloro-
form [8]. In view of these facts we turned our attention
to the practical preparation of butyl aryl tellurides.
Organotellurium compounds have been used as pre-
cursors of molecule fragments, such as dienes and ene-
diynes [1], present in the structure of important classes
of natural products [2]. Some of the transformations
involving organic tellurides developed in the last years
have already been applied in the total synthesis of natu-
ral products [3], what shows that this branch of organic
chemistry is not merely a potential synthetic tool, but
has been incorporated to the synthetic methodology
arsenal. Most of the synthetic methods developed are
based on transformations using vinylic tellurides [4].
Several years ago, Sonoda and coworkers [5] reported
the transformation of phenyl n-propyl telluride into phe-
2. Results and discussion
In this communication, we report the solventless
preparation of aryl tellurium trichlorides by reaction
of tellurium tetrachloride with the corresponding acti-
vated aromatic compounds. This reaction required in
the past prolonged heating of the reagents in carbon
tetrachloride or chloroform [8]. Initially we added a
*
Corresponding author. Tel.: +55 11 3091 2176; fax: +55 11 3815
5579.
E-mail addresses: lscst_rodrigo@yahoo.com.br (R.L.O.R. Cunha),
jvcomass@iq.usp.br (J.V. Comasseto).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.08.041

3632
R.L.O.R. Cunha et al. / Journal of Organometallic Chemistry 689 (2004) 3631–3636
R1
R1
R1
THF, BuBr
NaBH4/H2O
TeCl4
TeCl3
TeBu
no solvent
120˚C
0˚C to r.t., 1h
R
R
R
1a-g
2a-g
2a (73%); 2b (76%); 2c (72%);
2d (82%); 2e (69%); 2f (79%);
2g (68%); 2h (55%); 2i (72%).
1a R = H, R1 = 4-MeO
1b R = H, R1 = 4-EtO
1c R = 3-MeO, R1 = 4-MeO 1h R = H, R1 = 4-PhO
1f R = H, R1 = 4-Ph
1g R = R1 = Ph
1d R = 3-Me, R1 = 4-MeO
1e R = H, R1 = 4-Me
1i R = H, R1 = 4-HO
Scheme 1.
stoichiometric amount of anisole to a pre-heated flask in
an oil bath at 120 ꢁC containing tellurium tetrachloride.
After 3 min, p-anisyl tellurium trichloride was obtained
in a 98% isolated yield. As our interest was to prepare
aryl butyl tellurides to be used as sources of reactive aryl
organometallics, we performed the solventless reaction
with a number of activated aromatic compounds (1a–i)
and in situ transformed the aryl tellurium trichlorides
into the corresponding aryl butyl tellurides (2a–i), by
sequential reaction with aqueous sodium borohydride
and n-butyl bromide at 0 ꢁC (Scheme 1) [9].
The yields obtained for the tellurides 2a–i refer to the
overall process, corresponding to the formation of the
aryl tellurium trichlorides, reduction to the aryl telluro-
lates and alkylation with n-bromobutane. In the case of
the strongly activated substrates 1a–d and 1h–i the yields
were good and the reaction time for the electrophilic
aromatic substitution was around 3 min. The reaction
with toluene (1e) required reflux of a stoichiometric mix-
ture of the reactants for 12 h. For the less activated sub-
strates (1f and 1g) the reaction time for the electrophilic
aromatic substitution was around 10 min and the yields
were less satisfactory. However, the preparation of these
aryl tellurium trichlorides using solvents was also a low
yield process [8]. In the case of naphthalene (1g) an ex-
cess of substrate was required and the reaction was per-
formed by melting first the substrate in a flask in an oil
bath at 120 ꢁC, followed by the addition of tellurium tet-
rachloride. In all the cases, the aryl tellurium trichlorides
were not isolated. To perform the reduction followed by
alkylation, the crude residue was cooled to room tem-
perature, dissolved in tetrahydrofuran and mixed with
n-bromobutane. To the mixture was added an aqueous
solution of sodium borohydride at 0 ꢁC and the reaction
was allowed to stir at room temperature for 1 h. Usual
R
TeBu
R
Li
Scheme 2.
work-up and filtration through a silica gel column using
hexanes as the eluent gave the aryl butyl tellurides in the
yields shown in Scheme 1. The compounds obtained
were stable, except telluride 2i. In this case, telluride 2i
was transformed in situ into the corresponding diorgano
tellurium dichloride by reaction with sulfuryl chloride
[10] that was stable and could be isolated as colorless
crystals in a 84% yield.
The structures of the obtained aryl butyl tellurides
1
were confirmed by spectral data. GC–MS analysis, H
and 13C NMR spectra indicated the exclusive formation
of the isomers shown in (Scheme 1). The butyl tellurium
group is positioned in para to the more activating group
and, in the case of telluride 2g, the product obtained was
the b isomer. As mentioned before [5], phenyl n-propyl
telluride is an efficient source of phenyllithium. In this
way, the compounds presented in (Scheme 1) could be
source of para-substituted aryl lithiums (Scheme 2),
which are prepared mainly by lithium–halogen exchange
[11]. However, the halogenation of the aromatic rings
leads very often to mixture of regioisomers [12], in con-
trast to the telluration process using tellurium tetrachlo-
ride, which gives the para-isomer exclusively.
In order to confirm the generality of this transforma-
tion the prepared aryl butyl tellurides 2a–g were trans-
metallated with n-butyllithium followed by capture of
the para-substituted aryl lithiums with benzaldehyde as
described by Sonoda and coworkers [5]. The expected
benzhydrols 3a–g were isolated in good yields in all
cases (Scheme 3).
R1
R1
R1
OH
Ph
PhCHO
0˚C, 1h
n-BuLi, THF
TeBu
Li
-78˚C, 10 min
R
R
R
2a-g
3a-g
3a (73%); 3b (76%); 3c (72%); 3d (82%);
3e (69%); 3f (79%); 3g (68%)
Scheme 3.

R.L.O.R. Cunha et al. / Journal of Organometallic Chemistry 689 (2004) 3631–3636
3633
3. Conclusion
ꢁC and the corresponding aromatic compound (20
mmol) was added at once, dissolving the tellurium tetra-
chloride promptly. An evolution of HCl was observed
and a yellow solid was formed. The system was cooled
to room temperature and the trichloride was used crude
in the reduction/alkylation procedure.
In conclusion, we showed that aryl tellurium trichlo-
rides can be prepared avoiding the use of hazardous sol-
vents and that these compounds can be transformed in a
one pot procedure into aryl butyl tellurides, which are
sources of para-substituted aryl lithiums. As organolith-
iums can be transformed by transmetallation in any
other class of organometallic compounds in which the
metal is more electronegative than lithium, the sequence
of reactions described in this paper formally represents
an access to important para-substituted aryl organome-
tallics such as aryl copper, aryl cadmium, aryl magne-
sium and aryl zinc compounds.
4.2. General procedure for the preparation of aryl butyl
tellurides (2a–d, 2f, 2h and 2i)
The trichloride prepared previously was dissolved in
THF (80 mL) and bromobutane (5.48 g, 40 mmol)
was added. The mixture was cooled to 0 ꢁC and a solu-
tion of sodium borohydride (3 g, 80 mmol) in water (80
mL) was added dropwise. The mixture turned to dark
with the addition of the first drops and then to light yel-
low after the completion of the addition. The reaction
was stirred for further 20 min at room temperature
and quenched with saturated solution of NH4Cl (50
mL). The mixture was extracted with ethyl acetate
(2 · 80 mL) and washed with brine (2 · 60 mL). The or-
ganic phases were combined, dried over MgSO4 and
concentrated at reduced pressure. The desired telluride
was purified by silica gel column chromatography using
hexanes as eluent.
4-Methoxy-1-butyltellanylbenzene (2a) [95849-63-1]
(4.42 g, 76%). 1H NMR (200 MHz, CDCl3) d ppm
7.68 (d, J 8.8 Hz, 2H); 6.72 (d, J 8.8 Hz, 2H); 3.79 (s,
3H); 2.82 (t, J 7.5 Hz, 2H); 1.74 (qn, J 7.3 Hz, 2H);
1.16 (sext, J 7.3 Hz, 2H); 0.88 (t, J 7.3 Hz, 3H). 13C
NMR (75 MHz, CDCl3) d ppm 159.7 (C4), 140.9 (C2),
115.2 (C3), 100.6 (C1), 55.2 (OCH3), 33.9 (CH2CH3),
25.0 (TeCH2CH2), 13.4 (CH2CH3), 8.69 (TeCH2).
LRMS m/z (rel. int., ion) 294 (13, M+), 292 (12,
M+ ꢀ 2), 290 (7, M+ ꢀ 4), 237 (7), 235 (7), 233 (5),
108 (100), 77 (9), 57 (15). IR (neat, cmꢀ1) 3000 (m),
2957 (m), 2926 (m), 2865 (m), 2840 (m), 1879 (w),
1616 (w), 1586 (s), 1488 (s), 1457 (m), 1244 (s), 1176
(s), 1032 (m), 818 (m), 588 (w), 514 (m).
4-Ethoxy-1-butyltellanylbenzene (2b) [95849-64-2]
(4.27 g, 70%). 1H NMR (300 MHz, CDCl3) d ppm
7.66 (d, J 8.7 Hz, 2H), 7.75 (d, J 8.7 Hz, 2H), 4.02 (q,
J 7.0 Hz, 2H), 2.82 (t, J 7.5 Hz, 2H), 1.73 (qn, J 7.5
Hz, 2H), 1.41 (t, J 7.0 Hz, 3H), 1.37 (sext, J 7.2 Hz,
2H), 0.88 (t, J 7.4 Hz, 3H). 13C NMR (75 MHz, CDCl3)
d ppm 159.3 (C4), 141.1 (C2), 115.9 (C3), 100.6 (C1), 63.6
(OCH2CH3), 34,1 (CH2CH3), 25.2 (TeCH2CH2), 15.0
(OCH2CH3), 13.7 (CH2CH3), 8.96 (TeCH2). LRMS m/
z (rel. int., ion) 308 (20, M+), 306 (18, M+ ꢀ 2), 304
(11, M+ ꢀ 4), 251 (6), 249 (5), 247 (4), 223 (11), 221
(10), 219 (6), 122 (100), 94 (62), 57 (24). IR (neat,
cmꢀ1) 2976 (s), 2957 (s), 2926 (s), 2871 (m), 1970 (w),
1883 (w), 1585 (s), 1488 (s), 1391 (m), 1279 (m), 1242
(s), 1176 (m), 1048 (m), 821 (m), 515 (m). Anal. Calc.
for C12H18OTe: C, 47.12; H, 5.93. Found: C, 47.40, H,
6.04%.
4. Experimental section
All solvents and chemicals used were previously puri-
fied according to the usual methods [13]. THF was
distilled from sodium/benzophenone under N2, immedi-
ately before use in the transmetallation reactions. n-
Butyllithium was titrated using 1,10-phenanthroline as
indicator prior to use [14]. Tellurium tetrachloride was
prepared according to the literature procedure [9]. The
transmetallation reactions were carried out in dried
glassware, under an inert atmosphere of dried and deoxy-
genated N2. A dried and inert atmosphere is not re-
quired for the preparation of aryl butyl tellurides.
Column chromatography was carried out with Merck
silica gel (230–400 Mesh). Thin layer chromatography
(TLC) was performed on silica gel F-254 on aluminum.
1H and 13C NMR spectra were recorded on either a Var-
ian DPX-300, Bruker DRX-500 or a Bruker AC-200
spectrometers using as internal standard tetramethylsi-
lane and the central peak of CDCl3 (77 ppm), respec-
tively. Chemical shifts (d) are given in ppm, coupling
constants (J) in Hz and multiplicities are indicated by
s (singlet), d (doublet), t (triplet), q (quartet), qn (quin-
tet), sext (sextet), m (multiplet) and br (broad). Infrared
spectra were recorded on a Bomem MB-100 spectropho-
tometer. Peaks area reported in cmꢀ1 with indicated
relative intensities: s (strong, 67–100%); m (medium,
34–66%), w (weak, 0–33%). Low resolution mass spectr-
ometry was performed in a Shimadzu CGMS-17A/
QP5050A instrument. Elemental analysis was performed
at the Microanalytical Laboratory of the Chemistry
Institute – University of Sa˜o Paulo. The IUPAC names
were obtained using the software ChemDraw Ultraꢂ,
version 7.0.1.
4.1. General procedure for the preparation of aryl
tellurium trichlorides
A one-necked round-bottomed flask containing tellu-
rium tetrachloride (5.38 g, 20 mmol) was heated to 120

3634
R.L.O.R. Cunha et al. / Journal of Organometallic Chemistry 689 (2004) 3631–3636
3,4-Dimethoxy-1-butyltellanylbenzene (2c) (4.56 g,
1
(d, J 9.0 Hz, 2H), 2.89 (t, J 7.5 Hz, 2H), 1.76 (qn, J
7.5 Hz, 2H), 1.39 (sext, J 7.4 Hz, 2H), 0.90 (t, J 7.4
Hz, 3H). 13C NMR (75 MHz, CDCl3) d ppm 157.5
71%). H NMR (300 MHz, CDCl3) d ppm 7.33 (dd, J
8.1, 1.8 Hz, 1H), 7.26 (d, J 1.5 Hz, 1H), 6.72 (d, J 8.4
Hz, 1H), 3.88 (s, 3H), 3.87 (s, 3H), 2.86 (t, J 7.7 Hz,
2H), 1.76 (qn, J 7.7 Hz, 2H), 1.39 (sext, J 7.4 Hz, 2H),
0.90 (t, J 7.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) d
ppm 149.3 (C3), 149.0 (C4), 132.4 (C5), 122.5 (C2),
112.2 (C6), 100.4 (C1), 56.0 (3-OCHꢁ3), 55.8 (4-OCH3ꢁ),
33.9 (CH2CH3), 25.0 (TeCH2CH2), 13.4 (CH2CH3),
8.95 (TeCH2). LRMS m/z (rel. int., ion) 324 (18, M+),
322 (16, M+ ꢀ 2), 320 (10, M+ ꢀ 4), 267 (12), 265 (11),
263 (7), 138 (100), 123 (15), 94 (34), 79 (22), 57 (15).
IR (neat, cmꢀ1) 2997 (m), 2965 (s), 2927 (s), 2836 (m),
2052 (w), 1898 (w), 1843 (w), 1731 (w), 1576 (s), 1500
(s), 1250 (s), 1228 (s), 1139 (s), 1026 (s), 847 (m), 802
(m), 760 (m), 588 (m), 503 (w), 460 (w), 389 (w). Anal.
Calc. for C12H18O2Te: C, 44.78; H, 5.45. Found: C,
44.64; H, 5.45%.
4-Methoxy-3-methyl-1-butyltellanylbenzene (2d) (3.05
g, 50%). 1H NMR (300 MHz, CDCl3) d ppm 7.57–
7.54 (m, 2H), 6.67 (d, J 7.8 Hz, 1H), 3.81 (s, 3H), 2.82
(t, J 7.6 Hz, 2H), 2.18 (s, 3H), 1.74 (qn, J 7.5 Hz, 2H),
1.38 (sext, J 7.4 Hz, 2H), 0.89 (t, J 7.4 Hz, 3H). 13C
NMR (75 MHz, CDCl3) d ppm 158.1 (C4), 142.0 (C2),
138.6 (C6), 128.1 (C3), 111.2 (C5), 100.5 (C1), 55.5
(OCH3), 34.2 (CH2CH3), 25.3 (TeCH2CH2), 16.2
(CH3), 13.7 (CH2CH3), 8.90 (TeCH2). LRMS m/z (rel.
int., ion) 308 (16, M+), 306 (15, M+ ꢀ 2), 304 (10,
M+ ꢀ 4), 251 (9), 249 (9), 247 (6), 122 (100), 91 (11),
78 (21), 57 (11). IR (neat, cmꢀ1) 2956 (s), 2926 (s),
2866 (m), 2836 (m), 1993 (w), 1861 (w), 1774 (w), 1584
(m), 1488 (s), 1460 (m), 1293 (m), 1245 (s), 1176 (m),
1138 (s), 1032 (s), 883 (m), 805 (m), 699 (m), 592 (m),
500 (m), 438 (m). Anal. Calc. for C12H18OTe: C,
47.12; H, 5.93. Found: C, 47.12; H, 5.78%.
0
0
0
ðC1 Þ, 156.8 (C4), 140.5 (C2), 129.8 ðC3 Þ, 123.6 ðC4 Þ,
0
119.5 ðC2 Þ, 119.2 (C3), 104.0 (C1), 33.8 (CH2CH3),
24.9 (TeCH2CH2), 13.4 (CH2CH3), 8.77 (TeCH2).
LRMS m/z (rel. int., ion) 356 (19, M+), 354 (15,
M+ ꢀ 2), 352 (9, M+ ꢀ 4), 299 (5), 297 (4), 295 (2),
170 (100), 141 (19), 115 (11), 77 (35), 57 (33). IR (neat,
cmꢀ1) 3065 (w), 3068 (w), 2957 (m), 2926 (m), 2869
(w), 2029 (w), 1957 (w), 1888 (w), 1777 (w), 1721 (w),
1651 (w), 1576 (m), 1483 (s), 1239 (s), 1166 (m), 1009
(m), 866 (m), 751 (m), 691 (m), 486 (m). Anal. Calc.
for C16H18OTe: C, 54.30; H, 5.13. Found: C, 54.44; H,
5.33%.
4-Hydroxy-1-butyltellanylbenzene (2i) (3.98 g, 72%).
1H NMR (300 MHz, CDCl3) d ppm 7.58 (d, J 8.5 Hz,
2H), 6.70 (d, J 8.5 Hz, 2H), 5.44 (br s, 1H), 2.80 (t, J
7.6 Hz, 2H), 1.72 (qn, J 7.5 Hz, 2H), 1.36 (sext, J 7.5
Hz, 2H), 0.87 (t, J 7.3 Hz, 3H). 13C NMR (75 MHz,
CDCl3) d ppm 156.3 (C4), 141.3 (C3), 117.1 (C2), 100.5
(C1), 34.1 (CH2CH3), 25.2 (TeCH2CH2), 13.7
(CH2CH3), 9.15 (TeCH2). LRMS m/z (rel. int., ion)
280 (10, M+), 278 (9, M+ ꢀ 2), 276 (6, M+ ꢀ 4), 223
(6), 221 (5), 219 (4), 94 (100), 57 (23). IR (neat, cmꢀ1
)
3355 (br), 2957 (s), 2926 (s), 2869 (m), 1998 (w), 1883
(w), 1640 (w), 1576 (m), 1486 (s), 1375 (m), 1243 (s),
1171 (s), 823 (s), 695 (w), 512 (m).
4-Methyl-1-butyltellanylbenzene (2e) [56950-02-8]. To
a one-necked round-bottomed flask equipped with a re-
flux condenser containing tellurium tetrachloride (5.38
g, 20 mmol), toluene (2.13 mL, 20 mmol) was added
at once, dissolving the tellurium tetrachloride promptly.
The reaction was refluxed for 12 h and a yellow solid
was formed. The system was cooled to room tempera-
ture and the trichloride was used crude in the reduc-
4-Phenyl-1-butyltellanylbenzene (2f) (2.36 g, 35%). 1H
NMR (300 MHz, CDCl3) d ppm 7.70 (d, J 8.1, 2H), 7.48
(dd, J 7.2 Hz, 1.5 Hz, 2H), 7.32 (dd, J 8.1 Hz, 6.3 Hz,
2H), 7.35–7.28 (m, 2H), 7.26–7.22 (m, 1H), 2.84 (t, J
7.6 Hz, 2H), 1.74 (qn, J 7.5 Hz, 2H), 1.34 (sext, J 7.4
Hz, 2H), 0.85 (t, J 7.4 Hz, 3H). 13C NMR (75 MHz,
1
tion/alkylation procedure. (4.23 g, 77%) H NMR (300
MHz, CDCl3) d ppm 7.61 (d, J 8.1 Hz, 2H), 7.01 (d, J
7.8 Hz, 2H), 2.86 (t, J 7.5 Hz, 2H), 2.32 (s, 3H), 1.76
(qn, J 7.3 Hz, 2H), 1.38 (sext, J 7.4 Hz, 2H), 0.89 (t, J
7.2 Hz, 3H). 13C NMR (75 MHz, CDCl3) d ppm 139.0
(C2), 137.7 (C4), 130.3 (C3), 107.8 (C1), 34.2 (CH2CH3),
25.3 (TeCH2CH2), 21.5 (CH3), 13.7 (CH2CH3), 8.74
(TeCH2). LRMS m/z (rel. int., ion) 278 (12, M+), 276
(11, M+ ꢀ 2), 274 (7, M+ ꢀ 4), 221 (4), 219 (4), 217
(3), 92 (67), 91 (100), 57 (22). IR (neat, cmꢀ1) 3062
(m), 3015 (m), 2957 (s), 2924 (s), 2865 (m), 1631 (w),
1588 (w), 1563 (w), 1486 (m), 1457 (m), 1181 (w), 1162
(w), 1013 (w), 797 (s), 480 (s). Anal. Calc. for
C11H16Te: C, 47.90; H, 5.85. Found: C, 48.02; H, 5.74%.
b-Butyltellanylnaphthalene (2g) [95849-65-3]. A one-
necked round-bottomed flask containing naphthalene
(10.25 g, 80 mmol) was melted at 120 ꢁC and tellurium
tetrachloride (5.38 g, 20 mmol) was added at once. An
evolution of HCl was observed and a yellow solid was
formed. The system was cooled to room temperature
0
0
CDCl3) d ppm 140.2 ðC1 Þ, 139.9 (C4), 138.3 ðC3 Þ,
0
0
128.5 ðC2 Þ, 127.4 (C3), 127.1 ðC4 Þ, 126.6 (C2), 110.7
(C1), 33.7 (CH2CH3), 24.9 (TeCH2CH2), 13.2
(CH2CH3), 8.33 (TeCH2). LRMS m/z (rel. int., ion)
340 (15, M+), 338 (14, M+ ꢀ 2), 336 (8, M+ ꢀ 4), 283
(6), 281 (5), 279 (4), 154 (100), 153 (19), 152 (41), 77
(6), 57 (31). IR (neat, cmꢀ1) 3060 (m), 3026 (m), 2957
(s), 2925 (s), 2866 (m), 1947 (w), 1902 (w), 1801 (w),
1751 (w), 1663 (w), 1622 (w), 1596 (m), 1477 (s), 1003
(m), 825 (m), 756 (s), 697 (s), 491 (m). Anal. Calc. for
C16H18Te: C, 56.87; H, 5.37. Found: C, 57.15; H, 5.56%.
4-Phenoxy-1-butyltellanylbenzene (2h) (3.88 g, 55%).
1H NMR (300 MHz, CDCl3) d ppm 7.68 (d, J 8.7,
2H), 7.34 (dd, J 8.4 Hz, 7.4 Hz, 2H), 7.12 (tt, J 7.4
Hz, 1.1 Hz, 1H), 7.02 (dd, J 8.5 Hz, 1.0 Hz, 2H), 6.84

R.L.O.R. Cunha et al. / Journal of Organometallic Chemistry 689 (2004) 3631–3636
3635
and the trichloride was used crude in the reduction/alky-
1
lation procedure. (2.18 g, 35%) H NMR (300 MHz,
as eluent. Benzhydrols 3a [15], 3b [16], 3c [17], 3e [18],
3f [19], 3g [20] are known and the analytical data ob-
tained were in accordance with previously reported data.
(4-Methoxy-3-methyl-phenyl)-phenyl-methanol (3d)
(0.37 g, 82%). 1H NMR (300 MHz, CDCl3) d ppm
7.37–7.20 (m, 5H), 7.13–7.10 (m, 2H), 6.74 (d, J 8.7
Hz, 1H), 5.71 (s, 1H), 3.78 (s, 3H), 2.40 (br s, 1H),
2.18 (s, 3H). 13C NMR (75 MHz, CDCl3) d ppm 157.5
CDCl3) d ppm 8.21 (s, 1H), 7.80–7.71 (m, 3H), 7.63
(d, J 8.4 Hz, 1H), 7.47–7.43 (m, 2H), 2.96 (t, J 7.6 Hz,
2H), 1.80 (qn, J 7.5 Hz, 2H), 1.40 (sext, J 7.2 Hz, 2H),
0.89 (t, J 7.2 Hz, 3H). 13C NMR (75 MHz, CDCl3) d
ppm 137.9, 135.3, 134.5 (C9), 132.8 (C10), 128.4, 128.0,
127.5, 126.5, 126.4, 109.6 (C2), 34.3 (CH2CH3), 25.4
(TeCH2CH2), 13.7, 8.92 (TeCH2). LRMS m/z (rel. int.,
ion) 314 (12, M+), 312 (11, M+ ꢀ 2), 310 (7, M+ ꢀ 4),
257 (6), 255 (5), 253 (4), 128 (100), 127 (35), 57 (14).
IR (neat, cmꢀ1) 3049 (m), 2957 (s), 2925 (s), 2865 (m),
1946 (w), 1912 (w), 1829 (w), 1757 (w), 1701 (w), 1620
(m), 1581 (m), 1497 (m), 1458 (m), 1162 (m), 811 (s),
740 (s), 625 (m), 473 (s). Anal. Calc. for C14H16Te: C,
53.92; H, 5.17. Found: C, 54.01; H, 5.19%.
0
0
0
(C4), 144.4 ðC1 Þ, 136.0 (C3), 129.4 ðC3 Þ, 128.6 ðC2 Þ,
0
127.6 (C2), 127.0 (C1), 126.7 ðC4 Þ, 125.4 (C6), 110.0
(C5), 76.1 (CHOH), 55.6 (OCH3), 16.6 (CH3). LRMS
m/z (int. rel., ion) 228 (33, M+), 211 (6), 197 (4), 149
(38), 123 (100), 105 (60), 91 (25), 77 (54), 51 (19). IR
(neat, cmꢀ1) 3387 (br), 2950 (m), 2836 (w), 1609 (w),
1502 (m), 1457 (m), 1252 (m), 1130 (m), 1033 (m), 811
(m), 701 (w), 595 (w). Anal. Calc. for C15H16O2: C,
78.92; H, 7.06. Found: C, 78.60; H, 7.07%.
4-Hydroxy-1-butyldichloro-k4-tellanylbenzene (2j). To
a solution of crude 4-hydroxy-1-butyltellanylbenzene
in dry benzene (40 mL) at 10 ꢁC, sulfuryl chloride
(2.70 g, 20 mmol) was added. The reaction was stirred
for 20 min at room temperature, the solvent was re-
moved at reduced pressure and a colorless oil was ob-
tained. The oil was solubilized in dry dichloromethane
and hexanes was added until the precipitation of a white
solid. Then the solution was cooled in an ice bath and
the white solid was filtered off, washed with hexanes
and recrystallized from a dichloromethane/hexanes mix-
ture (85:15). (2.92 g, 84%); m.p.: 164–166 ꢁC, uncor-
Acknowledgements
The authors thank FAPESP, CAPES and CNPq for
financial support.
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rected. H NMR (300 MHz, CDCl3) d ppm 7.98 (d, J
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