A convenient synthesis of diacyl sulfides using a novel sulfur transfer reagent

Article abstract of DOI:10.1002/hc.10217

Various diacyl sulfides were synthesized by reaction of acyl chlorides with LiAlHSH. Reaction of glutaryl chloride with LiAlHSH afforded glutaric thioanhydride.

Full text of DOI:10.1002/hc.10217

Heteroatom Chemistry
Volume 14, Number 7, 2003
A Convenient Synthesis of Diacyl Sulfides
Using a Novel Sulfur Transfer Reagent
Mamoru Koketsu, Yoji Sekiya, and Hideharu Ishihara
Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501-1193, Japan
Received 29 May 2003; revised 18 June 2003
confirmed the usefulness of LiAlHSH as the reagent
ABSTRACT: Various diacyl sulfides were synthe-
for the introduction of sulfur.
sized by reaction of acyl chlorides with LiAlHSH.
Reaction of glutaryl chloride with LiAlHSH afforded
ꢀ
C
glutaric thioanhydride.
2003 Wiley Periodicals, Inc.
RESULTS AND DISCUSSION
Heteroatom Chem 14:633–635, 2003; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.10217
Diacyl sulfides 3 were conveniently prepared accord-
ing to the method shown in Scheme 1. The reaction
of 2 equiv. of acyl chlorides 1 with LiAlHSH 2 gave
diacyl sulfides in good yields (Table 1). The quanti-
tative formation of low molecular weight products,
3h–3j, was confirmed by TLC analysis. However, they
were lost considerably during concentration pro-
cess because they were volatile. Both aromatic and
aliphatic diacyl sulfides 3 were obtained in excellent
yields (Table 1). Moreover, we investigated the reac-
tion of glutaryl chloride with LiAlHSH 2 (Scheme 2).
Glutaric thioanhydride 4 was obtained by the reac-
tion in 89% yield.
For the synthesis of diacyl selenides and cyclic
selenoanhydrides using LiAlHSeH, the reactions
were carried out at 0◦C for 2 h in order to avoid
decomposition of the resulting selenium-containing
compounds [3c]. In contrast, in the present proce-
dure, higher temperatures and longer reaction times
could be used because of the stability of LiAlHSH
2 and the products. In conclusion, the synthesis us-
ing LiAlHSH 2 can give diacyl sulfides 3 and glutaric
thioanhydride 4 in good yields by mere stirring of
elementary sulfur and lithium aluminum hydride in
THF. It was confirmed that LiAlHSH 2 behaves like
LiAlHSeH, and represents an excellent reagent for
the introduction of sulfur. The present reaction can
be carried out under easier conditions without the
use of foul smelling and toxic materials, such as H2S
or thiocarboxylic acid.
INTRODUCTION
Some methods for synthesizing diacyl sulfides have
been reported [1]. These methods, however, have
some disadvantages, such as the use of expensive
reagent, the limited availability of the starting ma-
terials, severe conditions, and stench and toxicity of
the reagents. A more convenient method is required
to overcome these disadvantages. Recently, we de-
veloped a novel selenating reagent, LiAlHSeH [2],
which is generated by stirring selenium powder and
LiAlH4 in THF. This reagent is useful for preparing a
variety of different selenium-containing compounds
[3]. However, application of the same procedure to
the sulfur atom, while it seems reasonable, has been
been scarcely demonstrated [4]. In the present study,
we investigated the preparation of various diacyl sul-
fides from the corresponding acyl chlorides 1 using
LiAlHSH 2. Herein, we report a new method for
preparation of diacyl sulfides 3, in which we have
Correspondence to: Mamoru Koketsu; e-mail: koketsu@cc.gifu-
u.ac.jp.
Contract grant sponsor: Ministry of Education, Culture Sports,
Science and Technology of Japan.
Contract grant number: 14540490.
2003 Wiley Periodicals, Inc.
c
ꢀ
633

634 Koketsu, Sekiya, and Ishihara
SCHEME 1
SCHEME 2
eluent to give 0.614 g (84%) 3a as a white powder.
EXPERIMENTAL
General
1
Mp: 102.3–103.8◦C; H NMR (CDCl3) δ 7.43 (4H, t,
J = 7.8 Hz, Ar), 7.57 (2H, t, J = 7.8 Hz, Ar), 7.88 (4H,
d, J = 7.8 Hz, Ar); 13C NMR (CDCl3) δ 127.4, 128.0,
128.7, 134.4, 190.1; IR (KBr): 1718, 1671 cm−1; MS
(CI): m/z = 243 [M+ + 1] [3d].
Melting points were determined by use of a Yanag-
imoto micromelting point apparatus and are un-
corrected. IR spectra were measured on a Perkin-
Elmer 1600 spectrometer. H and 13C spectra were
1
recorded on a JEOL JNM-ꢀ400 spectrometer. Mass
spectra were obtained on a Shimadzu 9020-DF mass
spectrometer. Tetrahydrofuran was distilled from
sodium-benzophenone and immediately used.
Preparation of LiAlHSH 2: LiAlHSH 2 was pre-
pared in a method similar to that previously reported
[2]. To a suspension of sulfur powder (0.80 g, 10.0
mmol) in dry THF (100 ml) was added lithium alu-
minum hydride (0.38 g, 10.0 mmol) at room tem-
perature under an argon atmosphere. The mixture
was stirred for 30 min. The yellow sulfur powder was
consumed in less than 10 min. The reaction mixture
became a heterogeneous grayish suspension. Com-
pound 2 formed in situ was then ready for further
reaction.
Bis(2-methylbenzoyl) Sulfide (3b) [3d,5]
1
White powder; Mp: 52.7–53.7◦C; H NMR (CDCl3)
δ 2.40 (6H, s, CH3), 7.11 (4H, m, Ar), 7.26 (2H, d,
J = 7.6 Hz, Ar), 7.73 (2H, d, J = 7.6 Hz, Ar); 13C
NMR (CDCl3) δ 20.7, 125.7, 129.4, 131.7, 132.5, 136.5,
138.3, 187.1; IR (KBr): 1733, 1677 cm−1; MS (CI):
m/z = 271 [M+ + 1].
Bis(3-methylbenzoyl) Sulfide (3c) [3d]
1
White powder; Mp: 35.0–35.8◦C; H NMR (CDCl3) δ
2.25 (6H, s, CH3), 7.20 (2H, t, J = 7.6 Hz, Ar), 7.26
(2H, d, J = 7.6 Hz, Ar), 7.63 (2H, s, Ar), 7.66 (2H, d,
J = 7.6 Hz, Ar); 13C NMR (CDCl3) δ 21.0, 125.5, 128.5,
135.0, 136.8, 138.6, 185.0; IR (KBr): 1714, 1662 cm−1;
MS (CI): m/z = 271 [M+ + 1].
Dibenzoyl Sulfide (3a)
Bis(4-methylbenzoyl) Sulfide (3d) [3d]
Benzoyl chloride (0.843 g, 6.0 mmol) was added to
the suspension of LiAlHSH 2 (3.0 mmol), prepared
as described above. The reaction mixture was stirred
at room temperature for 3 h. The mixture was ex-
tracted with diethyl ether and washed with satu-
rated NaCl solution. The organic layer was dried
over sodium sulfate and evaporated to dryness. The
residue was purified by flash chromatography on sil-
ica gel with dichloromethane:n-hexane (1:2) as the
1
White powder; Mp: 68.5–70.0◦C; H NMR (CDCl3)
δ 2.04 (6H, s, CH3), 7.26 (4H, d, J = 8.4 Hz, Ar),
7.90 (4H, d, J = 8.4 Hz, Ar); 13C NMR (CDCl3) δ
21.7, 128.5, 129.6, 134.5, 145.5, 184.8; IR (KBr): 1715
cm−1; MS (CI): m/z = 271 [M+ + 1].
Bis(4-methoxybenzoyl) Sulfide (3e) [3d]
1
White powder; Mp: 81.7–82.8◦C; H NMR (CDCl3) δ
3.88 (6H, s, CH3), 6.94 (4H, d, J = 8.8 Hz, Ar), 8.00
(4H, d, J = 8.8 Hz, Ar); 13C NMR (CDCl3) δ 55.6,
114.0, 129.9, 130.9, 164.5, 183.8; IR (KBr): 1716,
1654 cm−1; MS (CI): m/z = 303 [M+ + 1].
TABLE 1 Synthesis of Diacyl Sulfides 3
R
Yield (%) of 3
R
Yield (%) of 3
C6H5
3a 85
3b 78
3c 89
3d 85
3e 97
3f 77
3g 79
C H5
3
(CH3)2CH
C5H11
C17H35
3h 5.4a
3i 9.9a
3j 6.6a
3k 81
3l 84
3m 79
2-CH3C6H4
3-CH3C6H4
4-CH3C6H4
4-CH3OC6H4
4-ClC6H4
C2H7
Bis(4-chlorobenzoyl) Sulfide (3f) [3d]
1
White powder; Mp: 72.2–73.2◦C; H NMR (CDCl3) δ
7.48 (4H, d, J = 8.4 Hz, Ar), 7.95 (4H, d, J = 8.4 Hz,
Ar); 13C NMR (CDCl3) δ 129.3, 129.8, 135.1, 141.2,
183.6; IR (KBr): 1713, 1678 cm−1; MS (CI): m/z = 311
[M+ + 1].
C6H5OCH2
4-NO2C6H4
aIt was confirmed by TLC analysis that product was formed
quantitatively.

A Convenient Synthesis of Diacyl Sulfides Using a Novel Sulfur Transfer Reagent 635
46.0, 195.5; IR (KBr): 1768 cm−1; MS (CI): m/z = 567
[M+ + 1].
Bis(4-nitrobenzoyl) Sulfide (3g) [3d]
White powder; Mp: 167.7–169.0◦C; 1H NMR (CDCl3)
δ 8.17 (4H, d, J = 8.0 Hz, Ar), 8.33 (4H, d, J = 8.0 Hz,
Ar); 13C NMR (CDCl3) δ 123.7, 130.7, 136.4, 150.0,
192.4; IR (KBr): 1702 cm−1; MS (CI): m/z = 333 [M+
+ 1].
Bis(phenoxyacetyl) Sulfide (3m)
1
Yellow liquid; H NMR (CDCl3) δ 4.59 (4H, s, CH2),
6.92 (4H, d, J = 8.4 Hz, Ar), 7.02 (2H, d, J = 8.4 Hz,
Ar), 7.28 (4H, t, J = 8.4 Hz, Ar); 13C NMR (CDCl3)
δ 114.3, 121.0, 121.5, 129.3, 172.4, 199.7; IR (neat):
1711 cm−1; MS (CI): m/z = 303 [M+ + 1]); HRMS
m/z = 302.0609 for C16H14O4S: found 302.0615.
Dipropionyl Sulfide (3h) [3d,5]
1
Yellow liquid; H NMR (CDCl3) δ 1.15 (6H, t, J =
7.4 Hz, CH3), 2.83 (4H, q, J = 7.4 Hz, CH2); 13C NMR
(CDCl3) δ 1.97, 41.7, 194.7; IR (neat): 1694 cm−1; MS
(CI): m/z = 147 [M+ + 1].
Glutaric Thioanhydride (4) [6]
Yellow liquid; 1H NMR (CDCl3) δ 2.09 (2H, m, CH2),
2.74 (4H, t, J = 6.0 Hz, CH2); 13C NMR (CDCl3) δ 18.4,
40.4, 197.4; IR (neat): 1694 cm−1; MS (CI): m/z = 131
[M+ + 1].
Dibutyryl Sulfide (3i) [3d]
1
Yellow liquid; H NMR (CDCl3) δ 0.90 (6H, t, J =
7.4 Hz, CH3), 1.63 (4H, m, CH2), 2.66 (4H, t, J =
7.4 Hz, CH2); 13C NMR (CDCl3) δ 13.2, 18.1, 47.7,
194.6; IR (neat): 1705 cm−1; MS (CI): m/z = 175 [M+
+ 1].
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Bis(2-methylpropionyl) Sulfide (3j) [3d,5]
1
Yellow liquid; H NMR (CDCl3) δ 1.21 (12H, d, J =
6.8 Hz, CH3), 2.89 (2H, m, CH); 13C NMR (CDCl3)
δ 18.6, 44.9, 198.2; IR (neat): 1705 cm−1; MS (CI):
m/z = 175 [M+ + 1].
[2] Ishihara, H.; Koketsu, M.; Fukuta, Y.; Nada, F. J Am
Chem Soc 2001, 123, 8408–8409.
Di-n-hexanoyl Sulfide (3k)
[3] (a) Koketsu, M.; Fukuta, Y.; Ishihara, H. J Org Chem
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[5] Mikolajczyk, M.; Kielbasin˜ski, P.; Schiebel, H. M. J
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1
Colorless liquid; H NMR (CDCl3) δ 0.90 (6H, t, J =
7.2 Hz, CH3), 1.33 (4H, m, CH2), 1.67 (8H, m, CH2),
2.75 (4H, t, J = 7.4 Hz, CH2); 13C NMR (CDCl3) δ 13.7,
22.2, 24.3, 30.9, 45.9, 194.8; IR (neat): 1764, 1713
cm−1; MS (CI): m/z = 231 [M+ + 1]; HRMS m/z =
230.1335 for C12H22O2S: found 230.1332.
Distearoyl Sulfide (3l) [3d]
White powder; Mp: 65.0–65.5◦C; H NMR (CDCl3) δ
0.88 (6H, t, J = 6.8 Hz, CH3), 1.26 (56H, s, CH2), 1.66
(4H, m, CH2), 2.74 (4H, t, J = 7.4 Hz, CH2); 13C NMR
(CDCl3) δ 14.1, 22.7, 28.8, 29.2, 29.3, 29.5, 29.7, 31.9,
1
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