Synthesis of Thiol, Selenol, and Tellurol Esters by the Reaction of Organochalcogeno Mercurials with Acid Chlorides

Article abstract of DOI:10.1021/om990589e

Summary: Thiol, selenol, and tellurol esters were prepared by the reaction of bis(organochalcogeno)mercurials with acid chlorides in chloroform or carbon tetrachloride and in the presence of tetrabutylammonium halides as catalysts.

Full text of DOI:10.1021/om990589e

Organometallics 1999, 18, 5183-5186
5183
Syn th esis of Th iol, Selen ol, a n d Tellu r ol Ester s by th e
Rea ction of Or ga n och a lcogen o Mer cu r ia ls w ith Acid
Ch lor id es
Claudio C. Silveira,* Antonio L. Braga, and Enrique L. Larghi
Departamento de Quı´mica, UFSM, Caixa Postal 5001, 97105-900 Santa Maria, RS, Brazil
Received J uly 27, 1999
Summary: Thiol, selenol, and tellurol esters were pre-
pared by the reaction of bis(organochalcogeno)mercurials
with acid chlorides in chloroform or carbon tetrachloride
and in the presence of tetrabutylammonium halides as
catalysts.
halides with mercaptans,13 selenols,14 or dichalco-
genides,15 as well as their alkali metal salts.16 In
addition, carboxylic acids are also transformed into thiol
and selenol esters by treatment with arylthio- or ar-
ylselenocyanates and tributyl phosphine in dichlo-
romethane.17 Group IIIA organyl chalcogenides (B and
Al) convert carboxylic acid esters into their thiol18 and
selenoll9 analogues. Also, aldehydes react under Tish-
chencko-type conditions to afford all of the isologues.20
Thiol esters have been prepared by the acid-catalyzed
hydrolysis of thioacetylenes.21 Miscellaneous methods
are summarized in ref 22.
Bis(organochalcogenyl)mercury compounds have been
long known, but aside from applications related to
inorganic chemistryl or solid-state chemistry in the
development of semiconductors,2 no organic chemistry
has been associated with this class of compounds. In
contrast, related parent compounds such as (organo-
chalcogenyl) cadmium,3 lead,4 thallium,5 and silver6
reagents have proved to be useful sources of nucleophilic
moieties. Reasoning that those mercury compounds
have never been reported as nucleophiles due to their
poor reactivity and low yields attained under classical
reaction conditions,3-6 it was decided to explore the
scope and limitations of the reaction of bis(organochal-
cogenyl)mercury compounds with acyl chlorides, as an
approach to the synthesis of organochalcogenol esters.
Since many of these methodologies require vigorous
reaction conditions, often dealing with moisture- or air-
sensitive reagents and due to the growing interest in
new organic strategies for the production of chalcogenol
ester compounds, we wish to report here a new method
for their synthesis based on the reaction of bis(orga-
nochalcogenyl)mercury compounds with acyl chlorides
under tetrabutylammonium halide catalysis, as shown
in eq 1. The starting mercurials, bis(phenylthiolate)Hg
(1), bis(phenylselenolate)Hg (2), bis(n-butyltellurolate)-
Hg (3), bis(ethanethiolate)Hg (4), and bis[(2-methyl)-2-
propanethiolate)]Hg (5), are stable solids, easily pre-
pared by the reaction of metallic Hg with the correspond-
ing thiols, diphenyl diselenide, or di-n-butyl ditelluride,
Thiol, selenol, and tellurol esters are useful synthetic
intermediates employed as mild acyl-transfer reagents,5a,7
building blocks for heterocyclic compounds (oxazole,8
â-lactone9), and precursors of acyl radicals10 and an-
ions11 and for asymmetric aldol reactions.12 These
compounds are usually available by the reaction of acyl
(11) Hiiro, T.; Morita, Y.; Inoue, T.; Kambe, N.; Ogawa, A.; Ryu, I.;
Sonoda, N. J . Am. Chem. Soc. 1990, 112, 455.
* Corresponding author. Phone: + 55.55.220.8754/220.8669. Fax:
+ 55.55.220.8754. E-mail: silveira@quimica.ufsm.br.
(1) (a) Lechner, J . Chem. Ber. 1915, 48, 1425. (b) Wertheim, E. J .
Am. Chem. Soc. 1929, 51, 3661. (c) Bradley, D. C.; Kunchur, N. R. J .
Chem. Phys. 1964, 40, 2258. (d) Liesk, Von J .; Klar, G. Z. Anorg. Allg.
Chem. 1977, 435, 103. (e) Dance, N. S.; J ones, C. H. W. J . Organomet.
Chem. 1978, 152, 175. (f) Okamoto, Y.; Yano, T. J . Organomet. Chem.
1971, 29, 99. (g) Paige, H. L.; Passmore, J . Inorg. Nucl. Chem. Lett.
1973, 9, 277.
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1975, 97, 3515. (b) Detty, M. R.; Wood, G. P. J . Org. Chem. 1980, 45,
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Org. Chem. 1958, 23, 363. (b) Zang, Y.; Yu, Y.; Lin, R. Synth. Commun.
1993, 23, 189.
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1989, 30, 1829. (c) Viana, L. H.; Dabdoub, M. J . Synth. Commun. 1992,
22, 1619.
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10.1021/om990589e CCC: $18.00 © 1999 American Chemical Society
Publication on Web 11/05/1999

5184 Organometallics, Vol. 18, No. 24, 1999
Notes
Sch em e 1
Sch em e 2
because of its instability under the employed experi-
mental conditions.
It was observed that the yield is related to the
reactivity of both the acyl chloride and the mercury
reagent. The change from S to Se and Te was ac-
companied by a decrease in yield. The addition of the
ammonium halide catalyst greatly improved the ef-
ficiency of the reaction. In the absence of n-Bu4NBr, the
reaction of benzoyl chloride with bis(phenylseleno)Hg
2 gave only a 53% yield, even after a 24 h reaction
period. The reaction between benzoyl chloride and 2 in
chloroform mediated by n-Bu4NBr was monitored by IR
spectroscopy,24 in order to obtain an insight into the
reaction course. It was observed that at the start of the
reaction the CdO stretching frequency of benzoyl
chloride was barely changed (=5 cm-1); it was consumed
at such a rate that less than 10% remained after 1 h.
Unexpectedly, however, no sign of the product (1680
cm-1) was detected. The characteristic band of Ph-
COSePh began to appear only after 1.5 h. At that time,
the presence of the selenol ester was also detected by
TLC. These observations rule out an anionic catalyst
effect25 on Hg(SePh)2 to produce a more intense selenol
ester band. Instead, strong absorptions at 1530, 1475,
and 1425 cm-1 were observed, which could not be
attributed to Hg(SePh)2 or to ClHgSePh when compared
with authentic spectra. Therefore, we tentatively sug-
gest that this transformation might follow a pathway
as depicted in Scheme 2: (step 1) coordination of the
mercury with the carbonyl and chlorine moieties to form
a complex in rapid equilibrium with reactants (the
magnitude of ∆ν ≈ 5 cm-1 suggests a weak interaction);
(step 2) the complex collapses into an intermediate (ν
≈ 1530, 1475, and 1425 cm-1 attributed to this inter-
mediate); (step 3) a halide anion reacts irreversibly the
intermediate, giving rise to the products. Here one can
see the important role played by the n-Bu4NX catalyst.
Ta ble 1. Syn th esis of Ch a lcogen ol Ester sa by
Rea ction of Bis(or ga n och a lcogen yl)m er cu r y w ith
Acyl Ch lor id es
entry
no.
C6H5S
(yield, %)
C6H5Se
(yield, %)
n-BuTe
(yield, %)
R
1
2
3
4
5
6
7
8
9
C6H5
98
99
99
98
99
72
72
97
94
72
99b
74
79
81c
94
74
70
82
81
70
39
44
p-ClC6H4
p-NO2C6H4
p-MeOC6H4
C6H5CH2
(C6H5)2CH
CH3
ClCH2
t-C4H9
n-C5H11
35
7
10
a
b
Isolated yields. 4 h at reflux. c 17 h at room temperature.
according to literature procedures.1,2 The mercury-bis-
(organochalcogenide) can deliver only one YR1 group
under the present conditions. The organochalcogen and
Hg moieties can be easily recovered from the RlYHgCl
by a procedure described previously.23
RCOCl
RCOYR1 + R1YHgCl
Hg(YR1)2
8
Y ) S, Se, Te
The reactions studied are outlined in Scheme 1 and
are performed in chloroform or carbon tetrachloride. Bis-
(organochalcogenates)Hg exhibit different reactivities.
Thus, compound 1 furnishes very high yields of the
products by reaction in chloroform at reflux for 4 h,
regardless of the structure of the acid chloride. Com-
pounds 4 and 5 as well as 2 react at room temperature
in chloroform and in the presence of a catalytic amount
of n-Bu4NBr (vide infra). The reactions as monitored by
TLC are completed after 5 h. Compound 3 (Te deriva-
tive) reacted best in carbon tetrachloride, and the use
of n-Bu4NCl instead of n-Bu4NBr was required.
The yields obtained are summarized in Table 1. The
reaction was studied in detail with compounds 1-3.
Compounds 1 and 2 reacted well with several acid
chlorides, furnishing the desired products in medium
to high yield. Fewer examples were studied with 3 since
lower yields were obtained in its reactions, mainly
Exp er im en ta l Section
1H (200 MHz) and 13C (50 MHz) NMR spectra were obtained
with a Bruker AC-200 spectrometer in CDCl3 with TMS as
the internal standard. IR spectra were recorded on a Bruker
IFS-28 or Perkin-Elmer 1310 spectrometer. Low-resolution
mass spectra were obtained with a Hewlett-Packard 5988-
8/5890 GC/MS spectrometer, operating at 70 eV. Elemental
(24) IR experiment: [ ] = 4 × 10-2 M in a NaCl cell of 0.2 mm
(Teflon) path, double-beam spectrophotometer, CHCl3 spectroscopic
grade, and all reagents were treated by extended time in a vacuum to
avoid humidity.
(25) (a) Hughes, E. D.; Ingold, C. K.; Roberts, R. M. G. J . Chem.
Soc. 1964, 3900. (b) Beletskaya, I. P.; Butin, K. P.; Ryabtsev, A. N.;
Reutov, O. A. J . Organomet. Chem. 1973, 59, 1.
(23) Fredga, A. Chem. Ber. 1938, 71B, 286.

Notes
Organometallics, Vol. 18, No. 24, 1999 5185
analyses were performed on a Vario EL analysensysteme, at
UFSM. Column chromatography was carried out with Merck
silica gel (230-400 mesh). Thin-layer chromatography (TLC)
was performed on silica gel 60 F-254. All solvents used were
previously dried and distilled according to the usual methods.27
Phenylthiol, ethanethiol, and tert-butylthiol were purchased
from Aldrich. Diphenyl diselenide28 and di-n-butyl ditelluride29
were prepared by literature procedures. The acid chlorides
were prepared by standard techniques30 from the carboxylic
acids obtained from commercial sources. All operations were
carried out in oven-dried glassware under an inert atmosphere
of dry argon.
Ca u tion ! The toxicity of mercury compounds is well-known,
and so, all operations should be carried out under a well-
ventilated hood, with all requirements for appropriate waste
disposal. Approximately up to 90% of total mercury was
recovered. Also, we suggest treatment with nitric acid and
recovering the mercury by reduction of the resulting salts with
metallic Fe.
Gen er a l P r oced u r e for th e Rea ction of 2, 4, a n d 5 w ith
Acyl Ch lor id es. To a stirred suspension of 2, 4, or 5 (1 mmol)
in chloroform (4 mL) under an argon atmosphere at room
temperature was added n-Bu4NBr (0.04 mmol). After stirring
for 2 min, the acyl chloride (1 mmol; dissolved in 1 mL of
solvent) was added by syringe. The reaction mixture was
stirred for 5 h, and the liquid phase was then evaporated in
vacuo. The solid residue was dissolved in ethyl acetate and
filtered through Celite.31 The organic phase was evaporated,
and the crude product was purified by silica gel column
chromatography, eluting with hexanes followed by ethyl
acetate, to give the appropriate alkanethiol or phenylselenol
ester.
Gen er a l P r oced u r e for t h e R ea ct ion of 3 w it h Acyl
Ch lor id es. To a stirred suspension of 3 (1 mmol) in carbon
tetrachloride (4 mL) under an argon atmosphere at room
temperature was added n-Bu4NCl (2 mmol; 2 equiv). After
stirring for 2 min, the acyl chloride (1 mmol, dissolved in 1
mL of solvent) was added by syringe. The reaction mixture
was stirred for a maximum period of 2 h, and the liquids then
were poured into 5% deactivated neutral alumina suspended
in CCl4 and filtered rapidly. The orange filtrate was evaporated
in vacuo, and the resulting crude liquid was purified by silica
gel column chromatography eluting with hexanes followed by
ethyl acetate, to afford the tellurol ester.
P r ep a r a tion of 1, 4, a n d 5. To a stirred solution of Hg-
(OAc)2 (1 equiv) in EtOH under argon at room temperature
was added RSH (2.05 equiv). After
a few minutes, the
suspension was filtered and the solids were washed with
EtOH, acetone, and ether. The solids were dried in vacuo. The
yields were from 80 to 100%.
Di(p h en ylsu lfen yl)m er cu r y (1): white solid; mp 149.8-
152.1 °C (lit.la mp 152.5-153.5 °C); 1H NMR (DMSO-d6) δ 7.36
(d, J ) 7.0 Hz, 2H), 7.19-7.06 (m, 3H); IR (KBr) 3080, 3000,
S-Eth yl th ioben zoa te: yield 99%, colorless oil. Spectro-
scopic data were in good agreement with the literature.22c
S-ter t-Bu tyl th ioben zoa te: yield 66%, white solid, mp
123.8-130.5 °C (dec); bp 75 °C/7 mmHg (lit.18a 110 °C/28
mmHg).
S-P h en yl th ioben zoa te: yield 98%, white solid, mp 54.8-
55.1 °C (lit.17 mp 55-56 °C). S-P h en yl p-ch lor oth ioben -
zoa te: yield 99%, white solid, mp 80.6-81.8 °C (lit.17 mp 79.5-
81.5 °C).
1440, 1310, 1030, 1010, 910, 740, 690 cm-1
.
Di(eth ylsu lfen yl)m er cu r y (4): white solid; mp 75.2-76.8
°C (lit.lb mp 76 °C); IR (KBr) 2950, 2918, 2856, 1441, 1365,
1260, 972, 769, 407 cm-1
.
Di(ter t-bu tylsu lfen yl)m er cu r y (5): white solid; mp 157.9-
159.4 °C (dec); IR (KBr) 2969, 2955, 2889, 1454, 1362, 1163,
1025, 575 cm-1
P r ep a r a tion of 2 a n d 3.
.
S-P h en yl p-n itr oth ioben zoa te: yield 99%, pale brownish
lf,g
solid, mp 151.3-153.0 °C (lit.13c mp 160 °C).
To a solution of diphenyl
diselenide or di-n-butyl ditelluride (1 equiv) in dioxane (3 mL/
mmol) was added metallic mercury (1.4 equiv). The solution
was vigorously stirred under argon for 30 min (for the
tellurium derivative) or 4 h (for the selenium derivative). The
solid product was filtered, washed with benzene and ether,
and dried in high vacuo. The yields were nearly quantitative.
Di(p h en ylselen en yl)m er cu r y (2): greenish solid; mp
146-148 °C (dec) (lit.lf mp 152-153 °C); IR (KBr) 3052, 1573,
S-P h en yl p-m eth oxyth ioben zoa te: yield 98%, pale yel-
low solid, mp 93.3-94.7 °C (lit.17 mp 94-95 °C).
S-P h en yl 2-p h en yleth a n eth ioa te: yield 99%, white solid,
mp 33.0-34.6 °C (lit.17 mp 33.0-33.5 °C).
S-P h en yl 2,2-d ip h en yleth a n eth ioa te: yield 72%, white
solid, mp 87.6-89.2 °C (lit.22g mp 84-85 °C).
S-P h en yl eth a n eth ioa te: yield 72%, colorless oil. Spec-
troscopic data were in good agreement with literature.5b
S-P h en yl 2-ch lor oeth a n eth ioa te: yield 97%, white solid,
mp 39.3-41.2 °C (lit.15a 43-43.5 °C).
S-P h en yl 2,2-d im eth ylp r op a n eth ioa te: yield 94%, color-
less oil. Spectroscopic data were in good agreement with
literature.13b
1471, 1435, 1299, 1070, 1018, 999, 902, 731, 688, 468 cm-1
.
Di(n -bu tyltellu r en yl)m er cu r y (3): light-brown-yellow
solid; mp 106.2 °C (dec); IR (KBr) 2954, 2869, 1637, 1459, 1376,
1242, 1155, 883, 703, 617 cm-1. Anal. Calcd for C8H18HgTe2:
C, 16.86; H, 3.18. Found: C, 16.74; H, 3.32.
Gen er a l P r oced u r e for t h e R ea ct ion of 1 w it h Acyl
Ch lor id es. To a stirred suspension of 1 (l mmol) in chloroform
(4 mL) under argon atmosphere at room temperature was
added n-Bu4NBr (0.04 mmol). After 2 min of stirring the acyl
chloride (1 mmol; dissolved in 1 mL of solvent) was added
slowly by a syringe. The reaction mixture was refluxed for 4
h, then cooled to room temperature and evaporated in vacuo.
The solid was resuspended in ethyl acetate and filtered
through Celite.31 The organic phase was evaporated, and the
crude product was purified by silica gel column chromatogra-
phy, eluting with hexanes followed by ethyl acetate, to give
the thiol ester.
S-P h en yl h exa n eth ioa te: yield 72%, colorless oil. Spec-
troscopic data were in good agreement with literature.22d
Se-P h en yl selen oben zoa te: yield 99%, yellowish solid, mp
38.3-39.8 °C (lit.3 mp 38.5-39.5 °C).
Se-P h en yl p-ch lor oselen oben zoa te: yield 74%, white
solid, mp 81.1-82.1 °C (lit.17 mp 83.5-84.5 °C).
Se-P h en yl p-n itr oselen oben zoa te: yield 79%, pale green
solid, mp 136.5-138.2 °C (lit.13c mp 137 °C).
Se-P h en yl p-m eth oxyselen oben zoa te: yield 81%, white
solid, mp 60.3-61.6 °C (lit.17 mp 62-63 °C).
Se-P h en yl 2-p h en yleth a n eselen oa te: yield 94%, yellow-
ish solid, mp 42.5-43.0 °C (lit.22a mp 41-43 °C).
Se-P h en yl 2,2-d ip h en yleth a n eselen oa te: yield 99%, yel-
lowish solid, mp 71.6-72.6 °C; 1H NMR δ 7.48-7.28 (m, 15H),
5.29 (s, 1H); 13C NMR δ 200.0, 137.5, 135.6, 129.3, 129.1, 128.9,
128.7, 127.7, 126.9, 68.2; LRMS m/z (relative intensity) 195
(M+ - SePh, 5), 167 (100); IR (KBr) 3025, 1755, 1665, 1555,
1475, 1285, 1070, 950, 825, 775, 605 cm-1. Anal. Calcd for
(26) Pearson, R. G. J . Am. Chem. Soc. 1963, 85, 3533.
(27) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals, 3rd ed.; Pergamon Press: New York, 1988.
(28) Sharpless, K. B.; Young, M. W. J . Org. Chem. 1975, 40, 947.
(29) Engman, L.; Cava, M. P. Synth. Commun. 1982, 12, 163.
(30) Vogel, A. I. Textbook of Practical Organic Chemistry; ELBS:
London, 1978. For 4-nitrobenzoyl chloride: Adams, R.; J enkins, R. L.
Org. Synth. Collect. I 1932, 394.
C
20H16OSe: C, 68.27; H, 4.33. Found: C, 68.38; H, 4.59.
(31) The solid residue from the filtration consisted of PhYHgX (X )
Cl, Br), isolated in high yield (=90%), from which PhYYPh and Hg
can be recovered (see ref 23).
Se-P h en yl eth a n eselen oa te: yield 70%, yellow oil. Spec-
troscopic data were in good agreement with literature.5b

5186 Organometallics, Vol. 18, No. 24, 1999
Notes
Se-P h en yl 2-ch lor oeth a n eselen oa te: yield 82%, yellow
Ben zen eselen en ylm er cu r ic ch lor id e (7): photosensitive
yellow solid, mp 174-180 °C (dec); 1H NMR (DMSO-d6) δ
7.53-7.49 (m, 2H), 7.15-7.13 (m, 3H); 13C NMR (DMSO-d6) δ
134.2, 128.9, 128.5, 125.7; IR (KBr) 3070, 2980, 1580, 1480,
1
solid (mp 35.5-36.9 °C); H NMR δ 7.45-7.32 (m, 5H), 4.14
(s, 2H); 13C NMR δ 196.6, 135.9, 129.5, 129.3, 125.3, 51.4; IR
(film) 3080, 2960, 1720, 1580, 1445, 1260, 1055, 970, 700 cm-1
.
1440, 1020, 1005, 730, 690 cm-1
.
Anal. Calcd for C8H7ClOSe: C, 41.14; H, 3.02. Found: C, 41.05;
H, 2.99.
n -Bu tyltellu r en ylm er cu r ic ch lor id e (8): yellowish solid,
mp 130.8-132.6 °C; 1H NMR (DMSO-d6) δ 3.18 (t, J ) 7.0
Hz, 2H), 1.85 (quint, J ) 7.0 Hz, 2H), 1.35 (sext, J ) 7.0 Hz,
2H), 0.96 (t, J ) 7.0 Hz, 3H); IR (KBr) 2954, 2869, 1618, 1459,
1244, 1180, 887, 617, 487 cm-1. 1-Eth a n esu lfen ylm er cu r ic
ch lor id e (9): white solid, mp 208-210 °C (dec); LRMS m/z
(relative intensity) 297 (M+, 47), 236 (10), 232 (14), 202 (100),
101 (10), 61 (98); IR (KBr) 3080, 1450, 1390, 1260, 1050, 980,
Se-P h en yl 2,2-d im eth ylp r op a n eselen oa te: yield 81%,
yellowish oil; 1H NMR δ 7.50-7.45 (m, 2H), 7.38-7.34 (m, 3H),
1.28 (s, 9H); 13C NMR δ 207.7, 136.3, 129.1, 128.6, 126.3, 49.9,
27.0; LRMS m/z (relative intensity) 242 (M+, 2), 57 (100); IR
(film) 3058, 2967, 1719, 1579, 1475, 1364, 1227, 1022, 907, 737,
689, 482 cm-1. Anal. Calcd for C11H14OSe: C, 54.54; H, 5.95.
Found: C, 54.87; H, 5.85.
Se-P h en yl h exa n eselen oa te: yield 70%, yellowish oil.
Spectroscopic data were in good agreement with literature.22e
Te-n -Bu tyl tellu r oben zoa te: yield 39%, yellow oil. Spec-
troscopic data were in good agreement with literature.20
Te-n -Bu tyl p-ch lor otellu r oben zoa te: yield 44%, yellow
oil. Spectroscopic data were in very good agreement with
literature.20
780, 640 cm-1
.
2-Meth yl-2-pr opan esu lfen ylm er cu r ic ch lor ide (10): pho-
tosensitive white solid, mp 135-150 °C (dec); LRMS m/z
(relative intensity) 325 (M+, 3), 236 (1), 202 (47), 101 (7), 57
(100); IR (KBr) 2780, 1460, 1370, 1160 cm-1
.
Te-n -Bu tyl 2-p h en yleth a n etellu r oa te: yield 35%, yellow
oil. Spectroscopic data were in good agreement with literature.22f
Te-n -Bu t yl 2,2-d im et h ylp r op a n et ellu r oa t e: yield 7%,
yellow oil. Spectroscopic data were in good agreement with
literature.20
Ack n ow led gm en t. The authors thank the following
agencies for financial support: FAPERGS, CNPq/
PADCT, and CAPES. E.L.L. thanks the CNPq for a
Master fellowship. Thanks are due to Prof. N. Petrag-
nani and Dr. T. Kaufman for revision of the manuscript.
Ben zen esu lfen ylm er cu r ic ch lor id e (6): white solid, mp
198 °C (dec); IR (KBr) 3047, 1571, 1476, 1436, 1021, 908, 738,
686, 482 cm-1
.
OM990589E