Synthesis of 5-formyl and 5-acyl-1,2-dithiole-3-ones

Article abstract of DOI:10.1080/10426500307824

The preparation of new 5-formyl-, 5-acetyl- and 5-propionyl-1,2-dithiole-3-ones by oxidation of the corresponding 1,2-dithiole-3-thiones with mercuric acetate is described.

Full text of DOI:10.1080/10426500307824

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis of 5-Formyl and 5-Acyl-1,2-dithiole-3-ones
S. Gargadennec a , B. Legouin a & J.-L. Burgot a
a Université de Rennes I , Rennes, France
Published online: 27 Oct 2010.
To cite this article: S. Gargadennec , B. Legouin & J.-L. Burgot (2003) Synthesis of 5-Formyl and 5-Acyl-1,2-dithiole-3-ones,
Phosphorus, Sulfur, and Silicon and the Related Elements, 178:8, 1721-1726, DOI: 10.1080/10426500307824
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Phosphorus, Sulfur, and Silicon, 178:1721–1726, 2003
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print
DOI: 10.1080/10426500390220880
SYNTHESIS OF 5-FORMYL
AND 5-ACYL-1,2-DITHIOLE-3-ONES
S. Gargadennec, B. Legouin, and J.-L. Burgot
Universite´ de Rennes I, Rennes, France
(Received February 12, 2003; accepted February 12, 2003)
The preparation of new 5-formyl-, 5-acetyl- and 5-propionyl-1,2-
dithiole-3-ones by oxidation of the corresponding 1,2-dithiole-3-thiones
with mercuric acetate is described.
Keywords: 5-Formyl (or 5-acyl)-1,2-dithiole-3-ones; 5-formyl(or 5-acyl)-
1,2-dithiole-3-thiones
1-(5-thioxo-5H-1,2-dithiole-3-yl)-ketones 1 together with the corre-
sponding 1,2-dithiole-3-ones 2 are patented for their pharmacological
properties, especially for their microbicidal ones.1−3
In the course of our studies devoted to the synthesis of new 1,2-
dithiole-3-thiones1,2 and to their physico-chemical properties,4,5 we
have determined water/n-octanol log P values of several 1,2-dithiole-3-
thiones and 3-ones in order to establish quantitative structure activity
relationships.6 With this aim, we have prepared new 1,2-dithiole-3-ones
Address correspondence to J.-L. Burgot, Laboratoire de Chimie Analytique (UPRES
2231), UFR des Sciences Pharmaceutiques et Biologiques, Universite´ de Rennes I, 35043
Rennes Cedex, France. E-mail: jean–louis.burgot@rennes1.fr
1721

1722
S. Gargadennec et al.
2 by reaction of mercuric acetate with the corresponding 1,2-dithiole-
3-thiones 1, three of which were new and also are described herein.
Mercuric acetate7 was preferred to benzonitrile oxide3 as the oxidant
because it led to better yields.
EXPERIMENTAL SECTION
Infrared spectra were obtained with a diffuse reflectance infrared
Fourier-transform 16-PC Perkin-Elmer. 1H NMR spectra were mea-
sured at the CRMPO, Rennes, France, in CDCl3 with a Bruker AM
300 MHz WB spectrometer and 13C NMR spectra with a Bruker AM
75.5 MHz WB spectrometer. Mass spectra were recorded on a varian
Mat 311 (Electronic impact 70 eV).
5 H-1,2-Dithiole-3-thiones
4-Ethyl-5-thioxo-5 H-1,2-dithiole-3-carbaldehyde 1c
Compound 1c was obtained from 4-ethyl-5-methyl-1,2-dithiole-3-
thione8 according to the standard procedure using NaNO2 in glacial
acetic acid1 with a yield of 17%. Red crystals; m.p. 76◦C (heptane);
IR:ν = 1674 cm−1; MS: m/z: 189.959 (calc. for C6H6OS3: 189.9581),
1H NMR δ = 1.26 (t, 3H, 3 J= 7.5 Hz, CH3); 3.10 (q, 2H, 3 J= 7.5 Hz,CH2);
10.24( s, 1H, CHO); 13C NMR δ = 14.7 (qt, 1 J= 129 Hz, 2 J= 5.4 Hz,
CH3); 22.7 (td, 1 J= 131 Hz, 2 J= 4.5 Hz, CH2); 155.1 (m, C-4); 159.6
(dt, 2 J= 3.4 Hz, 3 J= 4.5 Hz, C-5); 185.2 (d, 1 J= 189 Hz, C O); 217.2
(t, 3 J= 7 Hz, C S).
1-(4-Methyl-5-thioxo-5 H-1,2-dithiole-3-yl)-propan-1-one 1l
Compound 1l was obtained from 4-methyl-5-propyl-1,2-dithiole-3-
thione4 according to the standard procedure1 with a yield of 20%. Red
crystals; m.p. = 75◦C (hexane); IR:ν = 1700 cm−1; MS: m/z: 203.9732
1
(calc. for C7H8OS3: 203.9737); H NMR δ = 1.27 (t, 3H, 3 J= 7.2 Hz,
CH2-CH ); 2.46 (s, 3H, CH3 ); 2.99 (q, 2H, 3 J= 7.2 Hz, CH2); 13C NMR
3
δ = 7.7 (qt, 1 J= 129 Hz, 2 J= 4 Hz, CH2-CH3); 17.3 (q, 1 J= 131 Hz, CH3-
4); 37.0 (tq ,1 J= 129Hz, 2 J= 4Hz, CH2); 145.9 (q, 2 J= 6.2 Hz, C-4);
161.1 (q, 3 J= 5 Hz, C-5); 195.7 (q, 3 J= 5.3 Hz, C O); 213.3 (q, 3 J= 5.5
Hz, C S).
1-(4-Ethyl-5-thioxo-5 H-1,2-dithiole-3-yl)-propan-1-one 1m
Compound 1m was obtained from 4-ethyl-5-propyl-1,2-dithiole-3-
thione9 according to the standard procedure1 with a yield of 11%. Red
crystals; m.p. 45◦C (hexane); IR: ν = 1702 cm−1; MS: m/z: 217.9891

Synthesis of 5-Formyl and 5-Acyl-1,2-Dithiole-3-Ones
1723
(calc. for C8 H10OS3: 217.9894); 1H δ = 1.09 (t, 3H, 3 J= 7.3 Hz, CH -4);
3
1.20 (t, 3H, 3 J= 7.0 Hz, CH -5); 2.92 (q, 2H, 3 J= 7.3 Hz, CH -4 ); 3.14
3
2
(q, 2H, 3 J= 7.0 Hz, CH -5); 13C δ = 7.9 (qt, 1 J= 129 Hz , 2 J= 4.5 Hz,
2
CH3-5); 13.0 (qt, 1 J= 128 Hz, 2 J= 4.5 Hz, CH3-4); 24.4 (tq, 1 J= 131 Hz,
2 J= 4.5 Hz, CH2-4); 37.4 (tq, 1 J= 126 Hz, 2 J= 4.5 Hz, CH2-5); 151.6
(m, C-4); 163.6 (t, 3 J= 5 Hz, C-5); 196.2 (q, 3 J= 5.3 Hz, C O); 218.2 (t,
3 J= 7 Hz, C S).
5-Formyl and 5-Acyl-1,2-dithiole-3-ones
(General Procedure)
Two equivalents of mercuric acetate in 70 ml of boiling acetic acid are
added to 100 mL of a boiling solution containing one equivalent of the
corresponding 1-(5-thioxo-5H-1,2-dithiole-3-yl)-ketone 1. The mixture
was stirred and heated for 3 h. The solution was then allowed to reach
room temperature. After filtration and stripping off the solvent, the
crude product was purified by silica gel chromatography with toluene
to give the expected 5-acyl-1,2-dithiole-3-ones 2.
5-Oxo-5 H-1,2-dithiole-3-carbaldehyde 2a
Compound 2a was obtained from 1a1 with a yield of 30%. m.p. 83◦C
(ethylacetate); IR: ν = 1676, 1647 cm−1; MS: m/z: 145.9491 (calc. for
C4H2O2S2: 145.9496); 1H δ = 7.27 (s, 1H, H-4); 10.04 (s, 1H, CHO); 13
C
1
1
δ = 129.2 (d, J= 175 Hz, C-4); 163.9 (m, C-5); 182.5 (dd, J= 192 Hz,
3 J= 5 Hz, CHO); 193.8 (d, 2 J= 5.5 Hz, C-3).
4-Methyl-5-oxo-5 H-1,2-dithiole-3-carbaldehyde 2b
Compound 2b was obtained from 1b1 with an overall yield of 36%.
m.p. 79◦C (ethylacetate); IR: ν = 1670, 1647 cm−1; MS: m/z: 159.9652
1
(calc. for C5H4O2S2: 159.9653); H δ = 2.41(s, 3H, CH3); 10.26 (s, 1H,
CHO); 13C δ = 12.8 (q, CH3); 138.4 (m, C-4); 155.2 (m, C-5); 183.7 (d,
1 J= 190 Hz, CHO); 196.1 (q, C-3).
4-Ethyl-5-oxo-5 H-1,2-dithiole-3-carbaldehyde 2c
Compound 2c was obtained from 1c with a yield of 80%. m.p. 48◦C
(ethylacetate); IR: ν = 1670, 1645 cm−1; MS: m/z: 173.9809 (calc. for
C6H6O2S2: 173.9809); 1H δ = 1.26 (t, 3H, 3 J= 7.5 Hz, CH3); 2.88 (q, 2H,
3 J= 7.5 Hz, CH2); 10.24 (s, 1H, CHO); 13C NMR δ = 14.6 (qt, 1 J= 128.5
Hz, 2 J= 5 Hz, CH3); 20.8 (tq, 1 J= 131.5 Hz, 2 J= 4 Hz, CH2); 144.1 (m,
C-4); 155.6 (dt, 2 J= 35 Hz, 3 J= 4 Hz, C-5); 183.7 (d, 1 J= 189 Hz, CHO);
195.9 (t, 3 J= 6 Hz, C-3).

1724
S. Gargadennec et al.
5-Oxo-4-phenyl-5 H-1,2-dithiole-3-carbaldehyde 2d
Compound 2d was obtained from 1d1 with a yield of 75%. m.p.
153◦C (heptane); IR: ν = 1670, 1640 cm−1; MS: m/z: 221.9800 (calc.
1
for C10H6O2S2: 221.9809); H δ = 7.41 (m, 2H, C6H5-m); 7.51 (m, 3H,
C6H5-o, p); 9.82 (s, 1H, CHO); 13C NMR δ = 128.9 (d, 1 J= 161 Hz,
C6H5-m); 129.4 (t, 3 J= 6.5 Hz, C6H5-4); 130.2 (d, 1 J= 160 Hz, C6H5-p);
130.3 (dm, 1 J= 161 Hz, C6H5-o); 141.0 (t, 3 J= 4 Hz, C-4); 157.9 (d,
2 J= 35 Hz, C-5); 185.4 (d, 1 J= 194 Hz, CHO); 194.4 (s, C-3).
4-Methoxy-5-oxo-5 H-1,2-dithiole-3-carbaldehyde 2e
Compound 2e was obtained from 1e1 with a yield of 80%. m.p.
54◦C (hexane); IR: ν = 1670, 1632 cm−1; MS: m/z: 175.9599 (calc.
for C5H4O3S2: 175.9602); 1H δ = 4.19 (s, 3H, CH3); 10.11 (s, 1H, CHO);
13C NMR δ = 60.3 (q, 1 J= 148 Hz, CH3); 141.4 (d, 2 J= 34 Hz, C-5);
154.0 (q, 3 J= 4 Hz, C-4); 183.8 (d, 1 J= 194 Hz, CHO); 189.0 (s, C-3).
4-Chloro-5-oxo-5 H-1,2-dithiole-3-carbaldehyde 2f
1
Compound 2f was obtained from 1f with a yield of 70%. m.p.
89◦C (hexane); IR: ν = 1676, 1604 cm−1; MS: m/z: 181.9070 (calc. for
C4HClO2S2: 181.9077); 1H δ = 10.26 (s, 1H, CHO); 13C NMR δ = 130.9
2
1
(s, C-4); 153.1 (d, J= 34 Hz, C-5); 182.9 (d, J= 197 Hz, CHO); 187.7
(s, C-3).
5-Acetyl-1,2-dithiole-3-one 2g
Compound 2g was obtained from 1g2 with a yield of 50%. m.p.
119◦C (methanol); IR: ν = 1684, 1642 cm−1; MS: m/z: 159.9652 (calc.
1
for C5H4O2S2: 159.9653); H δ = 2.65 (s, 3H, CH3); 7.18 (s, 1H, H-4);
13C NMR δ = 27.6 (q, 1 J= 129 Hz, CH3); 125.2 (d, 1 J= 175 Hz, C-4);
165.4 (d, 2 J= 7 Hz, C-5); 190.6 (m, CH3C O); 194.7 (d, 2 J= 5.4 Hz,
C-3).
5-Acetyl-4-methyl-1,2-dithiole-3-one 2h
Compound 2h was obtained from 1h2 with a yield of 40%. m.p.
44◦C (methanol); IR: ν = 1671, 1646 cm−1; MS: m/z: 173.9809 (calc. for
C6H6O2S2: 173.9809); 1H δ = 2.31 (s, 3H, CH3-4); 2.65 (s, 3H, COCH );
3
13C NMR δ = 14.7 (q, CH3-4); 30.0 (q, 1 J= 129 Hz, CH3CO); 134 (q,
C-4); 157.3 (m, C-5); 192.0 (m, CH3C O); 195.9 (q, C-3).
5-Acetyl-4-ethyl-1,2-dithiole-3-one 2i
Compound 2i was obtained from 1i2 with a yield of 63%. m.p. 38◦C
(methanol); IR: ν = 1704, 1652 cm−1; MS: m/z: 187.9956 (calc. for
C7H8O2S2: 187.9956); 1H δ = 1.14 (t, 3H, CH2CH ); 2.64 (s, 3H, COCH );
3
3
2.76 (q, 2H, CH2); 13C NMR δ = 13.2 (qt, 1 J= 128 Hz, 2 J= 6.5 Hz,

Synthesis of 5-Formyl and 5-Acyl-1,2-Dithiole-3-Ones
1725
CH2CH3); 22.1 (tq, 1 J= 132 Hz, 2 J= 4.5 Hz, CH2); 29.6 (q , 1 J= 129 Hz,
COCH3); 139.6 (m, C-4); 157.1 (q, 3 J= 4.4 Hz, C-5); 191.9 (q, , 2 J= 6.5
Hz, COCH3); 195.6 (t, 3 J= 6 Hz, C-3).
5-Acetyl-4-phenyl-1,2-dithiole-3-one 2j
Compound 2j was obtained from 1j1 with a yield of 70%. m.p.
69◦C (hexane); IR: ν = 1664, 1646 cm−1; MS: m/z: 235.9954 (calc. for
C11H8O2S2: 235.9966); 1H δ = 2.02 (s, 3H, CH3); 7.29 (m, 2H, C6H5-m);
7.48 (m, 3H, C6H5-o, p); 13C NMR δ = 29.5 (q, 1 J= 130 Hz, CH3); 129.1
(d, 1 J= 160 Hz, C6H5-m); 129.7 (d, 1 J= 161 Hz, C6H5-o); 129.9 (m,
C6H5-p); 131.8 (m, C6H5-4); 136.1 (t, 3 J= 3.5 Hz, C-4); 161.8 (s, C-5);
194.1 (s, C-3); 194.4 (q, 2 J= 6.5 Hz, COCH3).
5-Propionyl-1,2-dithiole-3-one 2k
Compound 2k was obtained from 1k1 with a yield of 80%. m.p. 99–
100◦C (methanol); IR: ν = 1686, 1630 cm−1; MS: m/z: 173.9809 (calc. for
C6H6O2S2: 173.9809); 1H δ = 1.24 (t, 3H, CH3); 2.98 (q, 2H, CH2); 7.16
(s, 1H, H-4); 13C NMR δ = 7.6 (qt, 1 J= 129 Hz, 2 J= 4.5 Hz, CH3); 38.7
1
2
1
(tq, J= 126 Hz, J= 4.5 Hz, CH2); 124.3 (d, J= 175 Hz, C-4); 165.3
(d, 2 J= 8 Hz, C-5); 193.7 (m, COEt); 194.9 (d, 2 J= 5.4 Hz, C-3).
4-Methyl-5-propionyl-1,2-dithiole-3-one 2l
Compound 2l was obtained from 1l with a yield of 82%. m.p. 98–
99◦C (methanol); IR: ν = 1668, 1630 cm−1; MS: m/z: 187.9975 (calc. for
C7H8O2S2: 187.9966); 1H δ = 1.24 (t, 3H, CH -CH2); 2.29 (s, 3H, CH3-4);
3
2.93 (q, 2H, CH2); 13C NMR δ = 7.6 (qt, 1 J= 129 Hz, 2 J= 4.4 Hz, CH3-
1
1
2
CH2); 14.6 (q, J= 131 Hz, CH3-4); 35.9 (tq, J= 126 Hz, J= 4.4 Hz,
CH2); 133.7 (q, 2 J= 6.5 Hz, C-4); 157.2 (m, C-5); 195.2 (m, COEt); 195.9
(m, C-3).
4-Ethyl-5-propionyl-1,2-dithiole-3-one 2m
Compound 2m was obtained from 1m with a yield of 40%. m.p. 49–
50◦C (methanol); IR: ν = 1666, 1625 cm−1; MS: m/z: 202.0132 (calc.
1
for C8H10O2S2: 202.0122); H δ = 1.14 (t, 3H, CH CH2-4); 1.24 (t, 3H,
3
CH CH2CO); 2.76 (q, 2H, CH2-4); 2.95 (q, 2H, CH2-CO); 13C NMR δ =
3
7.6 (qt, 1 J= 129 Hz, 2 J= 4.5 Hz, CH3CH2CO); 13.2 (qt, 1 J= 128 Hz,
2 J= 5 Hz, CH3CH2-4); 22.1 (tq, J= 131 Hz,2 J= 4.5 Hz, CH2-4); 35.6
1
(tq, 1 J= 125 Hz, 2 J= 4.5 Hz,CH2CO); 139.3 (q, 3 J= 5.5 Hz, C-4); 157.0
(t, 3 J= 5 Hz, C-5); 195.2 (q, 3 J= 5.5 Hz, COEt); 195.9 (t, 3 J= 6 Hz, C-3).
4,5,6,7-Tetrahydro-4 H-benzo–1,2-dithiole-3,7-dione 2n
Compound 2n was obtained from 1n1 with a yield of 45%. m.p.
52–53◦C (hexane); IR: ν = 1684, 1654 cm−1; MS: m/z: 185.9805 (calc.

1726
S. Gargadennec et al.
for C7H6O2S2: 185.9809); 1H δ = 2.22 (m, 2H, CH2-CH -CH2); 2.69
2
(t, 2H, CH2-4); 2.74 (t, 2H, CH2CO); 13C NMR δ = 22.9 (t, 1 J= 131
1
1
Hz, CH2-CH2-CH2); 24.8 (t, J= 132 Hz, CH2-4); 38.8 (t, J= 130 Hz,
CH2CO); 141.9 (m, C-4); 154.8 (t, 3 J= 4.5 Hz, C-5); 193.1 (m, CH2CO);
195.1 (s, C-3).
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[3] M.-O. Christen and J.-L. Burgot, French Patent Appl., Fr 2676057; Chem. Abstr.,
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