-VERSUS -SIGMATROPIC REARRANGEMENT OF O-SUBSTITUTED ALLYL N-ACYLMONOTHIOCARBAMATES

Article abstract of DOI:10.1135/cccc19942650

Substituted allylic alcohols (2-buten-1-ol, 1-buten-3-ol, cinnamyl alcohol and 3-methyl-2-buten-1-ol) react with acyl isothiocyanates (4-chlorobenzoyl, 2,6-difluorobenzoyl, 3-phenylpropenoyl, 2-thienocarbonyl, 3-chloro-2-thienocarbonyl and 3-chloro-2-benzothienocarbonyl isothiocyanate) with the formation of highly reactive O-substituted allyl N-acylmonothiocarbamates, which either spontaneously or by heating in boiling benzene undergo <3,3>-sigmatropic rearrangement to S-substituted allyl N-acylmonothiocarbamates.The structure of S-series with isomerized allylic group affords the unequivocal evidence of the <3,3>-sigmatropic route of studied rearrangement.Further heating of <3,3>-rearranged N-(4-chlorobenzoyl)monothiocarbamates results in the <1,3>-sigmatropic shift of monothiocarbamate group.Using arylalkyl alcohols with the allylic double bond inserted into an aromatic system the obtained O-esters either do not undergo any rearrangement (benzyl alcohol) or undergo <1,3>-sigmatropic rearrangement (2- and 3-furylmethanol and 1-(2-furyl)ethanol) to the corresponding S-esters.For explanation of this reaction the tandem of <3,3>- and <1,3>-sigmatropic rearrangements is suggested.

Full text of DOI:10.1135/cccc19942650

2650
Ficeri, Kutschy, Dzurilla, Imrich:
[3,3]- VERSUS [1,3]-SIGMATROPIC REARRANGEMENT
OF O-SUBSTITUTED ALLYL N-ACYLMONOTHIOCARBAMATES
Vlastimir FICERI, Peter KUTSCHY, Milan DZURILLA and Jan IMRICH
Department of Organic Chemistry,
P. J. Safarik University, 041 67 Kosice, The Slovak Republic
Received December 16, 1993
Accepted October 15, 1994
Substituted allylic alcohols (2-buten-1-ol, 1-buten-3-ol, cinnamyl alcohol and 3-methyl-2-buten-1-ol)
react with acyl isothiocyanates (4-chlorobenzoyl, 2,6-difluorobenzoyl, 3-phenylpropenoyl, 2-thieno-
carbonyl, 3-chloro-2-thienocarbonyl and 3-chloro-2-benzo[b]thienocarbonyl isothiocyanate) with the
formation of highly reactive O-substituted allyl N-acylmonothiocarbamates, which either sponta-
neously or by heating in boiling benzene undergo [3,3]-sigmatropic rearrangement to S-substituted
allyl N-acylmonothiocarbamates. The structure of S-esters with isomerized allylic group affords the
unequivocal evidence of the [3,3]-sigmatropic route of studied rearrangement. Further heating of
[3,3]-rearranged N-(4-chlorobenzoyl)monothiocarbamates results in the [1,3]-sigmatropic shift of
monothiocarbamate group. Using arylalkyl alcohols with the allylic double bond inserted into an aro-
matic system the obtained O-esters either do not undergo any rearrangement (benzyl alcohol) or
undergo [1,3]-sigmatropic rearrangement (2- and 3-furylmethanol and 1-(2-furyl)ethanol) to the
corresponding S-esters. For explanation of this reaction the tandem of [3,3]- and [1,3]-sigmatropic
rearrangements is suggested.
The oxygen and sulfur containing 1,5-hexadiene systems of the type I (O-allyl mono-
thioesters1–4, monothiocarbamates5–8, mono-3 and dithiocarbonates6,9,10) are known to
undergo a catalyzed or non-catalyzed [3,3]-sigmatropic rearrangement to compounds of
the type II possessing the carbonyl and S-allyl instead of thiocarbonyl and O-allyl
groups present in I. It was found5,6 that substituents on allylic group, particularly
α-methyl, accelerate the reaction I → II. Reactivity also depends on the nature of group
R. O-Allyl monothioesters are less reactive than compounds with R bonded via hetero-
atom, e.g. O-allyl N,N-dialkylmonothiocarbamates. Reactivity of monothiocarbamates
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

O-Substituted Allyl N-Acylmonothiocarbamates
2651
is influenced by the nature of substituents on nitrogen atom8. O-Allyl N-phenylmono-
thiocarbamate rearranges to the corresponding S-allyl ester in boiling benzene during
48 h, whereas analogous N-benzoyl derivative requires only 9 h. In the present work we
have studied the preparation of a series of O-substituted allyl N-acylmonothiocarba-
mates (1 – 20) from 4-chlorobenzoyl, 2,6-difluorobenzoyl, 3-phenylpropenoyl,
2-thienocarbonyl, 3-chloro-2-thienocarbonyl and 3-chloro-2-benzo-[b]thienocarbonyl
isothiocyanate and substituted allyl alcohols. Our attention was predominantly focused
on the rearrangement of O- to S-substituted allyl N-acylmonothiocarbamates (21 – 40,
Scheme 1) with the aim to find out whether a [1,3]-sigmatropic rearrangement can be
competitive or consequent reaction to the expected [3,3]-sigmatropic rearrangement.
The selection of acyl isothiocyanates used in this study is based mainly on the expected
higher stability and better yields of corresponding O-substituted allyl N-acylmonothio-
carbamates (1 – 20) compared to products which can be obtained from other starting
compounds, e.g. acetyl or benzoyl isothiocyanate8.
It appeared that all of investigated O-substituted allyl esters are highly reactive.
Whereas unsubstituted O-allyl N-acylmonothiocarbamates rearrange in boiling benzene
during 9 – 30 h (yield 50 – 95%)8,11, the longest reaction time for O-substituted allyl
N-acylmonothiocarbamates is 3 h (yield 45 – 90%) under the same reaction conditions.
According to reactivity in the [3,3]-sigmatropic rearrangement the O-substituted allyl
esters 1 – 20 can be divided into three groups: (i) stable (8, 10, 11, 14, 17, 19) which
are isolable as pure compounds and undergo [3,3]-sigmatropic rearrangement by heat-
ing in boiling benzene; (ii) moderately stable (1, 3 – 5, 20) which can be isolated only
as a mixtures with rearranged products and the [3,3]-sigmatropic rearrangement can be
completed in boiling benzene; (iii) unstable (2, 6, 7, 9, 12, 13, 15, 16, 18) which can
not be isolated because the reaction of acyl isothiocyanates with substituted allyl alco-
hols at room temperature affords dirrectly the products of [3,3]-sigmatropic rearrange-
ment.
The highest reactivity exhibit the O-substituted allyl esters having the methyl group
in α-position. None of the O-(1-buten-3-yl) N-acylmonothiocarbamates can be isolated,
at least in a mixture with rearranged product, and only S-(2-butenyl)esters are obtained
already at room temperature. γ-Substitution leads to more stable O-esters in the case of
methyl group, compared to phenyl group, while compounds with two methyl groups in
γ-position of allylic system (4, 20) are less stable then γ-monomethyl derivatives. The
acyl group also influences the reactivity of O-substituted allyl N-acylmonothiocarba-
mates, but this influence is not well understood. It seems that a bulky groups R1 having
extended conjugated system enabling an effective mesomeric interaction with carbonyl
group, increase the stability of corresponding O-substituted allyl N-acylmonothiocarba-
mates, e.g. 8, 10, 17 and 19.
The structure of prepared compounds was proved by spectral methods. Except for
compounds 35 – 37 and 39 exhibiting in infrared spectra one broad intensive absorption
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Ficeri, Kutschy, Dzurilla, Imrich:
SCHEME 1
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

O-Substituted Allyl N-Acylmonothiocarbamates
2653
band of carbonyl vibrations at 1 650 – 1 690 cm−1, all S-substituted allyl esters show
two carbonyl absorption bands of CO−NH−CO grouping at 1 650 – 1 715 cm−1,
whereas O-substituted allyl esters show a single absorption band of ν(C=O) at 1 680 –
1 720 cm−1. Structural evidence provided by NMR spectroscopy can be demonstrated
1
on N-(3-phenylpropenoyl)monothiocarbamates 8, 10, 28 – 30. In H NMR spectra of
compounds 8 and 10, there are present the signals of OCH2 protons at 5.11 and 5.56
ppm, while 29 which is the functional group isomer of 8, exhibits the SCH2 signal at
3.93 ppm. In 13C NMR spectra of 8 and 10, there are present the triplets of OCH2 group
at 73.42 and 71.09 ppm. Corresponding rearranged products show doublets of SCH
groups at 41.66 ppm (28) and 49.58 ppm (30). The triplet of SCH2 group of 29 is
present at 32.21 ppm. As expected, the NMR data (see Experimental) of compounds 21 – 40
are in full agreement with the structure of products formed from starting compounds by
[3,3]-sigmatropic rearrangement. Posible [1,3]-sigmatropic rearrangement as a compe-
titive process to the [3,3]-sigmatropic rearrangement can be excluded. Anyway there is
described an example of competitive [1,3]-sigmatropic rearrangement of O-substituted
allyl N,N-dialkylmonothiocarbamates to S-substituted allyl esters by heating to 150 °C,
whereas at 130 °C the [3,3]-sigmatropic rearrangement takes place5. We have found
that the [1,3]-sigmatropic rearrangement can be a consecutive, but not competitive re-
action. For instance, heating of [3,3]-rearranged products 21 and 23 with α-substituted
allylic group in boiling toluene causes the [1,3]-sigmatropic rearrangement with the
formation of compounds 22 and 41 (Scheme 2).
If the reaction is started from O-ester 3, the product 23 is formed in boiling toluene
immediately and only after prolonged heating it changes to [1,3]-rearranged product 41
1
(TLC and H NMR). The driving force of observed [1,3]-sigmatropic rearrangement
can be ascribed to the conversion of thermodynamically less stable terminal double
bond to the more stable internal double bond7. In agreement with this explanation is the
stability of compound 22 obtained from 4-chlorobenzoyl isothiocyanate and 1-buten-3-ol
which does not rearrange by heating in boiling toluene.
In continuation of our study we obtained interesting results by investigation of mono-
thiocarbamates obtained from arylalkyl alcohols in which the allylic double bond is a
SCHEME 2
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2654
Ficeri, Kutschy, Dzurilla, Imrich:
part of aromatic system (benzyl alcohol, 2-furylmethanol, 1-(2-furyl)ethanol and
3-furylmethanol) and 4-chlorobenzoyl, 3-phenylpropenoyl and 3-chloro-2-
benzo[b]thienocarbonyl isothiocyanate (Scheme 3).
O-Benzyl esters 45 and 47 are very stable and even after 20 h of reflux in benzene
1
do not exhibit any tendency to rearrange (TLC and H NMR). On the other hand
2-furylmethanol and 1-(2-furyl)ethanol react with acyl isothiocyanates dirrectly with
the formation of [1,3]-rearranged products 51, 52, 54, 55 and 56 without the possibility
to isolate corresponding O-arylalkyl esters 42, 43, 46, 48 and 49. Products possessing
the medium reactivity are obtained from 3-furylmethanol. O-(3-Furylmethyl) esters 44
and 50 can be isolated and they undergo the [1,3]-sigmatropic rearrangement to
S-(3-furylmethyl) esters 53 and 57 by 3 h reflux in benzene. According to above men-
tioned activation effect of α-methyl group, we expected enhanced reactivity of
benzoyloxy group in O-[1-(3-nitrophenyl)ethyl] N-(4-chlorobenzoyl)monothiocarba-
mate (58). However, heating of compound 58 revealed that it is equally stable and
unreactive as compounds 45 and 47.
Unusually high reactivity of furan derivatives and unreactivity of benzyl esters indi-
cate some specific interaction between furan ring and monothiocarbamate functionality.
There might take place a tandem of [3,3]- and [1,3]-sigmatropic rearrangements or
dirrect [1,3]-sigmatropic rearrangement of O-arylalkyl to S-arylalkyl N-acylmonothio-
carbamates (Scheme 3). In the literature there is only limited information about analo-
gous [1,3]-sigmatropic rearrangements. O-Methyl N-acylmonothiocarbamates require
the BF3-catalysis12 whereas O-aryl N,N-diethylmonothiocarbamates undergo [1,3]-sig-
matropic rearrangement at 280 – 285 °C in diphenyl ether13. It was found that 2-furfu-
ryloxy-4,5-diphenyloxazole affords at 60 °C the isolable [3,3]-rearranged product,
similar to intermediate A (Scheme 3) which undergoes the [1,3]-sigmatropic shift of
hydrogen by heating to 90 °C. The same mechanism of [3,3]-sigmatropic rearrange-
ment followed by [1,3]-sigmatropic shift of amido group is proposed for 2-benzyloxy-
4,5-diphenyloxazole, although intermediate is not isolable14. All of our attempts to
isolate an intermediate of the type A during rearrangement of furyl derivatives in ben-
zene and acetonitrile at temperature below 80 °C failed. However, considering the un-
reactivity of O-benzyl N-acylmonothiocarbamates and the above mentioned literature
data it can be suggested that a tandem of [3,3]- and [1,3]-sigmatropic rearrangements is
probably the reason of high reactivity of O-(2-furylmethyl), O-[1-(2-furyl)ethyl] and
O-(3-furylmethyl) N-acylmonothiocarbamates. We assume that owing to relatively low
aromaticity of furan ring, the [3,3]-sigmatropic rearrangement with the formation of
species A proceeds smoothly. Electron withdrawing effect of carbonyl group enhances
the reactivity of sulfur atom and favours its interaction with exocyclic double bond.
This interaction probably results in the immediate [1,3]-sigmatropic shift of N-acyl-
monothiocarbamate group and transformation of transiently formed dihydrofuran inter-
mediate A onto furan ring in final product. Competitive [1,3]-sigmatropic hydrogen
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

O-Substituted Allyl N-Acylmonothiocarbamates
2655
shift is not observed; no products containing the methyl group can be isolated from the
mixture.
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2656
Ficeri, Kutschy, Dzurilla, Imrich:
EXPERIMENTAL
The infrared absorption spectra were recorded on an IR-75 (Zeiss, Jena) spectrometer in chloroform
(compounds 3, 5, 8, 10, 11, 14, 19, 21 – 41, 45, 50, 55 – 58) or in KBr pellets (compounds 44, 51 – 54);
the wavenumbers are given in cm−1
.
1H and 13C NMR spectra were measured on Tesla BS 487A
(80 MHz for H) and Tesla BS 567 (25.15 MHz for 13C) spectrometers in deuteriochloroform (com-
pounds 1, 3, 4, 8, 11, 14, 19 – 29, 31, 32, 34 – 36, 38 – 41, 44, 45, 47, 50, 52, 56 – 58) or in
hexadeuteriodimethyl sulfoxide (compounds 10, 30, 33, 37, 51, 54, 55) with tetramethylsilane as an
internal standard. Chemical shifts are given in ppm (δ scale), coupling constants J in Hz.
2-Buten-1-ol (mixture of isomers), trans-cinnamyl alcohol, benzyl alcohol, 2-furylmethanol and
3-furylmethanol (Aldrich), 1-buten-3-ol (Merck), 3-methyl-2-buten-1-ol and 1-(2-furyl)ethanol
(Fluka) were used as commercial chemicals. 4-Chlorobenzoyl isothiocyanate15, 2,6-difluorobenzoyl
isothiocyanate16, 3-phenylpropenoyl isothiocyanate17, 2-thienocarbonyl isothiocyanate18, 3-chloro-2-
thienocarbonyl isothiocyanate19, 3-chloro-2-benzo[b]thienocarbonyl isothiocyanate20 and 1-(3-nitro-
phenyl)ethanol21 were prepared according to the literature. The reactions were monitored by
thin-layer chromatography on Silufol plates (Kavalier, The Czech Republic) using benzene–acetone
(7 : 1) as eluent.
1
O-Substituted Allyl N-Acylmonothiocarbamates 1, 3 – 5, 8, 10, 11, 14, 17, 19, 20
Substituted allyl alcohol (18 mmol) was added to acyl isothiocyanate (15 mmol) in dry benzene (20 ml) and
the mixture was left asside at room temperature for 1 day (compounds 4, 11, 17 and 20), 2 days
(compounds 1, 3 and 14), 3 days (compound 10), 4 days (compounds 5 and 8) or 5 days (compound
19). Hexane (80 – 200 ml) was added to turbidity and mixture allowed to stand at 0 °C for 24 h. The
precipitate was filtered off and the product crystallized from a suitable solvent. Compounds 1, 3, 4,
5 and 20 were obtained only as mixtures with rearranged products 21, 23, 24, 25 and 40; the ratio of
constituents was determined by 1H NMR spectroscopy. In these cases the yields of mixtures are
given.
O-(2-Buten-1-yl) N-(4-chlorobenzoyl)monothiocarbamate (1), in the 1 : 1 mixture with 21; yield
80%. 1H NMR spectrum: 1.80 m, 3 H (CH3); 5.18 m, 2 H (OCH2); 5.97 m, 2 H (CH=CH); 7.53 d,
2 H and 7.91 d, 2 H, J = 8 (4-ClC6H4); 9.40 s, 1 H (NH).
O-Cinnamyl N-(4-chlorobenzoyl)monothiocarbamate (3), in the 1 : 1 mixture with 23; yield 60%.
1H NMR spectrum: 5.36 m, 2 H (OCH2); 6.62 m, 2 H (CH=CH); 7.47 m, 5 H (C6H5); 7.58 d, 2 H
and 7.92 d, 2 H, J = 8 Hz (4-ClC6H4); 9.35 s, 1 H (NH).
O-(3-Methyl-2-buten-1-yl) N-(4-chlorobenzoyl)monothiocarbamate (4), in the 3 : 1 mixture with
1
24; yield 83%. H NMR spectrum: 1.80 m, 6 H (2 × CH3); 5.18 m, 2 H (OCH2); 5.57 m, 1 H (=CH);
7.52 d, 2 H and 7.87 d, 2 H, J = 8 (4-ClC6H4); 9.39 s, 1 H (NH).
O-(2-Buten-1-yl) N-(2,6-difluorobenzoyl)monothiocarbamate (5); in the 1 : 1 mixture with 25;
1
yield 76%. H NMR spectrum: 1.80 m, 3 H (CH3); 5.00 m, 2 H (OCH2); 7.19 m, 2 H and 7.60 m, 1 H
(2,6-F2C6H3); 9.25 s, 1 H (NH).
O-(2-Buten-1-yl) N-(3-phenylpropenoyl)monothiocarbamate (8); yield 80%, m.p. 140 – 142 °C
(benzene–hexane). For C14H15NO2S (260.3) calculated: 64.34% C, 5.79% H, 5.36% N; found:
64.13% C, 5.74% H, 5.25% N. IR spectrum: 1 495 (NHCS), 1 625 and 1 675 (C=C), 1 715 (C=O),
1
3 380 (N−H). H NMR spectrum: 1.75 m, 3 H (CH3); 5.01 m, 2 H (OCH2); 5.90 m, 2 H (CH=CH);
7.09 d, 1 H and 7.86 d, 1 H, J = 16 (CH=CHCO); 7.45 m, 5 H (C6H5); 9.25 s, 1 H (NH). 13C NMR
spectrum: 17.81 q (CH3), 73.42 t (OCH2), 119.52 d and 145.88 d (CH=CHCO), 123.63 d and 133.26 d
(CH=CHCH3), 128.37, 128.93, 130.64 and 134.45 (C6H5), 163.27 s (C=O), 188.88 s (C=S).
O-Cinnamyl N-(3-phenylpropenoyl)monothiocarbamate (10); yield 90%, m.p. 126 – 128 °C
(acetone–water). For C19H17NO2S (323.4) calculated: 70.56% C, 5.30% H, 4.33% N; found: 70.70% C,
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

O-Substituted Allyl N-Acylmonothiocarbamates
2657
5.10% H, 4.61% N. IR spectrum: 1 490 (NHCS), 1 630 and 1 675 (C=C), 1 720 (C=O), 3 385 (N−H).
1H NMR spectrum: 5.56 m, 2 H (OCH2); 7.20 m, 2 H (CH=CH); 7.60 d, 1 H and 8.08 d, 1 H, J = 16
(CH=CHCO); 7.78 m, 10 H (2 × C6H5); 12.08 s, 1 H (NH). 13C NMR spectrum: 71.09 t (OCH2),
120.73 d and 143.43 d (CH=CHCO), 122.24 d and 133.76 d (CH=CHCH2), 126.29, 127.82, 128.42,
128.75, 130.17, 134.09 and 135.69 (2 × C6H5), 162.16 s (C=O), 188.44 s (C=S).
O-(2-Buten-1-yl) N-(2-thienocarbonyl)monothiocarbamate (11); yield 53%, m.p. 82 – 84 °C
(acetone–hexane). For C10H11NO2S2 (241.3) calculated: 49.77% C, 4.59% H, 5.80% N; found:
49.90% C, 4.38% H, 5.64% N. IR spectrum: 1 480 (NHCS), 1 675 (C=C), 1 690 (C=O), 3 410 (N−H).
1H NMR spectrum: 1.80 m, 3 H (CH3); 5.14 m, 2 H (OCH2); 5.98 m, 2 H (CH=CH); 7.28 m, 1 H,
7.83 m, 1 H and 8.20 m, 1 H (2-thienyl); 11.43 s, 1 H (NH).
O-(2-Buten-1-yl) N-(3-chloro-2-thienocarbonyl)monothiocarbamate (14); yield 50%, m.p.
40 – 42 °C (benzene–hexane). For C10H10ClNO2S2 (275.8) calculated: 43.55% C, 3.65% H, 5.08% N;
found: 43.26% C, 3.79% H, 5.21% N. IR spectrum: 1 480 (NHCS), 1 680 (C=O), 3 365 (N−H).
1H NMR spectrum: 1.83 m, 3 H (CH 3); 5.18 m, 2 H (OCH2); 6.02 m, 2 H (CH=CH); 7.18 d, 1 H and
7.78 d, 1 H, J = 5 (2,3-disubstituted thiophene); 10.10 s, 1 H (NH).
O-(2-Buten-1-yl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (17); yield 42%, m.p.
97 – 99 °C (benzene–hexane). For C14H12ClNO2S2 (325.8) calculated: 51.61% C, 3.71% H, 4.30% N;
found: 51.42% C, 3.59% H, 4.09% N. IR spectrum: 1 500 (NHCS), 1 690 (C=O), 3 380 (N−H).
1H NMR spectrum: 1.78 m, 3 H (CH3); 5.10 m, 2 H (OCH2); 5.93 m, 2 H (CH=CH); 7.56 m, 2 H
and 7.79 m, 2 H (2,3-disubstituted benzothiophene); 10.15 s, 1 H (NH).
O-Cinnamyl N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (19); yield 71%, m.p.
115 – 117 °C (benzene–hexane). For C19H14ClNO2S2 (387.9) calculated: 58.83% C, 3.46% H, 3.69% N;
found: 58.68% C, 3.39% H, 3.47% N. IR spectrum: 1 505 (NHCS), 1 700 (C=O), 3 380 (N−H).
1H NMR spectrum: 5.35 m, 2 H (OCH2); 6.70 m, 2 H (CH=CH); 7.40 m, 5 H (C6H5); 7.55 m, 2 H
and 7.90 m, 2 H (2,3-disubstituted benzothiophene); 10.19 s, 1 H (NH).
O-(3-Methyl-2-buten-1-yl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (20) in
the 2 : 1 mixture with 40. 1H NMR spectrum: 1.83 m, 3 H (CH3); 5.25 m, 2 H (OCH2); 5.68 m,
1 H (=CH); 7.68 m, 2 H and 7.98 m, 2 H (2,3-disubstituted benzothiophene); 10.18 s, 1 H (NH).
S-Substituted Allyl N-Acylmonothiocarbamates 21 – 41
A. A solution of the corresponding O-allyl ester or its mixture with rearranged product (3 mmol)
in benzene (10 ml) was refluxed for 0.5 h (compounds 34 and 37), 1 h (compound 30), 1.5 h (com-
pound 31), 2 h (compounds 21, 23 and 28) or 3 h (compounds 24, 39 and 40). The solvent was
evaporated and the residue crystallized from an appropriate solvent.
B. Substituted allyl alcohol (18 mmol) was added to acyl isothiocyanate (15 mmol) in anhydrous
benzene (20 ml) and the mixture was kept at room temperature for 1 day (compounds 22 and 32), 2
days (compound 36), 3 days (compounds 33, 35 and 38), 4 days (compounds 25 and 26) or 5 days
(compounds 27 and 29). Hexane (80 – 200 ml) was added to turbidity and mixture allowed to stand
at 0 °C for 24 h. The precipitate was filtered off and the product crystallized from a suitable solvent.
C. S-Substituted allyl N-(4-chlorobenzoyl)monothiocarbamate 21 or 23 (1 mmol) was refluxed in
toluene (8 ml) for 16 h. The mixture was filtered and products 22 or 41 precipitated by addition of
light petroleum, dried and crystallized from a suitable solvent.
S-(1-Buten-3-yl) N-(4-chlorobenzoyl)monothiocarbamate (21); yield 82%, m.p. 159 – 162 °C
(dec., benzene–hexane). For C12H12ClNO2S (269.8) calculated: 53.42% C, 4.48% H, 5.19% N;
found: 53.28% C, 4.56% H, 5.08% N. IR spectrum: 1 650 (C=C), 1 675 and 1 715 (C=O), 3 415
1
(N−H). H NMR spectrum: 1.53 d, 3 H, J = 7 (CH3); 4.32 m, 1 H (CH); 5.35 m, 2 H (=CH2); 6.09 m,
1 H (=CH); 7.55 d, 2 H and 8.05 d, 2 H, J = 8 (4-ClC6H4); 10.17 s, 1 H (NH).
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

2658
Ficeri, Kutschy, Dzurilla, Imrich:
S-(2-Buten-1-yl) N-(4-chlorobenzoyl)monothiocarbamate (22); yield 50% (procedure B) or 70%
(procedure C), m.p. 156 – 159 °C (dec., benzene–hexane). For C12H12ClNO2S (269.8) calculated:
53.42% C, 4.48% H, 5.19% N; found: 53.20% C, 4.62% H, 5.12% N. IR spectrum: 1 635 (C=C),
1
1 650 and 1 685 (C=O), 3 400 (N−H). H NMR spectrum: 1.75 m, 3 H (CH3); 3.65 m, 2 H (SCH2);
5.78 m, 2 H (CH=CH); 7.57 d, 2 H and 8.10 d, 2 H, J = 8 (4-ClC6H4); 11.30 s, 1 H (NH).
S-(1-Phenyl-2-propen-1-yl) N-(4-chlorobenzoyl)monothiocarbamate (23); yield 82%, m.p. 124 –
126 °C (benzene–hexane). For C17H14ClNO2S (331.8) calculated: 61.54% C, 4.25% H, 4.22% N;
found: 61.78% C, 4.09% H, 4.18% N. IR spectrum: 1 643 (C=C), 1 665 and 1 705 (C=O), 3 408
(N−H). 1H NMR spectrum: 5.36 m, 3 H (=CH2 and CH); 6.18 m, 1 H (=CH); 7.50 m, 5 H (C6H5);
7.45 d, 2 H and 7.91 d, 2 H, J = 8 (4-ClC6H4); 9.65 s, 1 H (NH).
S-(1-Buten-3-methyl-3-yl) N-(4-chlorobenzoyl)monothiocarbamate (24); yield 60%, m.p. 123 – 125 °C
(benzene). For C13H14ClNO2S (283.8) calculated: 55.02% C, 4.97% H, 4.93% N; found: 55.19% C,
5.13% H, 4.88% N. IR spectrum: 1 630 (C=C), 1 660 and 1 695 (C=O), 3 410 (N–H). 1H NMR
spectrum: 1.60 s, 6 H (2 × CH3); 5.15 m, 2 H (=CH2); 6.15 m, 1 H (=CH); 7.47 d, 2 H and 7.90 d,
2 H, J = 8 (4-ClC6H4).
S-(1-Buten-3-yl) N-(2,6-difluorobenzoyl)monothiocarbamate (25); yield 76%, m.p. 102 – 104 °C
(benzene–hexane). For C12H11F2NO2S (271.3) calculated: 53.13% C, 4.09% H, 5.16% N; found:
53.28% C, 3.91% H, 5.02% N. IR spectrum: 1 625 (C=C), 1 670 and 1 715 (C=O), 3 395 (N−H).
1H NMR spectrum: 1.45 d, 3 H, J = 7 (CH3); 4.26 m, 1 H (CH); 5.28 m (=CH2); 6.03 m, 1 H (=CH);
7.12 m, 2 H and 7.57 m, 1 H (2,6-F2C6H3); 9.28 s, 1 H (NH).
S-(2-Buten-1-yl) N-(2,6-difluorobenzoyl)monothiocarbamate (26); yield 83%, m.p. 133 – 135 °C
(benzene–hexane). For C12H11F2NO2S (271.3) calculated: 53.13% C, 4.09% H, 5.16% N; found:
53.27% C, 4.15% H, 5.31% N. IR spectrum: 1 620 (C=C), 1 660 and 1 715 (C=O), 3 400 (N−H). 1H NMR
spectrum: 1.76 m, 3 H (CH3); 3.60 m, 2 H (SCH2); 5.68 m, 2 H (CH=CH); 7.13 m, 2 H and 7.62 m,
1 H (2,6-F2C6H3); 9.38 s, 1 H (NH).
S-(1-Phenyl-2-propen-1-yl) N-(2,6-difluorobenzoyl)monothiocarbamate (27); yield 50%, m.p.
126 – 129 °C (dec., benzene–hexane). For C17H13F2NO2S (333.4) calculated: 61.24% C, 3.93% H,
4.20% N; found: 60.96% C, 3.71% H, 4.45% N. IR spectrum: 1 620 (C=C), 1 670 and 1 710 (C=O),
3 400 (N−H). 1H NMR spectrum: 5.40 m, 3 H (=CH2 and CH); 6.30 m, 1 H (=CH); 7.00 – 7.80 m,
8 H (C6H5 and 2,6-F2C6H3); 9.26 s, 1 H (NH).
S-(1-Buten-3-yl) N-(3-phenylpropenoyl)monothiocarbamate (28); yield 72%, m.p. 119 – 122 °C
(dec., benzene–hexane). For C14H15NO2S (261.3) calculated: 64.34% C, 5.79% H, 5.36% N; found:
64.13% C, 5.74% H, 5.25% N. IR spectrum: 1 625 and 1 655 (C=C), 1 670 and 1 700 (C=O), 3 390
1 H (=CH); 6.90 d, 1 H and 7.90 d, 1 H, J = 16 Hz (CH=CH); 7.47 m, 5 H (C6H5); 9.65 s, 1 H
(NH). 13C NMR spectrum: 19.52 q (CH3), 41.66 d (CH), 115.71 t (=CH2), 118.81 d and 146.02 d
(CH=CH), 128.44, 128.93, 130.76 and 134.23 (C6H5), 138.45 d (=CH), 164.91 s and 170.45 s (C=O).
S-(2-Buten-1-yl) N-(3-phenylpropenoyl)monothiocarbamate (29); yield 80%, m.p. 131 – 133 °C
(acetone–water). For C14H15NO2S (261.3) calculated: 64.34% C, 5.79% H, 5.36% N; found: 64.18% C,
5.90% H, 5.12% N. IR spectrum: 1 620 and 1 660 (C=C), 1 690 and 1 715 (C=O), 3 395 (N−H).
1H NMR spectrum: 2.05 m, 3 H (CH3); 3.93 m, 2 H (SCH2); 6.05 m, 2 H (CH=CH); 7.23 d, 2 H and
8.15 d, 2 H, J = 16 (CH=CHCO); 7.95 m, 5 H (C6H5); 11.42 s, 1 H (NH). 13C NMR spectrum: 17.69 q
(CH3), 32.21 t (SCH2), 118.89 d and 145.99 d (CH=CHCO), 125.35 d and 129.90 d (CH=CHCH2),
128.48, 128.97, 130.76 and 134.30 (C6H5), 164.95 s and 170.99 s (C=O).
S-(1-Phenyl-2-propen-1-yl) N-(3-phenylpropenoyl)monothiocarbamate (30); yield 87%, m.p.
127 – 129 °C (tetrachloromethane). For C19H17NO2S (323.4) calculated: 70.56% C, 5.30% H,
4.33% N; found: 70.41% C, 5.19% H, 4.03% N. IR spectrum: 1 625 and 1 645 (C=C), 1 670 and
1 710 (C=O), 3 395 (N−H). 1H NMR spectrum: 5.52 m, 3 H (=CH2 and CH); 6.50 m, 1 H (=CH);
7.10 d, 1 H and 8.01 d, 1 H, J = 16 (CH=CH); 7.63 m, 10 H (2 × C6H5); 11.70 s, 1 H (NH).
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O-Substituted Allyl N-Acylmonothiocarbamates
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13C NMR spectrum: 49.58 d (CH), 116.44 t (=CH2), 119.25 d and 143.57 d (CH=CH), 127.00,
127.79, 127.86, 128.27, 128.76, 130.27, 133.83 and 139.54 (2 × C6H5), 137.08 d (=CH), 164.14 s
and 167.39 s (C=O).
S-(1-Buten-3-yl) N-(2-thienocarbonyl)monothiocarbamate (31); yield 90%, m.p. 96 – 98 °C (ben-
zene–hexane). For C10H11NO2S2 (241.3) calculated: 49.77% C, 4.59% H, 5.80% N; found: 49.62% C,
4.51% H, 5.50% N. IR spectrum: 1 640 (C=C), 1 665 and 1 695 (C=O), 3 410 (N−H). 1H NMR
spectrum: 1.54 d, 3 H, J = 7 (CH3); 4.38 m, 1 H (CH); 5.30 m, 2 H (=CH2); 6.12 m, 1 H (=CH);
7.30 m, 1 H, 8.86 m, 1 H and 8.10 m, 1 H (2-thienyl); 10.15 s, 1 H (NH).
S-(2-Buten-1-yl) N-(2-thienocarbonyl)monothiocarbamate (32); yield 67%, m.p. 142 – 145 °C
(dec., benzene–hexane). For C10H11NO2S2 (241.3) calculated: 49.77% C, 4.59% H, 5.80% N; found:
49.81% C, 4.43% H, 5.99% N. IR spectrum: 1 630 (C=C), 1 655 and 1 675 (C=O); 3 410 (N−H).
1H NMR spectrum: 1.79 m, 3 H (CH3); 3.63 m, 2 H (SCH2); 5.90 m, 2 H (CH=CH); 7.28 m, 1 H,
7.83 m, 1 H and 8.28 m, 1 H (2-thienyl); 11.53 s, 1 H (NH).
S-(1-Phenyl-2-propen-1-yl) N-(2-thienocarbonyl)monothiocarbamate (33); yield 52%, m.p.
129 – 131 °C (benzene–hexane). For C15H13NO2S2 (303.4) calculated: 59.38% C, 4.32% H, 4.62% N;
found: 59.56% C, 4.18% H, 4.39% N. IR spectrum: 1 635 (C=C), 1 655 and 1 675 (C=O), 3 405
(N−H). 1H NMR spectrum: 5.37 m, 3 H (=CH2 and CH); 6.25 m, 1 H (=CH); 7.20 m, 1 H, 7.66 m,
1 H and 8.12 m, 1 H (2-thienyl); 7.42 m, 5 H (C6H5); 11.20 s, 1 H (NH).
S-(1-Buten-3-yl) N-(3-chloro-2-thienocarbonyl)monothiocarbamate (34); yield 56%, m.p.
55 – 56 °C (tetrachloromethane–hexane). For C10H10ClNO2S2 (275.8) calculated: 43.55% C, 3.65% H,
5.08% N; found: 43.38% C, 3.50% H, 4.91% N. IR spectrum: 1 670 and 1 685 (C=O), 3 375 (N−H).
1H NMR spectrum: 1.50 d, 3 H, J = 7 (CH3); 4.38 m, 1 H (CH); 5.30 m, 2 H (=CH2); 6.05 m, 1 H
(=CH); 7.17 d, 1 H and 7.75 d, 1 H, J = 5 (2,3-disubstituted thiophene); 9.50 s, 1 H (NH).
S-(2-Buten-1-yl) N-(3-chloro-2-thienocarbonyl)monothiocarbamate (35); yield 60%, m.p.
75 – 77 °C (benzene–hexane). For C10H10ClNO2S2 (275.8) calculated: 43.55% C, 3.65% H, 5.08% N;
1
found: 43.72% C, 3.44% H, 5.31% N. IR spectrum: 1 650 (C=O), 3 360 (N−H). H NMR spectrum:
1.75 m, 3 H (CH3); 3.69 m, 2 H (SCH2); 5.75 m, 2 H (CH=CH); 7.17 d, 1 H and 7.78 d, 1 H, J = 5
(2,3-disubstituted thiophene); 9.55 s, 1 H (NH).
S-(1-Phenyl-2-propen-1-yl) N-(3-chloro-2-thienocarbonyl)monothiocarbamate (36); yield 61%,
m.p. 66 – 69 °C (dec., benzene–hexane). For C15H12ClNO2S2 (337.8) calculated: 53.33% C, 3.58% H,
1
4.15% N; found: 53.12% C, 3.43% H, 3.92% N. IR spectrum: 1 680 (C=O), 3 370 (N−H). H NMR
spectrum: 5.39 m, 3 H (=CH2 and CH); 6.50 m, 1 H (=CH); 7.10 d, 1 H and 7.70 d, 1 H, J = 5
(2,3-disubstituted thiophene); 10.13 s, 1 H (NH).
S-(1-Buten-3-yl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (37); yield 60%, m.p.
231 – 234 °C (dec., benzene–hexane). For C14H12ClNO2S2 (325.8) calculated: 51.61% C, 3.71% H,
1
4.30% N; found: 51.45% C, 3.52% H, 4.17% N. IR spectrum: 1 670 (C=O), 3 370 (N−H). H NMR
spectrum: 1.52 d, 3 H, J = 7 (CH3); 4.37 m, 1 H (CH); 5.28 m, 2 H (=CH2); 6.01 m, 1 H (=CH);
7.58 m, 2 H and 7.93 m, 2 H (2,3-disubstituted benzothiophene); 9.60 s, 1 H (NH).
S-(2-Buten-1-yl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (38); yield 45%, m.p.
122 – 124 °C (benzene–hexane). For C14H12ClNO2S2 (325.8) calculated: 51.61% C, 3.71% H, 4.30% N;
1
found: 51.43% C, 3.63% H, 4.29% N. IR spectrum: 1 670 and 1 690 (C=O), 3 375 (N−H). H NMR
spectrum: 1.75 m, 3 H (CH3); 3.93 m, 2 H (SCH2); 5.78 m, 2 H (CH=CH); 7.58 m, 2 H and 7.95 m,
2 H (2,3-disubstituted benzothiophene); 9.65 s, 1 H (NH).
S-(1-Phenyl-2-propen-1-yl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (39); yield
60%, m.p. 98 – 100 °C (tetrachloromethane). For C19H16ClNO2S2 (387.9) calculated: 58.83% C,
3.64% H, 3.61% N; found: 58.69% C, 3.39% H, 3.43% N. IR spectrum: 1 660 (C=O), 3 370 (N−H).
1H NMR spectrum: 5.39 m, 3 H (=CH2 and CH); 6.30 m, 1 H (=CH); 7.40 m, 7 H and 7.90 m, 2 H
(C6H5 and 2,3-disubstituted benzothiophene); 9.60 s, 1 H (NH).
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Ficeri, Kutschy, Dzurilla, Imrich:
S-(1-Butene-3-methyl-3-yl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (40); yield
50%, m.p. 111 – 113 °C (benzene–acetone). For C15H14ClNO2S2 (339.9) calculated: 53.00% C,
4.15% H, 4.12% N; found: 53.19% C, 4.07% H, 4.19% N. IR spectrum: 1 665 and 1 690 (C=O),
3 375 (N−H). 1H NMR spectrum: 1.68 s, 6 H (2 × CH3); 5.30 m, 2 H (=CH2); 6.30 m, 1 H (=CH);
7.68 m, 2 H and 7.95 m, 2 H (2,3-disubstituted benzothiophene); 9.48 s, 1 H (NH).
S-Cinnamyl N-(4-chlorobenzoyl)monothiocarbamate (41); yield 80%, m.p. 146 – 148 °C
(benzene–hexane). For C17H14ClNO2S (331.8) calculated: 61.54% C, 4.25% H, 4.22% N; found:
61.75% C, 4.12% H, 4.41% N. IR spectrum: 1 645 (C=C), 1 670 and 1 710 (C=O), 3 410 (N−H).
1H NMR spectrum: 4.18 m, 2 H (CH2S); 7.00 m, 2 H (CH=CH); 7.75 m, 5 H (C6H5); 7.85 d, 2 H
and 8.42 m, 2 H, J = 8 (4-ClC6H4); 11.70 s, 1 H (NH).
O-Arylalkyl N-Acylmonothiocarbamates 44, 45, 47, 50
Benzyl alcohol or 3-furylmethanol (6 mmol) was added to a solution of corresponding acyl isothio-
cyanate (5.57 mmol) in anhydrous benzene (10 ml) and the mixture was kept at room temperature for
3 days. Hexane (100 ml) was added and the mixture allowed to stand at 0 °C for 24 h. The precipi-
tate was filtered off and crystallized from a suitable solvent.
O-(3-Furylmethyl) N-(4-chlorobenzoyl)monothiocarbamate (44); yield 86%, m.p. 117 – 119 °C
(benzene–light petroleum). For C13H10ClNO3S (295.7) calculated: 52.80% C, 3.41% H, 4.74% N;
found: 52.58% C, 3.38% H, 4.63% N. IR spectrum: 1 520 (NHCS), 1 680 (C=O), 3 390 (N−H).
1H NMR spectrum: 5.53 s, 2 H (OCH2); 6.53 d, 1 H, J = 2 (furan 4-H); 7.47 m, 4 H and 7.77 d, 2 H,
J = 8 (4-ClC6H4, furan 2-H and 5-H); 9.11 s, 1 H (NH). 13C NMR spectrum: 66.18 t (OCH2), 110.45,
118.92, 142.19 and 143.56 (3-furyl), 129.19, 129.26, 131.32 and 139.68 (4-ClC6H4), 161.93 s (C=O),
188.54 s (C=S).
O-Benzyl N-(3-phenylpropenoyl)monothiocarbamate (45); yield 80%, m.p. 110 – 112 °C
(benzene–hexane). For C17H15NO2S (297.4) calculated: 68.66% C, 5.08% H, 4.71% N; found:
68.51% C, 5.30% H, 4.49% N. IR spectrum: 1 550 (NHCS), 1 635 (C=C), 1 680 (C=O), 3 380 (N−H).
1H NMR spectrum: 5.65 s, 2 H (OCH2); 7.09 d, 2 H and 7.86 d, 2 H, J = 16 (CH=CH); 7.45 m, 10 H
(2 × C6H5); 9.38 s, 1 H (NH).
O-Benzyl N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (47); yield 90%, m.p.
113 – 114 °C (benzene–light petroleum). For C17H12ClNO2S2 (361.9) calculated: 56.42% C, 3.34% H,
3.87% N; found: 56.21% C, 3.29% H, 3.72% N. IR spectrum: 1 515 (NHCS), 1 700 (C=O), 3 395
1
(N−H). H NMR spectrum: 5.75 s, 2 H (OCH2); 7.55 m, 7 H and 7.95 m, 2 H (C6H5 and 2,3-disub-
stituted benzothiophene); 10.24 s, 1 H (NH).
O-(3-Furylmethyl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (50); yield 83%,
m.p. 108 °C (benzene–hexane). For C15H10ClNO3S2 (351.8) calculated: 51.21% C, 2.86% H, 3.98% N;
found: 51.14% C, 2.68% H, 3.75% N. IR spectrum: 1 500 (NHCS), 1 685 (C=O), 3 380 (N−H).
1H NMR spectrum: 5.63 s, 2 H (OCH2); 6.68 d, 1 H, J = 2 (4-H); 7.60 m, 4 H and 7.95 m, 2 H
(furan 2-H and 5-H and 2,3-disubstituted benzothiophene); 10.20 s, 1 H (NH).
S-Arylalkyl N-Acylmonothiocarbamates 51 – 57
A solution of corresponding O-arylalkyl ester (3 mmol) in benzene (10 ml) was refluxed for 3 h
(compounds 53 and 57). In the case of not isolable O-arylalkyl esters, the products were formed al-
ready at room temperature by standing of corresponding acyl isothiocyanate (5.57 mmol) with aryl-
alkyl alcohol (6 mmol) in benzene (10 ml) for 2 days (compound 55), 3 days (compounds 51 and
52), 4 days (compound 56). The solvent was evaporated and the residue crystallized from an appro-
priate solvent.
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S-(2-Furylmethyl) N-(4-chlorobenzoyl)monothiocarbamate (51); yield 40%, m.p. 141 – 144 °C
(dec., benzene–hexane). For C13H10ClNO3S (295.9) calculated: 52.80% C, 3.41% H, 4.71% N;
1
found: 52.61% C, 3.20% H, 4.51% N. IR spectrum: 1 625 and 1 700 (C=O), 3 450 (N−H). H NMR
spectrum: 4.18 s, 2 H (SCH2); 6.35 m, 2 H and 7.55 m, 1 H (2-furyl); 7.65 d, 2 H and 7.95 d, 2 H,
J = 8 (4-ClC6H4). 13C NMR spectrum: 23.30 t (SCH2), 111.10, 120.95, 140.58 and 143.20 (2-furyl),
128.42, 130.10, 130.62 and 137.83 (4-ClC6H4), 165.37 s and 169.48 s (C=O).
S-[1-(2-Furyl)ethyl] N-(4-chlorobenzoyl)monothiocarbamate (52); yield 62%, m.p. 121 – 124 °C
(dec., benzene–light petroleum). For C14H12ClNO3S (309.8) calculated: 54.28% C, 3.90% H, 4.52% N;
1
found: 54.03% C, 3.77% H, 4.63% N. IR spectrum: 1 620 and 1 690 (C=O), 3 430 (N−H). H NMR
spectrum: 1.75 d, 3 H, J = 7 (CH3); 4.93 q, 1 H (CH); 6.30 m, 2 H and 7.35 m, 1 H (2-furyl); 7.39 d,
2 H and 7.93 d, 2 H, J = 8 (4-ClC6H4). 13C NMR spectrum: 19.45 q (CH3), 36.69 d (CH), 106.76,
110.45, 142.07 and 154.31 (2-furyl), 129.19, 129.45, 130.12 and 139.94 (4-ClC6H4), 164.87 s and
171.93 s (C=O).
S-(3-Furylmethyl) N-(4-chlorobenzoyl)monothiocarbamate (53); yield 50%, m.p. 144 – 146 °C
(benzene–hexane). For C13H10ClNO3S (295.7) calculated: 52.80% C, 3.41% H, 4.74% N; found:
1
52.73% C, 3.25% H, 4.85% N. IR spectrum: 1 620 and 1 690 (C=O), 3 450 (N−H). H NMR spec-
trum: 3.98 s, 2 H (SCH2); 6.42 m, 1 H and 7.43 m, 2 H (3-furyl); 7.45 d, 2 H and 7.98 d, 2 H, J = 8
(4-ClC6H4); 11.36 s, 1 H (NH). 13C NMR spectrum: 24.15 t (SCH2), 11.60, 121.05, 142.34 and
142.96 (3-furyl), 129.97, 130.65, 139.08 and 140.57 (4-ClC6H4), 165.70 s and 170.44 s (C=O).
S-(2-Furylmethyl) N-(3-phenylpropenoyl)monothiocarbamate (54); yield 62%, m.p. 144 – 146 °C
(methanol–water). For C15H13NO3S (287.3) calculated: 62.71% C, 4.56% H, 4.87% N; found:
62.43% C, 4.39% H, 4.72% N. IR spectrum: 1 630 (C=C), 1 665 and 1 710 (C=O), 3 400 (N−H).
1H NMR spectrum: 4.22 s, 2 H (SCH2); 6.33 m, 2 H and 7.39 m, 1 H (2-furyl); 6.85 d, 1 H and 7.85 d,
1 H, J = 16 (CH=CH); 7.45 m, 5 H (C6H5); 11.03 s, 1 H (NH).
S-(2-Furylmethyl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (55); yield 53%,
m.p. 151 – 154 °C (dec., benzene–hexane). For C15H10ClNO3S2 (351.8) calculated: 51.21% C, 2.86% H,
3.98% N; found: 50.89% C, 2.67% H, 3.87% N. IR spectrum: 1 670 and 1 690 (C=O), 3 370 (N−H).
1H NMR spectrum: 4.55 s, 2 H (SCH2); 6.68 m, 2 H and 7.78 m, 1 H (2-furyl); 7.90 m, 2 H and
8.27 m, 2 H (2,3-disubstituted benzothiophene); 11.70 s, 1 H (NH).
S-[1-(2-Furyl)ethyl] N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (56); yield 66%,
m.p. 122 – 124 °C (benzene–hexane). For C16H12ClNO3S2 (365.9) calculated: 52.52% C, 3.31% H,
3.83% N; found: 52.38% C, 3.18% H, 3.59% N. IR spectrum: 1 650 and 1 680 (C=O), 3 355 (N−H).
1H NMR spectrum: 1.78 d, 3 H, J = 7 (CH3); 5.10 q, 1 H, J = 7 (CH); 6.15 m, 2 H and 7.48 m, 1 H
(2-furyl); 7.12 m, 2 H and 7.98 m, 2 H (2,3-disubstituted benzothiophene); 9.68 s, 1 H (NH).
S-(3-Furylmethyl) N-(3-chloro-2-benzo[b]thienocarbonyl)monothiocarbamate (57); yield 50%,
m.p. 137 – 139 °C (benzene–hexane). For C15H10ClNO3S2 (351.8) calculated: 51.21% C, 2.86% H,
3.98% N; found: 50.98% C, 2.61% H, 3.74% N. IR spectrum: 1 660 and 1 675 (C=O), 3 370 (N−H).
1H NMR spectrum: 4.13 s, 2 H (SCH2); 6.53 m, 1 H and 7.50 m, 2 H (3-furyl); 7.65 m, 2 H and
7.95 m, 2 H (2,3-disubstituted benzothiophene); 9.70 s, 1 H (NH).
O-[1-(3-Nitrophenyl)ethyl] N-(4-Chlorobenzoyl)monothiocarbamate 58
The product was obtained according to procedure for compounds 44, 45, 47 and 49; the reaction time
was 12 days. Yield 60%, m.p. 130 – 131 °C (chloroform–light petroleum). For C16H13ClN2O4S
(364.8) calculated: 52.68% C, 3.59% H, 3.84% N; found: 52.40% C, 3.43% H, 3.76% N. IR spec-
1
trum: 1 630 (NO2)s, 1 486 (NHCS), 1 540 (NO2)as, 1 725 (C=O), 3 410 (N−H). H NMR spectrum:
1.75 d, 3 H, J = 7 (CH3); 6.60 q, 1 H, J = 7 (CH); 7.53 m, 2 H, 7.82 m, 3 H and 7.53 m, 3 H
(4-ClC6H4 and 3-NO2C6H4); 9.18 s, 1 H (NH).
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