A one-pot synthesis of tetrahydro-2,5-dioxofuran-3-yl alkylcarbamodithioates

Article abstract of DOI:10.1080/10426500903251340

An efficient one-pot synthesis of tetrahydro-2,5-dioxofuran-3-yl alkylcarbamodithioates via three-component reaction of maleic anhydride, CS2, and primary amines in good yields is described. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon and the
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A One-Pot Synthesis of Tetrahydro-2,5-
dioxofuran-3-yl Alkylcarbamodithioates
Issa Yavari a & Ashraf S. Shahvelayati a
a Chemistry Department, Islamic Azad University , Science and
Research Branch , Ponak, Tehran, Iran
Published online: 02 Aug 2010.
To cite this article: Issa Yavari & Ashraf S. Shahvelayati (2010) A One-Pot Synthesis of Tetrahydro-2,5-
dioxofuran-3-yl Alkylcarbamodithioates, Phosphorus, Sulfur, and Silicon and the Related Elements,
185:8, 1726-1731, DOI: 10.1080/10426500903251340
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Phosphorus, Sulfur, and Silicon, 185:1726–1731, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500903251340
A ONE-POT SYNTHESIS OF
TETRAHYDRO-2,5-DIOXOFURAN-3-YL
ALKYLCARBAMODITHIOATES
Issa Yavari and Ashraf S. Shahvelayati
Chemistry Department, Islamic Azad University, Science and Research Branch,
Ponak, Tehran, Iran
An efficient one-pot synthesis of tetrahydro-2,5-dioxofuran-3-yl alkylcarbamodithioates via
three-component reaction of maleic anhydride, CS2, and primary amines in good yields is
described.
Keywords Carbamodithioate; maleic anhydride; one-pot synthesis; primary amine
INTRODUCTION
Organic carbamodithioates have received much attention due to their interesting
chemistry and wide utility as radical precursors and intermediates in organic synthe-
sis.1–4 They also have a variety of applications in agriculture as pesticides, as well as
in the rubber industry as vulcanization accelerators, and as antioxidants.5–7 Because they
have strong metal-binding capacity, they can act as inhibitors of enzymes and have a
profound effect on biological systems.8,9 Recently, a variety of reagents and catalysts
including Mitsunobu’s reagent,10 solid LiClO4/N,N-dimethylformamide,11 dimethylsul-
foxide,12 and Cs2CO3/tetrabutylammonium iodide13 have been used for the synthesis of
carbamodithioates.
As part of our current studies on the development of new routes in approach to the
synthesis of organosulfur compounds,14–19 we describe an efficient synthesis of functional-
ized carbamodithioates containing a cyclic anhydride moiety. Similar reactions of amines,
carbon disulfide, and maleimides with dithiocarbamic acids have been reported.20
RESULTS AND DISCUSSION
The reaction of primary amines (1), carbon disulfide, and maleic anhydride
(2) in MeCN at room temperature produced tetrahydro-2,5-dioxofuran-3-yl alkylcar-
bamodithioates (3) in fairly good yields after purification (Scheme 1). Compounds 3a–3m
are stable, and they are recovered unchanged after reflux in toluene for 12 h. The structures
1
of compounds 3a–3m were determined by IR, H NMR, and 13C NMR spectral data.
Received 6 June 2009; accepted 11 August 2009.
Address correspondence to Issa Yavari, Chemistry Department, Islamic Azad University, Science and
Research Branch, Ponak, Tehran, Iran. E-mail: yavarisa@modares.ac.ir
1726

ONE-POT SYNTHESIS OF CARBAMODITHIOATE
1727
O
O
S
RR'NH
O
O
CS2
+
+
R'RN
S
O
O
2
1
3
Yield (%) of 3
1,3
__________R_________________________________________
R'
i-Pr
Et
sec-Bu
n-Bu
Cyclohexyl
C6H5CH2
4-Cl-C6H4CH2
4-Me-C6H4CH2
4-MeO-C6H4CH2
2-Furylmethyl
CH3CHOHCH2
Ph
H
H
H
H
H
H
a
b
c
d
e
f
g
h
i
j
85
87
79
83
92
92
60
89
H
H
H
H
90
93
93
11
20
k
l
m
H
H
Et
Et
Scheme 1 Formation of tetrahydro-2,5-dioxofuran-3-yl alkylcarbamodithioates (3).
The mass spectra of these compounds displayed molecular ion peaks at appropriate
1
m/z values. The H NMR spectra of 3a–3m exhibited characteristic ABX systems for
the CH2-CH moieties. The proton-decoupled 13C NMR spectra of 3a–3m showed three
distinct resonances for C O and C S groups. The reaction of aniline or diethylamine
with CS2 and maleic anhydride produced the corresponding carbamodithioate 3l or 3m in
low yields.
Compounds 3c and 3k possess two stereogenic centers, and can exist as a mixture
of two diastereoisomers. The NMR spectra of these compounds are consistent with the
presence of two diastereoisomers (see the Experimental section). The methylene protons
of the benzyl group in 3f–3i are diastereotopic and exhibit characteristic AB systems.
A tentative mechanism for this transformation is proposed in Scheme 2. It is conceiv-
able that the initial event is the formation of a xanthate salt 4 from two equivalents of the
amine and CS2. Nucleophilic attack of this salt on 2, and subsequent elimination of RNH2,
leads to carbamodithioates 3.
S
2
+
3
RHN
S
+
RNH3
2 RNH2
CS2
- RNH2
4
Scheme 2 A plausible mechanism for formation of carbamodithioates 3.

1728
I. YAVARI AND A. S. SHAHVELAYATI
In conclusion, we have described a convenient route to tetrahydro-2,5-dioxofuran-3-yl
alkylcarbamodithioates from primary alkylamines, CS2, and maleic anhydride. Mild condi-
tions of dithiocarbonization, availability of the initial compounds, possibility of structural
variations, and good preparative yields makes the developed synthesis of carbamodithioates
a rather promising process.
EXPERIMENTAL
Maleic anhydride, CS2, and amines 1 were obtained from Fluka and were used
without further purification. Other procedural details are as follows: mp: Electrothermal-
1
9100 apparatus; IR Spectra: Shimadzu IR-460 spectrometer. H and 13C NMR spectra:
Bruker DRX-300 AVANCE instrument; in CDCl3 at 300 and 75 MHz, respectively; δ in
ppm, J in Hz; EI-MS (70 eV): Finnigan-MAT-8430 mass spectrometer, in m/z. Elemental
analyses (C, H, N) were performed with a Heraeus CHN-O-Rapid analyzer.
General Procedure for the Preparation of Compounds 3
A mixture of amine 1 (2 mmol) in CS2 (1.2 mL) was stirred for 1 h, then a solution of
maleic anhydride (0.20 g, 2 mmol) in MeCN (2 mL) was added slowly. After completion
of the reaction (1–2 h), as indicated by TLC (AcOEt/hexane, 2:1), the solvent was removed
under reduced pressure, and the residue was purified by dry-flash chromatography using a
1:3 mixture of AcOEt/petroleum ether as eluent to afford pure dithiocarbamates 3. Further
purification was done by recrystallization from a mixture of CHCl3/hexane.
Tetrahydro-2,5-dioxofuran-3-yl iso-propylcarbamodithioate (3a). Pale
yellow crystals; yield: 0.44 g (85%); mp 164–165◦C. IR (KBr) (νmax/cm−1): 3443, 1729,
1699, 1471, 1453, 1397, 1265, 1203. EI-MS: 233 (M+, 9), 191 (12), 187 (11), 133 (15),
100 (100), 43 (18); Anal. Calcd. for C8H11NO3S2 (233.2): C, 41.19; H, 4.75; N, 6.01%.
Found: C, 41.43; H, 4.81; N, 6.07%. 1H NMR: δ = 1.43 (3H, d, 3J 6.9, Me), 1.46 (3H, d,
2
3
2
3
3J 6.9, Me), 3.08 (1H, dd, J 18.0, J 8.0, CH), 3.23 (1H, dd, J 18.0, J 3.9, CH), 3.65
(1H, br s, NH), 4.51 (1H, dd, 3J 8.0, 3J 3.9, CH), 5.23 (1H, sept, 3J 6.9, CH). 13C NMR:
δ = 18.3 (Me), 18.6 (Me), 36.6 (CH2), 43.9 (CH), 50.8 (CHN), 175.4 (C O), 176.0
(C O), 201.4 (C S).
Tetrahydro-2,5-dioxofuran-3-yl ethylcarbamodithioate (3b). Pale yellow
crystals; yield: 0.38 g (87%); mp 121–122◦C. IR (KBr) (νmax/cm−1): 3423, 2569, 1718,
1708, 1436, 1328, 1250, 1121. EI-MS: 219 (M+, 8), 191 (14), 173 (13), 133 (19), 86 (100),
29 (16); Anal. Calcd. for C7H9NO3S2 (219.2): C, 38.35; H, 4.14; N, 6.39%. Found: C,
38.62; H, 4.10; N, 6.48%. 1H NMR: δ = 1.22 (3H, t, 3J 7.2, Me), 3.1 (1H, dd, 2J 18.1, 3J
8.5, CH), 3.3 (1H, dd, 2J 18.1, 3J 3.6, CH), 4.07 (2H, q, 3J 7.2, CH2), 4.42 (1H, dd, 3J 8.5,
3J 3.6, CH), 10.6 (1H, br s, NH). 13C NMR: δ = 12.2 (Me), 36.8 (CH2), 40.4 (CH2), 45.7
(CH2N), 175.7 (C O), 175.8 (C O), 200.4 (C S).
Tetrahydro-2,5-dioxofuran-3-yl sec-butylcarbamodithioate (3c). Pale yel-
low crystals; yield: 0.39 g (79%); mp 111–113◦C. IR (KBr) (νmax/cm−1): 3435, 2568, 1727,
1717, 1460, 1387, 1284, 1115. EI-MS: 247 (M+, 12), 201 (11), 191 (13), 133 (17), 114
(100), 57 (40); Anal. Calcd. for C9H13NO3S2 (247.3): C, 43.71; H, 5.30; N, 5.67%. Found:
C, 43.52; H, 5.41; N, 5.70%. Major isomer (55%): 1H NMR: δ = 0.89 (3H, t, 3J 7.3, Me),
1.42 (3H, d, 3J 6, Me), 1.83–1.85 (2H, m, CH2), 3.07–3.10 (2H, m, CH2), 4.28–4.30 (1H,
m, CH), 5.06–5.08 (1H, m, CH). 13C NMR: δ = 11.4 (Me), 16.6 (Me), 25.6 (CH2), 36.6
(CH2), 43.8 (CH), 56.6 (CH-N), 175.5 (C O), 176.1 (C O), 205.1 (C S). Minor isomer

ONE-POT SYNTHESIS OF CARBAMODITHIOATE
1729
1
3
3
(45%): H NMR: δ = 0.89 (3H, t, J 7.3, Me), 1.46 (3H, d, J 6.0, Me), 2.13–2.15 (2H,
m, CH2), 3.24–3.26 (2H, m, CH2), 4.28–4.30 (1H, m, CH), 5.06–5.08 (1H, m, CH). 13C
NMR: δ = 11.5 (Me), 16.9 (Me), 25.7 (CH2), 36,8 (CH2), 43.9 (CH), 56.7 (CH-N), 175.5
(C O), 176.1 (C O), 205.1 (C S).
Tetrahydro-2,5-dioxofuran-3-yl n-butylcarbamodithioate (3d). Pale yellow
crystals; yield: 0.41g (83%); mp 139–140◦C. IR (KBr) (νmax/cm−1): 3444, 2605, 1733,
1703, 1437, 1361, 1284, 1194. EI-MS: 247 (M+, 7), 201 (12), 191 (15), 133 (18), 114
(100), 57 (25), 43 (18); Anal. Calcd. for C9H13NO3S2 (247.2): C, 43.71; H, 5.30; N,
1
3
5.67%. Found: C, 43.01; H, 5.42; N, 5.59%. H NMR: δ = 0.95 (3H, t, J 7.2, Me),
1.36–1.38 (2H, m, CH2), 1.61–1.63 (2H, m, CH2), 3.07 (1H, dd, 2J 18.0, 3J 8.7, CH), 3.3
(1H, dd, 2J 18.0, 3J 3.9, CH), 4.00 (1H, t, 3J 7.6, CH2), 4.42 (1H, dd, 3J 8.7, 3J 3.9, CH),
10.98 (1H, br s, NH). 13C NMR: δ = 14.0 (Me), 20.4 (CH2), 29.0 (CH2), 36.9 (CH2), 45.1
(CH), 45.6 (CH2), 175.9 (C O), 176.0 (C O), 200.7 (C S).
Tetrahydro-2,5-dioxofuran-3-yl cyclohexylcarbamodithioate (3e). Pale
yellow crystals; yield: 0.50 g (92%); mp 186–187◦C. IR (KBr) (νmax/cm−1): 3462, 2532,
1743, 1701, 1465, 1396, 1284, 1199. EI-MS: 273 (M+, 9), 192 (100), 174 (36), 140 (17),
81 (17), 55 (34), 41 (25); Anal. Calcd. for C11H15NO3S2 (273.3): C, 48.34; H, 5.53; N,
1
5.13%. Found: C, 48.01; H, 5.65; N, 5.23%. H NMR: δ = 1.20–2.40 (10 H, m, 5 CH2),
2
3
2
3
3
3.06 (1H, dd, J 18.0, J 8.3, CH), 3.23 (1H, dd, J 18.0, J 3.9, CH), 4.25 (1H, dd, J
8.3, 3J 3.9, CH), 4.8 (1H, br s, NH). 13C NMR: δ = 25.4 (CH2), 26.3 (CH2), 26.4 (CH2),
27.7 (CH2), 27.9 (CH2), 36.6 (CH2), 43.7 (CH), 58.8 (CHN), 176.2 (C O), 176.9 (C O),
201.7 (C S).
Tetrahydro-2,5-dioxofuran-3-yl benzylcarbamodithioate (2f). Yellow crys-
tals; yield: 0.49 g (92%); mp 139–140◦C. IR (KBr) (νmax/cm−1): 3404, 2560, 1706, 1688,
1425, 1349, 1174, 1107. EI- MS: 281 (M+, 11), 235 (7), 149 (21), 148 (70), 91 (100), 65
(18), 45 (8). Anal. Calcd. for C12H11NO3S2 (281.3): C, 51.23; H, 3.94; N, 4.98%. Found:
C, 51.4; H, 4.11; N, 5.09%. 1H NMR: δ = 3.06 (1H, dd, 2J 18, 3J 8.0, CH), 3.32 (1H, dd,
2J 18.0, 3J 3.9, CH), 3.65 (1H, bs, NH), 4.46 (1H, dd, 3J 8.0, 3J 3.9, CH), 5.20 (2 H, ABq,
νꢀAB = 22 Hz, 2JAB 14.2, CH2), 7.30–7.42 (5H, m, CH-arom). 13C NMR: δ 36.6 (CH2),
45.7 (CH), 48.2 (CH2N), 128.6 (CH), 129.0 (2CH), 129.3 (2CH), 134.9(C), 174.4 (C O),
175.8 (C O), 200.4 (C S).
Tetrahydro-2,5-dioxofuran-3-yl 4-chlorobenzylcarbamodithioate (3g).
Pale yellow crystals; yield: 0.38 g (60%); mp 139–140◦C. IR (KBr) (νmax/cm−1): 3481,
2598, 1742, 1721, 1492, 1346, 1203, 1089. EI-MS: 317 (M+2, 6), 315 (M+, 20), 269 (8),
187 (11), 182 (68), 125 (100), 91 (10); Anal. Calcd. for C12H10NO3S2Cl (315.7): C, 45.65;
H, 3.51; N, 4.44%. Found: C, 45.23; H, 3.60; N, 4.52%. 1H NMR: δ 3.10 (1H, dd, 2J 18,
3J 8.2, CH), 3.27 (1H, dd, 2J 18.0, 3J 3.9, CH), 4.44 (1H, dd, 3J 8.2, 3J 3.9, CH), 5.15 (2H,
2
3
3
ABq, νꢀAB = 7 Hz, JAB 10.1, CH2) 7.28 (d, J 8.0, 2CH), 7.38 (2H, d, J 8.0, 2CH),
10.17 (1H, br s, NH). 13C NMR: δ = 36.5 (CH2), 45.7 (CH), 47.5 (CH2N), 129.1 (2CH),
130.9 (2CH), 133.3 (C), 134.5 (C), 175.7 (C O), 175.8 (C O), 200.2 (C S).
Tetrahydro-2,5-dioxofuran-3-yl 4-methylbenzylcarbamodithioate (3h).
Pale yellow crystals; yield: 0.52 g (89%); mp 172–174◦C. IR (KBr) (νmax/cm−1): 3481,
2590, 1747, 1720, 1492, 1346, 1272, 1196. EI-MS: 295 (M+, 6), 249 (7), 162 (48), 105
(100), 91 (13); Anal. Calcd. for C13H13NO3S2 (295.3): C, 52.87; H, 4.44; N, 4.74%.
1
2
Found: C, 52.95; H, 4.29; N, 4.87%. H NMR: δ = 2.33 (3 H, s, Me), 3.04 (1 H, dd, J
18.0, J 9.0, CH), 3.32 (1 H, dd, J 18.0, J 3.6, CH), 4.45 (1 H, dd, J 9.0, 3J 3.6, CH),
3
2
3
3
5.15 (2 H, ABq, νꢀAB = 11 Hz, JAB = 14.0, CH2), 7.12 (2 H, d, 3J 7.8, 2 CH), 7.32 (2 H,

1730
I. YAVARI AND A. S. SHAHVELAYATI
d, 3J 7.8, 2 CH). 13C NMR: δ = 21.6 (Me), 36.7 (CH2), 45.7 (CH), 48.0 (CH2N), 129.3 (2
CH), 129.6 (2 CH), 132.0 (C), 138.4 (C), 174.8 (C O), 175.8 (C O), 200.4 (C S).
Tetrahydro-2,5-dioxofuran-3-yl 4-methoxybenzylcarbamodithioate (3i).
Pale yellow crystals; yield: 0.57 g (90%); mp 130–131◦C. IR (KBr) (νmax/cm−1): 3370,
2560, 1721, 1712, 1428, 1300, 1252, 1193. EI-MS: 311 (M+, 9), 265 (4), 178 (34), 121
(100), 91 (9.5), 77 (13.5); Anal. Calcd. for C13H13NO4S2 (311.3): C, 50.15; H, 4.21; N,
5.16%. Found: C, 49.85; H, 4.30; N, 5.23%. 1H NMR: δ 3.03 (1 H, dd, 2J 18.0, 3J 8.7, CH),
2
3
3
3
3.27 (1 H, dd, J 18.0, J 3.6, CH), 3.8 (3 H, s, Me), 4.43 (1 H, dd, J 8.7, J 3.6, CH),
5.14 (2 H, ABq, νꢀAB = 16.0 Hz, JAB 14.2, CH2), 6.84 (2 H, d, 3J 6.2, 2 CH), 7.4 (2 H,
d, 3J 6.2, 2 CH). 13C NMR: δ 36.7 (CH2), 45.8 (CH), 47.7 (CH2), 55.6 (Me), 114.3 (2CH),
127.2 (CH), 131.0 (2CH), 159.8 (C-OMe), 175.0 (C O), 175.8 (C O), 200.5 (C S).
Tetrahydro-2,5-dioxofuran-3-yl (furan-2-yl)methylcarbamodithioate (3j).
Pale yellow crystals; yield: 0.46 g (93%); mp 105–106◦C. IR (KBr) (νmax/cm−1): 3449,
2549, 1726, 1704, 1411, 1331, 1243, 1103. EI-MS: 271 (M+, 9), 25 (9), 187 (11), 139
(78), 81 (100), 45 (8), 29 (18); Anal. Calcd. for C10H9NO4S2 (271.3): C, 44.27; H, 3.34; N,
5.16%. Found: C, 44.54; H, 3.42; N, 5.22%. 1H NMR: δ = 3.07 (1 H, dd, 2J 18.0, 3J 9.0,
CH), 3.34 (1 H, dd, 2J 18.0, 3J 3.8, CH), 4.47 (1 H, dd, 3J 9.0, 3J 3.8, CH), 5.20 (2 H, ABq,
νꢀAB = 8 Hz, JAB 14.2, CH2), 6.32–7.35 (3 H, m, CH-furyl), 7.28 (1 H, br s, NH). 13C
NMR: δ 36.7 (CH2), 41.0 (CH), 45.7 (CH2), 110.8 (CH), 110.9 (CH), 143.0 (CH), 147.9
(C), 175.3 (C O), 175.4 (C O), 199.8 (C S).
Tetrahydro-2,5-dioxofuran-3-yl 2-hydroxypropylcarbamodithioate (3k).
Pale yellow crystals; yield: 0.46 g (93%); mp 157–159◦C. IR (KBr) (νmax/cm−1): 3436,
3380, 2349, 1735, 1704, 1456, 1368, 1262, 1208, 1131. EI-MS: 249 (M+, 9), 231 (45),
203(8), 191 (10), 133 (17), 116 (100), 45 (28); Anal. Calcd. for C8H11NO4S2 (249.2): C,
1
38.55; H, 4.45; N, 5.62%. Found: C, 38.63; H, 4.52; N, 5.74%. Major isomer (80%): H
2
NMR: δ = 1.20 (3 H, d, 3J 6.0, Me), 3.15 (1 H, dd, J 19, 3J 6.3, CH), 3.27 (1 H, dd, 2J
3
19.0, J 3.9, CH), 3.34 (1 H, br s, OH), 3.77–3.80 (2 H, m, CH2-N), 4.23–4.25 (1 H, m,
3
3
CH-O), 4.60 (1 H, dd, J 6.3, J 3.9, CH). 13C NMR: δ = 21.7 (Me), 36.5 (CH2), 46.8
(CH), 60.0 (CH2), 63.4 (CH), 172.5 (C O), 177.0 (C O), 200.5 (C S). Minor isomer
(20%): 1H NMR: δ = 1.16 (3 H, d, 3J 6.0, Me), 3.13 (1 H, dd, 2J 19.0, 3J 6.3, CH), 3.26 (1
H, dd, 2J 19.0, 3J 3.9, CH), 3.34 (1 H, br-s, OH), 3.86–3.90 (2 H, m, CH2-N), 4.21–4.23 (1
H, m, CH-O), 4.55 (1 H, dd, 3J 6.3, 3J 3.9, CH), 4.87 (1 H, br s, NH). 13C NMR: δ = 21.6
(Me), 36.3 (CH2), 46.7 (CH), 51.9 (CH2), 63.3 (CH), 172.4 (C O), 176.9 (C O), 200.1
(C S).
Tetrahydro-2,5-dioxofuran-3-yl phenylcarbamodithioate (3l). Pale Yellow
oil; yield: 0.06 g (11%); IR (KBr) (νmax/cm−1): 3400, 2535, 1710, 1660, 1425, 1347, 1160.
EI- MS: 268 (M+1, 10), 267 (M+, 8), 221 (9), 134 (100), 92 (23), 65 (16), 45 (8). Anal.
Calcd. for C11H9NO3S2 (267.3): C, 49.43; H, 3.39; N, 5.24%. Found: C, 50.02; H, 4.04; N,
5.30%. 1H NMR: δ = 3.32 (1 H, dd, 2J 8.0, 3J 3.5, CH), 3.52 (1 H, br s, NH), 4.24 (1 H, dd,
3J 5.5, 3J 3.5, CH), 4.64 (1 H, dd, 2J 8.0, 3J 5.5, CH), 7.22–7.54 (5 H, m, CH-arom). 13
C
NMR: δ 37.8 (CH2), 43.5 (CH), 125.2 (CH), 129.5 (2CH), 129.8 (2CH), 135.0 (C), 173.4
(C O), 175.9 (C O), 200.1 (C S).
Tetrahydro-2,5-dioxofuran-3-yl diethylcarbamodithioate (3m). Pale yel-
low crystals; yield: 0.10 g (20%); mp 118–119◦C. IR (KBr) (νmax/cm−1): 3423, 2565,
1718, 1705, 1430, 1321, 1120. EI-MS: 247 (M+, 7), 219 (24), 190 (100), 176 (13), 116
(23), 29 (16); Anal. Calcd. for C9H13NO3S2 (247.3): C, 43.72; H, 5.29; N, 5.67%. Found:
C, 42.90; H, 5.20; N, 5.72%. 1H NMR: δ = 1.19 (3 H, t, 3J 7.2, Me), 1.24 (3 H, t, 3J 7.2,

ONE-POT SYNTHESIS OF CARBAMODITHIOATE
1731
Me), 3.15 (1 H, dd, 2J 18.0, 3J 8.4, CH), 3.37 (1H, dd, 2J 18.0, 3J 3.6, CH), 3.77 (2 H, q,
3J 7.2, CH2), 4.02 (2 H, q, 3J 7.2, CH2), 5.25 (1 H, dd, 3J 8.4, 3J 3.6, CH). 13C NMR: δ =
13.2 (Me), 14.4 (Me) 36.4 (CH2), 41.7 (CH2), 43.2 (CH2), 51.3 (CH), 171.3 (C O), 171.4
(C O), 193.8 (C S).
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