Amine-carbon disulfide promoted synthesis of novel benzo[e][1,3]thiazepin-5(1H)-one derivatives

Article abstract of DOI:10.1002/jhet.3794

In this paper, a simple method is introduced for the synthesis of novel 4-substituted-3-thioxo-3,4-dihydrobenzo[e][1,3]thiazepin-5(1H)-one derivatives. The synthesis is based on a two-step reaction of 2-methylbenzoic acid, an amine, and carbon disulfide. In the first step, 2-methylbenzoic acid reacts with sulfuric acid in ethanol, followed by the reaction with N-bromosuccinimide to produce ethyl 2-(bromomethyl)benzoate. Amine and carbon disulfide react in a separate flask in basic medium to give carbamodithioate salt. Carbamodithioate and ethyl 2-(bromomethyl)benzoate react together in dimethylformamide to produce the desired 4-substituted-3-thioxo-3,4-dihydrobenzo[e][1,3]thiazepin-5(1H)-one derivatives. The method is simple and fast and is applicable to a wide variety of substrates and gives the desired products in high isolated yields.

Full text of DOI:10.1002/jhet.3794

Received: 15 July 2019
DOI: 10.1002/jhet.3794
Revised: 27 September 2019
Accepted: 1 October 2019
A R T I C L E
Amine-carbon disulfide promoted synthesis of novel benzo
[e][1,3]thiazepin-5(1H)-one derivatives
Mohammad Sadegh Asgari1 | Saeed Bahadorikhalili1 | Mehdi Asadi2
Parviz Rashidi Ranjbar1 | Bagher Larijani3 | Rahmatollah Rahimi4
Mohammad Mahdavi3
|
|
1School of Chemistry, College of Science,
Abstract
University of Tehran, Tehran, Iran
2Department of Medicinal Chemistry,
Faculty of Pharmacy, Tehran University
of Medical Sciences, Tehran, Iran
3Department of Medicinal chemistry,
Faculty of Pharmacy and Pharmaceutical
Sciences Research Center, Tehran
University of Medicinal Sciences,
Tehran, Iran
In this paper, a simple method is introduced for the synthesis of novel
4-substituted-3-thioxo-3,4-dihydrobenzo[e][1,3]thiazepin-5(1H)-one derivatives.
The synthesis is based on a two-step reaction of 2-methylbenzoic acid, an amine,
and carbon disulfide. In the first step, 2-methylbenzoic acid reacts with sulfuric
acid in ethanol, followed by the reaction with N-bromosuccinimide to produce
ethyl 2-(bromomethyl)benzoate. Amine and carbon disulfide react in a separate
flask in basic medium to give carbamodithioate salt. Carbamodithioate and ethyl
2-(bromomethyl)benzoate react together in dimethylformamide to produce the
desired 4-substituted-3-thioxo-3,4-dihydrobenzo[e][1,3]thiazepin-5(1H)-one deriv-
atives. The method is simple and fast and is applicable to a wide variety of sub-
strates and gives the desired products in high isolated yields.
4Department of Chemistry, Iran
University of Science and Technology,
Tehran, Iran
Correspondence
Dr Mohammad Mahdavi, Department of
Medicinal Chemistry, Faculty of
Pharmacy and Pharmaceutical Sciences
Research Center, Tehran University of
Medicinal Sciences, Tehran, Iran.
Email: mahdavi_chem@yahoo.com
1 | INTRODUCTION
class of compounds. In spite of the reports on the synthesis
of benzothiazepinone derivatives, there is a hot challenge
Benzothiazepinone and its derivatives are of high interests
due to the biological activities. Derivatives of benzothia-
zepinone show antimicrobial agent,[1] calcium channel
blockers,[2] antifungal,[3] tumor inhibitor,[4] kinase-3β in-
hibitor,[5] and antipsychotic and anticonvulsant.[6] Regard-
ing the significance of benzothiazepinone derivatives,
several efforts have been focused on the synthesis of this
class of organic compounds. The reaction of 2-amino-
thiophenol with α,β-unsaturated carboxylic acid derivatives
using tetrabutylammonium fluoride,[7] the reaction of alde-
hydes and 2-mercapto-N-phenylacetamide[8] and the reac-
tion of thiosalicylic acid with epoxides[9] are a number of
reported methods for the synthesis of benzothiazepinone
derivatives. In addition, the multicomponent[10] and solid
phase syntheses[11] are widely used for the synthesis of this
among several organic chemists to design efficient methods
for the synthesis of these compounds.
The use of amine-CS2 is an interesting approach for
the synthesis of heteroatom-containing organic com-
pounds. The reaction of amine and carbon disulfide
is an appropriate and atom efficient method for the
synthesis of several heterocycles with complex struc-
tures. This method is well reviewed and showed an
appropriate method for the synthesis of a wide variety
of organic compounds.[12] The reactions with car-
badiimides[13]
,
quinones,[14] fluoronitrobenzene,[15]
and ethyl bromopyruvate[16] are only a number of the
reported reactions, showing the significance of amine-
CS2 approach in the synthesis of complex organic
compounds.
J Heterocyclic Chem. 2019;1–6.
wileyonlinelibrary.com/journal/jhet
© 2019 Wiley Periodicals, Inc.
1

2
ASGARI ET AL.
Regarding the significant role of benzo[e][1,3]
results are observed when DMF is used as solvent for the
reaction. In addition, the reaction was performed in DMF
in various temperatures. The results showed that raising
the temperature has negative affect on the product forma-
tion. Based on the optimization results, performing the
reaction in DMF solvent in room temperature was selected
as optimal reaction conditions.
thiazepin-5(1H)-one in several biological applications and
the versatility of amine-CS2 approach in organic synthesis,
we hereby report the amine-CS2 reaction with ethyl
2-(bromomethyl)benzoate for the synthesis of 4-alkyl-
3-thioxo-3,4-dihydrobenzo[e][1,3]thiazepin-5(1H)-one
derivatives. The reaction scheme is presented in Scheme 1.
Based on the reaction performance in the optimized
conditions, several amines were used as starting mate-
rials for the synthesis of benzo[e][1,3]thiazepin-5(1H)-
one derivatives. The synthesized products are presented
in Scheme 1. It can be observed that various aromatic
and aliphatic amines have been used and successfully
gave the desired products in good isolated yields. Aro-
matic substrates bearing electron donating or electron
withdrawing functionalities have successfully partici-
pated in the reaction and gave the desired benzo[e][1,3]
thiazepin-5(1H)-one in high isolated yields. Aliphatic
amines have also participated successfully in the reaction
to give the product.
Based on the reaction performance, a possible mecha-
nism is proposed, which is suggested in Scheme 2. Reac-
tion of amine (3) with carbon disulfide takes place by a
nucleuphilic attack and resulted in the formation of the
carbamodithioate salt (5). In addition, 2-methylbenzoic
acid undergoes an esterification reaction in the presence
of sulfuric acid and gives ethyl 2-methylbenzoate (8).
Ethyl 2-methylbenzoate reacts with N-bromosuccinimide
2 | RESULTS AND DISCUSSION
The desired 4-substituted-3-thioxo-3,4-dihydrobenzo[e]
[1,3]thiazepin-5(1H)-one derivatives are synthesized in
two steps from 2-methylbenzoic acid, amine derivatives,
and carbon disulfide. In the first step, 2-methylbenzoic
acid reacts with ethanol in acidic conditions, followed by
the reaction with N-bromosuccinimide (NBS) and forms
ethyl 2-(bromomethyl)benzoate. The product of the reac-
tion of amine derivatives with carbon disulfide in basic
media reacts to ethyl 2-(bromomethyl)benzoate and gives
the corresponding 4-alkyl-3-thioxo-3,4-dihydrobenzo[e]
[1,3]thiazepin-5(1H)-one. For finding the optimal reaction
conditions, the reaction of aniline with the other compo-
nents was selected as a model reaction. At first, the effect
of different variables on the reaction performance was
studied. The optimization results are presented in Table 1.
Performing the reaction in several solvents with various
properties were studied. Various protic and aprotic sol-
vents with different polarities were used as the reaction
media and the effect of the solvent was studied on the
reaction performance. It can be observed that the best
TABLE 1 Optimal conditions for the synthesis of benzo[e][1,3]
thiazepin-5(1H)-ones
Entry
Solvent
H2O
Temp., ꢀC
r.t.
Time, h
12
Yield, %a
1
10
27
39
21
14
0
2
EtOH
MeOH
CH2Cl2
CHCl3
Toluene
DMSO
DMF
r.t.
12
3
r.t.
12
4
r.t.
12
5
r.t.
12
6
r.t.
12
7
r.t.
12
65
11
42
64
81
81
78
79
68
8
0
12
9
DMF
r.t.
4
10
11
12
13
14
15
DMF
r.t.
8
DMF
r.t.
12
DMF
r.t.
24
DMF
50
12
DMF
75
12
DMF
100
12
SCHEME 1 Synthesis of benzo[e][1,3]thiazepin-5(1H)-ones
by the reaction of amine, carbon disulfide and ethyl
2-(bromomethyl)benzoate
Note. Reaction conditions: ethyl 2-(bromomethyl)benzoate (1 mmol),
carbamodithioate (1 mmol), and solvent (3 mL).
aIsolated yield.

ASGARI ET AL.
3
SCHEME 2 Suggested mechanism for the
reaction
in a free radical mechanism and undergoes a radical bro-
mination reaction and gives ethyl 2-(bromomethyl)benzo-
ate (2). Cyclization reaction of ethyl 2-(bromomethyl)
benzoate and carbamodithioate leads to the 4-substituted-
3-thioxo-3,4-dihydrobenzo[e][1,3]thiazepin-5(1H)-ones.
spectra were obtained on a Nicolet Magna FT-IR
550 spectrophotometer (potassium bromide disks).
Nuclear magnetic resonance spectra were recorded on a
Brucker Bruker FT-500spectrometers using tetramethyl
silane (TMS) as internal standard in pure deuterated sol-
vents. Chemical shifts are given in the δ scale in parts
per million (ppm) and singlet (s), doublet (d), triplet (t),
multiplet (m), and doublets of doublet (dd) are recorded.
3 | CONCLUSIONS
1
The copies of H NMR and 13C NMR spectra are pro-
In this paper, a simple and efficient method is introduced for
the synthesis of 4-substituted-3-thioxo-3,4-dihydrobenzo[e]
[1,3]thiazepin-5(1H)-one derivatives from amines, carbon
disulfide and 2-methylbenzoic acid. The method showed to
be efficient in the synthesis of the products by using various
aliphatic or aromatic amines. By this method, the products
are obtained in good isolated yields.
vided in the Supporting information. Mass spectra were
recorded on an Agilent Technology (HP) mass spec-
trometer operating at an ionization potential of 70 eV.
The elemental analysis was performed with an Elemetar
Analysen system GmbH VarioEL CHNS mode. Purifica-
tion of all products was conducted by column chroma-
tography on silica gel using petroleum ether and ethyl
acetate as eluent.
4 | EXPERIMENTAL SECTION
4.1 | General remarks
4.2 | General procedure for the synthesis
of ethyl 2-(bromomethyl)benzoate
All the solvents, reagents, and chemicals were pur-
chased from Merck, Acros and Sigma-Aldrich Chemical
Companies. The chemicals and solvents were used in
the reactions as received without and purifications. Thin
layer chromatography was carried out on silica gel
254 analytical sheets obtained from Fluka. Column
chromatography was carried out on the column of silica
gel 60 Merck (230-240 mesh) in glass columns (2 or
3 cm diameter) using 15 to 30 grams of silica gel per 1 g
of the crude mixture. Melting points were taken on a
Kofler hot stage apparatus and are uncorrected. The IR
2-Methylbenzoic acid (18.36 mmol) was dissolved in eth-
anol (12.5 mL), and then sulfuric acid (98%, 0.6 mL) was
added. The mixture was refluxed for 24 hours and then
cooled to room temperature. The produced ethyl
2-methylbenzoate was extracted by ethyl acetate and
water and purified using a shot column chromatography
by using silica gel as stationary phase and hexane as
eluent.
The purified ethyl 2-methylbenzoate (48.72 mmol)
was dissolved in carbon tetrachloride (38 mL) and added
drop wise to a stirring mixture of benzoyl proxide and N-

4
ASGARI ET AL.
bromosuccinimide (57 mmol) at 0ꢀC. After the addition
was completed, the reaction mixture was heated and
stirred under reflux conditions for 3.5 hours. Then, the
reaction mixture was stirred overnight at room tempera-
ture. The precipitate was filtered was washed with 1M
NaOH and was dried over sodium sulfate. The solvent
was evaporated to get the product.
199.18, 166.67, 139.27, 133.33, 132.74, 132.02, 131.36,
131.21, 130.51, 129.60, 128.86, 128.21, 127.33, 122.65,
43.51; Anal Calcd for: C15H10ClNOS2, C, 56.33, H,
3.15, N, 4.38 found: C, 56.37, H, 3.21, N, 4.35; MS (70 eV):
m/z = 318 (M+).
4.4.3 | 8-(2-Methoxy-phenyl)-7-thioxo-7,8-
dihydro-5H-6-thia-8-aza-benzocyclohepten-
9-one (6c)
4.3 | General procedure for the synthesis
of 4-alkyl-3-thioxo-3,4-dihydrobenzo[e][1,3]
thiazepin-5(1H)-one
Yellowish oil; isolated yield: 89%; 0.280 g; IR (KBr):
υ = 3029 (C H aromatic), 1679 (C O), 1109 (C S),
Amine derivative (2 mmol) and NaOH (2.2 mmol) were
dissolved ethanol (5 mL) and stirred at 0ꢀC. Carbon disul-
fide (3 mmol) was added, and the mixture was stirred for
2 hours. The precipitate was filtered and washed with
cold ethanol and dried in reduced pressure. The product
(1 mmol) and ethyl 2-(bromomethyl)benzoate (1 mmol)
were added to a flask containing DMF (5 mL) and stirred
for 12 hours. After the reaction completion, monitored by
TLC, the reaction mixture was poured onto cold water
and extracted by ethyl acetate and purified by short col-
umn chromatography.
722 (C S) cm−1 1H NMR (500 MHz, DMSO-d6) δ
;
7.84 (d, J = 7.7 Hz, 1H), 7.53 (t, J = 7.7 Hz, 1H), 7.40
(t, J = 7.9 Hz, 1H), 7.31 (d, J = 8.7 Hz, 1H), 7.22 (d,
J = 8.6 Hz, 1H), 6.97 (t, J = 9.2 Hz, 1H), 6.88 (d,
J = 8.7 Hz, 2H), 4.61-4.17 (m, 2H), 3.76 (s, 3H); 13C
NMR (126 MHz, DMSO-d6) δ 196.66, 167.03, 158.97,
139.23, 133.07, 132.73, 131.74, 130.85, 129.94, 129.65,
129.29, 128.07, 127.13, 114.16, 55.49, 44.45; Anal
Calcd for: C16H13NO2S2, C, 60.93, H, 4.15, N, 4.44
found: C, 60.98, H, 4.19, N, 4.49; MS (70 eV): m/
z = 315 (M+).
4.4 | Characterization of the products
4.4.4 | 7-Thioxo-8-o-tolyl-7,8-dihydro-5H-
6-thia-8-aza-benzocyclohepten-9-one (6d)
4.4.1 | 8-Phenyl-7-thioxo-7,8-dihydro-5H-
6-thia-8-aza-benzocyclohepten-9-one (6a)
Yellowish oil; isolated yield: 92%; 0.275 g; IR (KBr):
υ = 3027 (C H aromatic), 1680 (C O), 1110 (C S),
1
Yellowish oil; isolated yield: 81%; 0.230 g; IR (KBr):
723 (C S) cm−1; H NMR (500 MHz, DMSO-d6) δ 7.83
υ = 3026 (C H aromatic), 1679 (C O), 1109 (C S),
(d, J = 7.6 Hz, 1H), 7.59-7.52 (m, 2H), 7.39 (t,
J = 7.2 Hz, 1H), 7.18-7.04 (m, 4H), 4.66-4.07 (m, 2H),
2.29 (s, 3H); 13C NMR (126 MHz, DMSO-d6) δ 196.05,
167.02, 135.01, 132.48, 131.66, 130.78, 130.52, 130.15,
129.28, 127.93, 126.51, 125.14, 123.09, 121.95, 45.87,
18.27; Anal Calcd for: C16H13NOS2, C, 64.18, H, 4.38, N,
4.68 found: C, 64.21, H, 4.45, N, 4.66; MS (70 eV): m/
z = 299 (M+).
1
723 (C S) cm−1; H NMR (500 MHz, DMSO-d6) δ 7.86
(d, J = 7.5 Hz, 1H), 7.49-7.45 (m, 1H), 7.41-7.33 (m, 2H),
7.27-7.15 (m, 3H), 6.97 (d, J = 6.8 Hz, 2H), 4.70-4.00 (m,
2H); 13C NMR (126 MHz, DMSO-d6) δ 195.19, 166.82,
139.33, 134.54, 132.66, 131.41, 131.07, 129.80, 129.21,
128.94, 128.09, 126.36, 122.80, 118.64, 45.29; Anal Calcd
for: C15H11NOS2, C, 63.13, H, 3.89, N, 4.91 found: C,
63.16, H, 3.95, N, 4.85; MS (70 eV): m/z = 285 (M+).
4.4.5 | 7-Thioxo-8-m-tolyl-7,8-dihydro-5H-
6-thia-8-aza-benzocyclohepten-9-one (6e)
4.4.2 | 8-(3-Chloro-phenyl)-7-thioxo-7,8-
dihydro-5H-6-thia-8-aza-benzocyclohepten-
9-one (6b)
Yellowish oil; isolated yield: 89%; 0.266 g; IR (KBr):
υ = 3026 (C H aromatic), 1681 (C O), 1110 (C S),
Yellowish oil; isolated yield: 76%; 0.243 g; IR (KBr):
725 (C S) cm−1 1H NMR (500 MHz, DMSO-d6) δ
;
υ = 3023 (C H aromatic), 1681 (C O), 1112 (C S),
7.88-7.82 (m, 1H), 7.49 (t, J = 7.4 Hz, 1H), 7.40 (t,
J = 7.5 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.17-7.01 (m,
2H), 6.85-6.68 (m, 2H), 4.60-4.13 (m, 2H), 2.33 (s, 3H);
13C NMR (126 MHz, DMSO-d6) δ 196.44, 165.91, 137.61,
135.49, 133.62, 130.99, 128.33, 127.93, 127.85, 126.76,
1
725 (C S) cm−1; H NMR (500 MHz, DMSO-d6) δ 7.86
(d, J = 7.6 Hz, 1H), 7.50-7.46 (m, 1H), 7.40 (t, J = 7.3 Hz,
1H), 7.31 (d, J = 7.3 Hz, 1H), 7.27-7.13 (m, 2H), 7.01 (s,
2H), 4.62-4.09 (m, 2H); 13C NMR (126 MHz, DMSO-d6) δ

ASGARI ET AL.
5
125.70, 124.50, 122.49, 120.84, 45.80, 21.10; Anal Calcd
for: C16H13NOS2, C, 64.18, H, 4.38, N, 4.68 found: C,
64.22, H, 4.45, N, 4.71; MS (70 eV): m/z = 299 (M+).
4.4.9 | 8-(2-Diethylamino-ethyl)-7-thioxo-
7,8-dihydro-5H-6-thia-8-aza-
benzocyclohepten-9-one (6i)
Yellowish oil; isolated yield: 92%; 0.283 g; IR (KBr):
4.4.6 | 7-Thioxo-8-p-tolyl-7,8-dihydro-5H-
6-thia-8-aza-benzocyclohepten-9-one (6f)
υ = 3026 (C H aromatic), 1679 (C O), 1114 (C S),
1
726 (C S) cm−1; H NMR (500 MHz, DMSO-d6) δ 7.87
(d, J = 7.6 Hz, 1H), 7.54 (t, J = 7.6 Hz, 1H), 7.42 (t,
J = 6.9 Hz, 1H), 7.27 (d, J = 7.4 Hz, 1H), 4.49 (t,
J = 6.5 Hz, 2H), 4.35-4.02 (m, 2H), 2.94 (t, J = 6.0 Hz,
2H), 2.72 (q, J = 5.0 Hz, 4H), 0.99 (t, J = 5.5 Hz, 6H); 13C
NMR (126 MHz, DMSO-d6) δ 198.06, 166.94, 139.15,
132.48, 132.21, 131.15, 129.56, 128.20, 61.30, 51.89, 45.47,
37.19, 14.49; Anal Calcd for: C15H20N2OS2, C, 58.41, H,
6.54, N, 9.08 found: C, 58.36, H, 6.52, N, 9.01; MS (70 eV):
m/z = 308 (M+).
Yellowish oil; isolated yield: 85%; 0.254 g; IR (KBr):
υ = 3024 (C H aromatic), 1677 (C O), 1112 (C S),
722 (C S) cm−1; 1H NMR (500 MHz, DMSO-d6) δ 7.84 (d,
J = 7.6 Hz, 1H), 7.47 (t, J = 7.2 Hz, 1H), 7.38 (t, J = 7.4 Hz,
1H), 7.33 (d, J = 7.6 Hz, 1H), 7.08-6.99 (m, 4H), 4.51-4.21
(m, 2H), 2.30 (s, 3H); 13C NMR (126 MHz, DMSO-d6) δ
196.86, 166.40, 136.36, 136.08, 133.71, 133.00, 132.71,
132.14, 129.32, 127.00, 122.63, 121.97, 46.26, 21.21; Anal
Calcd for: C16H13NOS2, C, 64.18, H, 4.38, N, 4.68 found: C,
64.13, H, 4.40, N, 4.62; MS (70 eV): m/z = 299 (M+).
ORCID
Mohammad Mahdavi https://orcid.org/0000-0002-
4171-7310
4.4.7 | 8-(3-Bromo-phenyl)-7-thioxo-7,8-
dihydro-5H-6-thia-8-aza-benzocyclohepten-
9-one (6g)
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Yellowish oil; isolated yield: 80%; 0.290 g; IR (KBr): υ = 3025
(C H aromatic), 1678 (C O), 1109 (C S), 724 (C S) cm−1; 1H
NMR (500 MHz, DMSO-d6) δ 7.84 (d, J = 7.3 Hz, 1H), 7.46
(t, J = 7.4 Hz, 1H), 7.38 (t, J = 7.3 Hz, 1H), 7.30 (d, J = 7.6 Hz,
1H), 7.13-7.00 (m, 2H), 6.80-6.68 (m, 2H), 4.64-4.32 (m, 2H);
13C NMR (126 MHz, DMSO-d6) δ 196.13, 166.80, 139.49,
137.97, 132.63, 132.29, 131.35, 131.04, 130.36, 129.76,
128.68, 128.01, 127.16, 123.39, 45.05; Anal Calcd for:
C15H10BrNOS2, C, 49.46, H, 2.77, N, 3.85 found: C, 49.43, H,
2.80, N, 3.79; MS (70 eV): m/z = 362 (M+).
4.4.8 | 8-Cyclohexyl-7-thioxo-7,8-dihydro-
5H-6-thia-8-aza-benzocyclohepten-
9-one (6h)
Yellowish oil; isolated yield: 76%; 0.221 g; IR (KBr):
υ = 3027 (C H aromatic), 1680 (C O), 1110 (C S),
1
725 (C S) cm−1; H NMR (500 MHz, DMSO-d6) δ 7.84
(d, J = 7.8 Hz, 1H), 7.61 (d, J = 7.6 Hz, 1H), 7.52 (t,
J = 7.4 Hz, 1H), 7.38 (t, J = 7.5 Hz, 1H), 4.57-4.25 (m,
2H), 1.91-1.84 (m, 2H), 1.72-1.66 (m, 2H), 1.56 (d,
J = 12.7 Hz, 1H), 1.36-1.00 (m, 5H); 13C NMR (126 MHz,
DMSO-d6) δ 194.72, 167.04, 139.55, 133.83, 132.68,
131.97, 131.73, 130.83, 129.91, 128.97, 128.16, 127.98,
127.69, 126.65, 61.38, 56.40, 44.81, 31.42, 25.51, 25.10,
14.47; Anal Calcd for: C15H17NOS2, C, 61.82, H, 5.88, N,
4.81 found: C, 61.87, H, 5.91, N, 4.85; MS (70 eV): m/
z = 291 (M+).
[10] a) S.-J. Tu, X.-D. Cao, W.-J. Hao, X.-H. Zhang, S. Yan, S.-
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SUPPORTING INFORMATION
Additional supporting information may be found online
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How to cite this article: Asgari MS,
Bahadorikhalili S, Asadi M, et al. Amine-carbon
disulfide promoted synthesis of novel benzo[e][1,3]
thiazepin-5(1H)-one derivatives. J Heterocyclic
Chem. 2019;1–6. https://doi.org/10.1002/jhet.3794