Facile selective synthesis of new furo[3,4-d[-1,3-thiazoles

Article abstract of DOI:10.1080/17415993.2012.700458

In presence of triethylamine, the reaction of substituted 2-aroyl-hydrazinecarbothioamides with 1,4-Diphenyl-but-2-yne-1,4-dione afforded novel furo[3,4-d]-1,3-thiazoles in good yield. The reaction mechanism suggests that the second molecule of 1,4-Diphen

Full text of DOI:10.1080/17415993.2012.700458

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Facile selective synthesis of new
furo[3,4-d]-1,3-thiazoles
Ashraf A. Aly a b , Alaa A. Hassan a , Husam R.M. Al-Qalawi b &
Esam A. Ishak b c
a Department of Chemistry, Faculty of Science , El-Minia
University , 61519-El-Minia, Egypt
b Department of Chemistry, College of Science , Al-Jouf
University , Sakaka , Saudi Arabia
c Department of Chemistry, Faculty of Science , Al-Azhar
University , Cairo , Egypt
Published online: 10 Aug 2012.
To cite this article: Ashraf A. Aly , Alaa A. Hassan , Husam R.M. Al-Qalawi & Esam A. Ishak (2012)
Facile selective synthesis of new furo[3,4-d]-1,3-thiazoles, Journal of Sulfur Chemistry, 33:4,
419-426, DOI: 10.1080/17415993.2012.700458
To link to this article: http://dx.doi.org/10.1080/17415993.2012.700458
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Journal of Sulfur Chemistry
Vol. 33, No. 4, August 2012, 419–426
Facile selective synthesis of new furo[3,4-d]-1,3-thiazoles
Ashraf A. Alya,b*, Alaa A. Hassan,a Husam R.M. Al-Qalawib and Esam A. Ishakbc
aDepartment of Chemistry, Faculty of Science, El-Minia University, 61519-El-Minia, Egypt;
bDepartment of Chemistry, College of Science, Al-Jouf University, Sakaka, Saudi Arabia;
cDepartment of Chemistry, Faculty of Science, Al-Azhar University, Cairo, Egypt
In presence of triethylamine, the reaction of substituted 2-aroyl-hydrazinecarbothioamides with
1,4-Diphenyl-but-2-yne-1,4-dione afforded novel furo[3,4-d]-1,3-thiazoles in good yield. The reaction
mechanismsuggeststhatthesecondmoleculeof1,4-Diphenyl-but-2-yne-1,4-dionebehavedasanoxidizing
agent.
Ph
4
O
2
3
5
ArCO
HN
PhOC
+
Ph
S
CH3CN
1
COPh
+ Et3N
+
2 PhOC
NH
N
reflux1-3 d
COPh
5(10-15%)
2
N
N
S
H2N
1a-d
Ar
4a-d
O
Ph
4
5
O
2
3
Ph
S
CH3CN
1
+
+
Et3N
1a-d
2
N
reflux 8-14 h
HN
Ar
NH
6a-d
O
Keywords: N-aryl-hydrazinecarbothioamides;1,4-Diphenyl-but-2-yne-1,4-dione;triethylamine;bi-nucleophilic
attack; furo[3,4-d]-1,3-thiazoles
1. Introduction
The chemistry of 1,4-diphenylbut-2-yne-1,4-dione (DBD) has been extensively investi-
gated. For example, DBD reacts with benzimidazole-2-thione to produce 2-(acylvinylthio)-
benzimidazoles (1), while diarylazines react with DBD to produce pyridazines via Diels–Alder
reactions (2). Thioamides and their derivatives occupy a distinctive place among the other
N,S-containing compounds used in the synthesis of heterocyclic systems due to their accessibility
*Corresponding author. Email: ashrafaly63@yahoo.com
ISSN 1741-5993 print/ISSN 1741-6000 online
© 2012 Taylor & Francis
http://dx.doi.org/10.1080/17415993.2012.700458
http://www.tandfonline.com

420 A.A. Aly et al.
Ph
COR
O
O
HN
NH
N
CH3CN, reflux
24-48 h
Ar
+
O
2
Ph
Ph
ROCHNN
S
HN
1a-d
SH
3a-e
Ph
1and 3
a
b
c
C6H5-
4-HO-C6H4-
4-CH3O-C6H4-
4-Cl-C6H4-
d
Scheme 1. 1,3-Thiazine formation from the reaction of 2-aroyl-hydrazinecarbothioamides
1a–1d with DBD (2).
and their ability to act as difunctional nucleophiles. The heterocyclizations of 1,4-disubstituted
thiosemicarbazides – in basic or acidic media and under various reaction conditions – have been
investigated (3, 4). In addition, four-, five-, six- and seven-membered heterocyclic compounds
were prepared by the reaction of thiosemicarbazide derivatives with α- and β-haloketones (5, 6).
The N2 of the thiosemicarbazide group is a softer nucleophilic center than the harder and more
powerful terminal nitrogen N1. Some time ago, we synthesized a large number of heterocyclic ring
systems such as thiazoles, imidazoles, thiazines, thiadiazoles, thiadiazines, pyrazines and inda-
zoles from the reactions of thiosemicarbazides with π-deficient compounds (7–10).Aly et al. (11)
reported that thiosemicarbazides show unusual reactivity toward 2,3-diphenylcyclopropenone,
giving a variety of pyridazinethiones and 1,2,4-triazolo[4,3-b]-pyridazinethiones. The synthesis
of furothiazoles is still of considerable interest in organic chemistry (for a recent review on thiazole
synthesis, see (12)). Moreover, thiazoles are ubiquitous building blocks in medicinal chemistry
and can be found in numerous natural products (e.g. epothilone) (13, 14) and biologically impor-
tant compounds including the anticancer drug dasatinib, antiviral clinical candidate TMC435350
and antidiabetic drug candidate MB06322 (15).
Interestingly, numerous manuscripts reporting the selective addition of the nucleophilic-amino
group to π-deficient acetylenic bonds suggest that it predominantly occurs in the presence of Lewis
acids and/or under weakly basic conditions (16–18). We have recently reported that DBD (2)
under neutral conditions reacts with N-substituted-hydrazino-carbothioamides 1a–1d to form the
corresponding Nꢀ-[6-benzoyl-4-phenyl-2H-1, 3-thiazin-2-ylidene]-substituted-hydrazides 3a–3d
(Scheme 1) (19). In this paper, we repeated the cycloaddition between compounds 1 and 2 in the
presence of triethyl amine, with the goal to investigate the selective cyclization process of the
adducts.
2. Results and discussion
Thus, upon adding a solution of 2 in acetonitrile to an acetonitrile solution of 1a–1d and tri-
ethylamine, the reaction proceeds to give furo[3,4-d]-1,3-thiazoles 4a–4d in 70–82% yield in
addition to dibenzoylethylene (5) in 10–15% yield (Scheme 2). We chose compounds 1a–1d hav-
ing aryl groups with electron donating and withdrawing substituents on the benzene ring in order
1
to examine their effect on reactivity. The structural proof for 4a–4d was based upon mass, H
NMR, 13C NMR and IR spectral as well as elemental analyses. For example, mass spectrometry
and elemental analysis provided the molecular formula of 4a as C24H15N3O2S. The IR spectrum
=
did not reveal any absorptions due to C S, NH or OH groups. However, a sharp band appeared

Journal of Sulfur Chemistry 421
Ph
4
5
O
3
ArCO
HN
PhOC
+
Ph
S
CH3CN
2
1
COPh
+ Et3N
+
NH
2PhOC
N
reflux1-3 d
2
COPh
5(10-15%)
N
N
S
H2N
Ar
N
4a-d
1a-d
O
Ph
4
O
2
3
5
Ph
S
CH3CN
1
+
2
+
Et3N
1a-d
reflux 8-14 h
HN
Ar
NH
6a-d
O
Ar
Yield of 6 (%)
Yield of 4 (%)
1, 4 and 6
a
b
c
C6H5-
75
77
82
70
76
78
83
72
4-HO-C6H4-
4-CH3O-C6H4-
4-Cl-C6H4-
d
Scheme 2. Synthesis of various furo[3,4-d]-1,3-thiazoles 4a–4d and 6a–6d.
at νmax = 1080 cm−1 which was assigned to C O stretching. The 13C NMR spectrum revealed
−
=
carbon signals at δC = 190.0, 158.8, 153.2, 153.0, 143.0 and 119.0 corresponding to the C O,
C-1, C-3, C-4, C-2 and C-5 carbons in 4a, respectively (see Section 4).
The second derivative 4b was identified as (E)-(4,6-Diphenylfuro[3,4-d]thiazol-2-yl)diazenyl)
(4-hydroxyphenyl)methanone. The IR spectrum of 4b revealed a broad absorption band at νmax
=
3450–370 cm−1 corresponding to the hydroxyl group and another at νmax = 1060 cm−1 that we
−
assign to a C O stretch. The carbonyl groups of the dibenzoyl acetylene derivatives disappeared
in the 13C NMR spectra of the products. The phenolic OH resonated as a broad singlet in the 1H
NMR at δH = 8.80. Five distinctive carbon signals for the azomethine and furan carbons appeared
at δC = 154.0 (C-1), 153.4 (C-3), 153.0 (C-4), 143.2 (C-2) and 119.0 (C-5).
One pot reaction of 1 and 2 in the presence of triethylamine is initiated by the nucleophilic
attack of the nitrogen lone pair in triethylamine on the acetylenic bond leading to salt 7 as
suggested by the mechanism shown in Scheme 3. The addition of few drops of triethylamine to
the reaction mixtures produced very low percentage yields of the products 4a–4d. Whereas the
addition of triethylamine in equimolar quantity together with the starting materials produced the
reaction products 4a–4d by the percentage yields shown in Scheme 3. Consequently, this result
supports the involvement of triethylamine in the reaction pathway as a catalyst. It is reasonable
that the sulfur atom of amido group is the most nucleophilic center in the starting substrates (11).
However, under basic conditions, the negatively charged imino group rather than the sulfur-
thione is more nucleophilic in acylthiocarbohydrazides (3, 4). Consequently, under our weakly
basic reaction conditions, the nucleophilic-diethylamino group will predominantly occur at the
π-deficient acetylenic bond in the presence of Lewis acids (3, 4). This would then be followed
by a proton transfer to the vinylic carbon followed by the nucleophilic attack of the negatively
charged imino at the ethylenic bond that ultimately results in the elimination of the triethylamine
molecule to give 8 (Scheme 3). The sulfur lone pair would then complete the cyclization process
to form salt 9, which accompanied by proton transfer from NH-3 to produce intermediate 10.
The tautomerism of 10 to form 11 followed by the elimination of water would ultimately form

422 A.A. Aly et al.
Ph
O
H
Ph
ArCO
HN
..
:S
1
+
2
+ :
Et3N
NH
O
-Et3N
Et3N+
COPh
H
N
-
HN
O
N
NH
S
Ar
8
PhOC
7
Ph
O
-
OH
O
Ph
OH
Ph
O
O
Ph
+
S
~H-transfer
-H2O
Ph
S
Ph
S
N
N
HN
N
NH
H
HN
O
NH
Ar
HN
9
NH
Ar
10
Ar
Ph
O
11
Ph
O
O
1)
2
S
4a-d
5
+
2) -H2
N
HN
O
NH
Ar
6a-d
Scheme 3. Plausible mechanism of formation of 4a–4d and 6a–6d.
compounds 6 (Scheme 3). The oxidation of compounds 6 by the action of a second molecule of
2 would finally afford compounds 4 and 5 (Scheme 3).
The oxidation of 6 by 2 is supported by the observation that upon reacting equal equiv-
alents of 1a–1d, 2 and triethylamine, the corresponding 4,6-Diphenylfuro[3,4-d]thiazol-2-yl)
arylhydrazides 6a–6d were obtained (Scheme 2). The elemental analyses and the spectral data of
compounds 6a–6d proved that they are the reduced form of compounds 6a–6d (see Section 4).
For example, the mass spectra and elemental analysis of 6a provide its molecular formula as
C24H17N3O2S, whereas the molecular formula for 4a is C24H15N3O2S. The IR spectrum of
6a revealed a broad absorption band at νmax = 3350–3260 cm−1 for the NH NH stretch (see
−
1
−
Section 4). The NH NH protons of 6a were observed as two broad singlets in the H NMR spec-
=
trum at δH = 10.50 and 6.00. The carbon signals of C O, C-1, C-3, C-4, C-2 and C-5 appeared
at δC = 171.7, 160.2, 152.8, 152.0, 138.7 and 108.0, respectively.
3. Conclusions
Substituted 2-aroyl-hydrazinecarbothioamides can change and can react with acetylenic
π-deficient compounds under slightly basic condition. Moreover and owing to the presence of
more than two nucleophilic sites in the starting material, various heterocycles can be obtained.
4. Experimental section
4.1. General procedures
1
Melting points are uncorrected. H- and 13C-NMR spectra were recorded in chloroform-d3
and measured on a Bruker AM 400 (400.134 MHz and 100.60 MHz) instrument. The chem-
ical shifts (δ’s) were measured versus the internal standard TMS. Elemental analyses were
performed by the Microanalysis Center of the Institute für Anorganische Chemie, Technische

Journal of Sulfur Chemistry 423
Universität Braunschweig, Germany. Mass spectra were obtained on a Finnigan MAT 8430 spec-
trometer at 70 eV. The IR spectra were obtained on a Nicolet 320 FT-IR using KBr pellets.
N-substituted-hydrazinocarbothioamides 1a–1d were prepared according to the literature (20).
4.2. General procedure for preparation of compounds 3
To a 500 ml two-necked round bottom flask containing a solution of 1a–1d (2 mmol) in acetonitrile
(200 ml) and triethylamine (0.202 g, 2 mmol), a solution of 2 (0.688 g, 4 mmol) in acetonitrile
(50 ml)wasaddeddropwisewithstirringfor30 minatroomtemperature.Themixturewasrefluxed
for 1–3 days (the reaction was monitored by TLC). The solvent was evaporated under vacuum
and the solid residue was dissolved in dry acetone (50 ml) and the solution was chromatographed
on thin layer plates (silica gel) using chloroform. The mobile phases containing products 4a–4d
as the slowest migrating zones, whereas compound 5 was separated as the fastest migrating zone.
Compound 5 was identified by means of an authentic sample. All zones were extracted and the
obtained products were recrystallized from the stated solvents.
4.3. (E)-((4,6-Diphenylfuro[3,4-d]thiazol-2-yl)diazenyl)(phenyl)methanone (4a)
Orange crystals (ethanol), mp 222 ◦C, yield: 0.64 g (75%). IR (νmax, cm−1): 3010–3000 (Ar CH),
−
1
=
−
=
−
1690 (C O), 1080 (C O). H NMR (400 MHz, CDCl3): δH 8.30 (d, 2H, J 8.0 Hz, Ar H), 8.00
=
−
=
−
−
(d, 2H, J 7.8 Hz, Ar H), 7.82 (d, 2H, J 1.0 Hz, Ar H), 7.70–7.50 (m, 4H, Ar H), 7.40 (t, 2H,
13
=
−
−
=
J 8.0, 1 Hz, Ar H), 7.38–7.20 (m, 3H, Ar H). C NMR (100 MHz, CDCl3): δC 190.0 (C O),
−
−
158.8 (C-1), 153.2 (C-3), 153.0 (C-4), 143.0 (C-2), 135.3 (Ar C), 129.90 (o-Ar 2CH), 129.0
−
−
−
−
−
(m-Ar 2CH), 128.2 (Ar C), 128.0 (o-Ar 2CH), 127.2 (m-Ar 4CH), 127.0 (p-Ar 2CH), 126.3
+
−
−
−
(Ar C), 126.0 (o-Ar 2CH), 125.8 (p-Ar CH), 119.0 (C-5); m/z (70 eV, %): 409 [M ] (100),
366 (20), 332 (30), 324 (50), 304 (24), 276 (24), 76 (54); C24H15N3O2S (409.46): Calcd: C, 70.40;
H, 3.69; N, 10.26; S, 7.83. Found: C, 70.20; H, 3.60; N, 10.15; S, 7.75%.
4.4. (E)-((4,6-Diphenylfuro[3,4-d]thiazol-2-yl)diazenyl)(4-hydroxyphenyl)methanone (4b)
Orange crystals (methanol), mp 250 ◦C, yield: 0.66 g (77%). IR (νmax, cm−1): 3450–3370
1
−
=
−
(OH), 3012–3008 (Ar CH), 1692 (C O), 1060 (C O). H NMR (400 MHz, CDCl3): δH 8.80
=
−
=
−
(s, 1H, OH), 8.20 (d, 2H, J 8.0 Hz, Ar H), 7.96 (d, 2H, J 7.8 Hz, Ar H), 7.80 (d, 2H,
J 1.0 Hz, Ar H), 7.75–7.62 (m, 3H, Ar H), 7.40–7.22 (m, 5H, Ar H). 13C NMR (100 MHz,
=
−
−
−
− −
CDCl3): δC 188.9 (CO), 162.0 (Ar C OH), 160.0 (C-1), 153.4 (C-3), 153.0 (C-4), 143.2 (C-2),
127.9 (Ar C), 131.6 (o-Ar 2CH), 130.8 (Ar 2C), 129.4 (Ar C), 129.2 (m-Ar 2CH), 128.6
(m-Ar 2CH), 128.2 (o-Ar 2CH), 126.7 (p-Ar CH), 125.0 (o-Ar 2CH), 122.4 (m-Ar 2CH),
119.0 (C-5); m/z (70 eV, %): 425 [M+] (100), 408 (28), 350 (22), 332 (18), 304 (40), 276 (16),
272 (16), 258 (34), 216 (24), 92 (30), 76 (54); C24H15N3O3S (425.46): Calcd: C, 67.75; H, 3.55;
N, 9.88; S, 7.54. Found: C, 67.65; H, 3.50; N, 9.74; S, 7.50%.
−
−
−
−
−
−
−
−
−
−
4.5. (E)-((4,6-Diphenylfuro[3,4-d]thiazol-2-yl)diazenyl)(4-methoxyphenyl)methanone (4c)
Pale orange crystals (methanol), mp 198 ◦C, yield: 0.72 g (82%). IR (νmax, cm−1): 3020–3001
1
−
=
−
−
(Ar CH), 1694 (C O), 1044 (C O). H NMR (400 MHz, CDCl3): δH 8.20 (d, 2H, Ar H), 3.85
−
−
−
=
(s, 3H, CH3), 8.00 (d, 2H, Ar H), 7.74 (d, 2H, Ar H), 7.45 (t, 2H, Ar H), 7.40 (t, 2H, J 7.8,
1.0 Hz,Ar H), 7.36 (m, 1H,Ar H), 7.30–7.10 (m, 3H,Ar H); 13C NMR (100 MHz, CDCl3): δC
−
−
−
−
−
188.8 (CO), 164.2 (C O), 160.4 (C-1), 153.4 (C-4), 152.8 (C-3), 140.8 (C-2), 131.0 (o-Ar 2CH),
130.0 (Ar C), 129.6 (Ar C), 129.2 (m-Ar 4CH), 128.8 (p-Ar CH), 128.6 (o-Ar 4CH), 127.6
−
−
−
−
−

424 A.A. Aly et al.
−
−
−
−
(Ar C), 125.7 (p-Ar CH), 116.0 (m-Ar 2CH), 119.0 (C-4), 54.6 (CH3 O); m/z (70 eV, %):
439 [M+] (100), 408 (18), 376 (24), 362 (16), 346 (20), 332 (24), 304 (32), 296 (16), 270 (24),
220 (26), 128 (32), 274 (26), 106 (36), 92 (26), 76 (34); C25H17N3O3S (439.49): Calcd: C, 68.32;
H, 3.90; N, 9.56; S, 7.30. Found: C, 68.20; H, 3.90; N, 9.62; S, 7.24%.
4.6. (E)-(4-Chlorophenyl) ((4,6-Diphenylfuro[3,4-d]thiazol-2-yl)diazenyl)methanone (4d)
Pale orange crystals (ethanol), mp 210 ◦C, yield: 0.62 g (70%). IR (νmax, cm−1): 3060–3008
1
−
=
−
−
(Ar CH), 1692 (C O), 1035 (C O). H NMR (400 MHz, CDCl3): δH 8.12–8.08 (m, 2H,Ar H),
−
=
−
=
−
7.80–7.64 (m, 4H, Ar H), 7.50 (t, 2H, J 7.8, 1 Hz, Ar H), 7.42 (t, 2H, J 7.8, 1.0 Hz, Ar H),
7.34–7.26 (m, 2H, Ar H), 7.10–7.08 (m, 2H, Ar H); 13C NMR (100 MHz, CDCl3): δC 188.0
− −
−
−
−
(CO), 160.4 (C-1), 154.0 (C-4), 152.8 (C-3), 142.4 (C-2), 139.6 (Ar C Cl), 133.2 (Ar 2C),
−
−
−
−
−
131.0 (o-Ar 4CH), 130.3 (m-Ar 2CH), 129.2 (m-Ar 4CH), 128.6 (Ar C), 127.2 (o-Ar 2CH),
−
−
126.4 (p-Ar CH), 125.6 (p-Ar CH), 118.7 (C-5); m/z (70 eV, %): 445 [M+2] (12), 444 [M+1]
(38), 443 [M+] (100), 410 (18), 408 (22), 382 (16), 380 (24), 368 (24), 352 (16), 350 (26), 290
(12), 284 (18), 282 (18), 242 (18), 240 (22), 112 (32), 76 (46); C24H14ClN3O2S (443.90): Calcd:
C, 64.94; H, 3.18; Cl, 7.99; N, 9.47; S, 7.22. Found: C, 64.80; H, 3.08; Cl, 8.02; S, 7.12%.
4.7. General procedure
By applying the same procedure mentioned before, to a 500 ml two-necked round bottom flask
containing a solution of 1a–1d (2 mmol) in acetonitrile (200 ml) and triethylamine (0.202 g,
2 mmol), a solution of 2 (0.344 g, 2 mmol) in acetonitrile (30 mL) was added dropwise with
stirring for 30 min at room temperature. The mixture was refluxed for 8–14 h (the reaction was
monitored by TLC). The solvent was evaporated under vacuum and the solid residues were
treated with absolute ethanol (200 ml); compounds 6a–6d were separated and recrystallized from
the stated solvents.
4.8. N-(4,6-Diphenylfuro[3,4-d]thiazol-2-yl)benzohydrazide (6a)
Yellow crystals (methanol), mp 322 ◦C, yield: 0.63 g (76%). IR (νmax, cm−1): 3350–3260
1
−
−
=
−
(NH NH), 3040–3012 (Ar CH), 1690 (C O), 1040 (C O); H NMR (400 MHz, CDCl3):
=
−
−
δH 10.50 (s, 1H, CONH), 8.20 (d, 2H, J 7.8 Hz, Ar H), 8.10–8.04 (m, 4H, Ar H), 7.60–7.65
(m, 2H, Ar H), 7.60 (t, 2H, J 7.8, 1.0 Hz, Ar H), 7.50–7.36 (m, 5H, Ar H), 6.00 (s, 1H,
N H). C NMR (100 MHz, CDCl3): δC 171.1 (CO), 160.2 (C-1), 152.8 (C-3), 152.0 (C-4),
138.7 (C-2), 130.0 (Ar 2C), 128.6 (Ar C), 128.4 (o-Ar 2CH), 127.6 (o-Ar 4CH), 126.8
(m-Ar 2CH), 127.0 (m-Ar 4CH), 126.2 (p-Ar 2CH), 125.8 (p-Ar CH), 108.0 (C-5); m/z
(70 eV, %): 411 [M+] (100), 338 (28), 326 (30), 306 (22), 278 (20), 248 (24), 242 (12), 78 (42);
C24H17N3O2S (411.48): Calcd: C, 70.05; H, 4.16; N, 10.21; S, 7.79. Found: C, 70.12; H, 4.08;
N, 10.11; S, 7.65%.
−
=
−
−
13
−
−
−
−
−
−
−
−
−
4.9. N-(4,6-Diphenylfuro[3,4-d]thiazol-2-yl)-4-hydroxybenzohydrazide (6b)
Yellow crystals (methanol), mp 340 ◦C (decomp.), yield: 0.67 g (78%). IR (νmax, cm−1): 3450–
1
−
−
=
−
3230 (OH, NH NH), 3090–3010 (Ar CH), 1686 (C O), 1040 (C O); H NMR (400 MHz,
−
CDCl3): δH 10.50 (s, 1H, CONH), 9.40 (s, 1H, OH), 8.20–8.10 (m, 4H, Ar H), 7.84 (d, 2H,
=
−
=
−
−
J 8.0, 1.0 Hz, Ar H), 7.48 (d, 2H, J 7.8, 1.0 Hz, Ar H), 7.42–7.34 (m, 4H, Ar H), 6.72–
6.65 (m, 2H, Ar H), 6.10 (s, 1H, N H); 13C NMR (100 MHz, CDCl3): δC 164.8 (CO), 162.4
−
−
−
−
−
(C OH), 160.0 (C-1), 152.6 (C-3), 151.8 (C-4), 138.7 (C-2), 130.8 (Ar C), 130.3 (Ar C), 127.8

Journal of Sulfur Chemistry 425
−
−
−
−
−
(o-Ar 2CH), 127.6(o-Ar 2CH), 127.2(o−Ar 2CH), 126.8(m-Ar 2CH), 126.4(m-Ar 2CH),
−
−
−
−
125.8 (p-Ar CH), 125.6 (Ar C), 125.3 (p-Ar CH), 116.0 (m-Ar 2CH), 107.8 (C-5); m/z
(70 eV, %): 427 [M+] (100), 410 (24), 334 (38), 306 (32), 274 (16), 260 (20), 218 (24), 200 (18),
93 (32), 76 (48); C24H17N3O3S (427.48): Calcd: C, 67.43; H, 4.01; N, 9.83; S, 7.50. Found: C,
67.30; H, 3.98; N, 9.85; S, 7.40%.
4.10. N-(4,6-Diphenylfuro[3,4-d]thiazol-2-yl)-4-methoxybenzohydrazide (6c)
Yellow crystals (methanol), mp 316 ◦C, yield: 0.73 g (83%). IR (νmax, cm−1): 3340–3260
1
−
−
=
−
(NH NH), 3060–3012 (Ar CH), 1688 (C O), 1030 (C O); H NMR (400 MHz, CDCl3):
−
=
−
δH 10.40 (s, 1H, CONH), 8.18–8.12 (m, 4H, Ar H), 7.90 (d, 2H, J 7.8 Hz, Ar H), 7.50 (t, 2H,
=
−
=
−
−
J 7.7, 0.8 = Hz, Ar H), 7.45 (t, 2H, J 7.7, 0.8 Hz, Ar H), 7.38–7.32 (m, 2H, Ar H), 7.17
(d, 2H, J 8.0, 1.0 Hz, Ar H), 6.01 (s, 1H, N H), 3.92 (s, 3H, CH3); 13C NMR (100 MHz,
=
−
−
− −
CDCl3): δC 165.2, 163.0 (Ar O C), 160.2 (C-1), 152.7 (C-3), 151.7 (C-4), 138.6 (C-2), 130.3
(Ar C), 129.0 (Ar C), 128.5 (o-Ar 4CH), 128.2 (m-Ar 2CH), 127.8 (m-Ar 2CH), 126.2
−
−
−
−
−
−
−
−
−
−
(p-Ar CH), 125.2 (o-Ar 2CH), 124.7 (Ar C+), 124.4 (p-Ar CH), 114.4 (m-Ar 2CH), 108.0
−
(C-5), 55.4 (CH3 O); m/z (70 eV, %): 441 [M ] (100), 426 (28), 410 (22), 384 (34), 364 (30),
348 (18), 272 (26), 106 (34), 92 (24), 76 (54); C25H19N3O3S (441.50): Calcd: C, 68.01; H, 4.34;
N, 9.52; S, 7.26. Found: C, 68.10; H, 4.30; N, 9.43; S, 7.20%.
4.11. 4-Chloro-N-((4,6-Diphenylfuro[3,4-d]thiazol-2-yl)diazenyl)benzohydrazide (6d)
Yellowcrystals (ethanol), mp 308 ◦C, yield:0.64 g (72%); IR (νmax, cm−1): 3330–3250(NH NH),
−
1
−
=
3050–3010 (Ar CH), 1690 (C O); H NMR (400 MHz, CDCl3): δH 10.38 (s, 1H, CONH), 8.22
−
−
−
=
(d, 2H, Ar H), 8.10 (d, 2H, Ar H), 7.80–7.68 (m, 4H, Ar H), 7.48 (t, 2H, J 8.0, 1.0 Hz,
−
=
−
−
−
Ar H), 7.42 (t, 2H, J 8.0, 1.0 Hz, Ar H), 7.35–7.32 (m, 2H, Ar H), 6.00 (s, 1H, N H);
13C NMR (100 MHz, CDCl3): δC 164.8 (CO), 160.4 (C-1), 152.6 (C-3), 151.4 (C-4), 138.8 (C-2),
− −
−
−
−
−
136.6 (Ar C Cl), 130.1 (Ar C), 129.8 (Ar C), 128.6 (o-Ar 2CH), 128.4 (Ar C), 128.0
−
−
−
−
−
(m-Ar 2CH), 127.4 (o-Ar 2CH), 127.0 (m-Ar 4CH), 126.3 (p-Ar CH), 125.8 (o-Ar 2CH),
+
−
124.8 (p-Ar CH), 106.8 (C-5); m/z (70 eV, %): 447 [M+2] (15), 446 [M+1] (36), 445 [M ]
(100), 412 (22), 410 (24), 384 (18), 382 (20), 370 (26), 354 (18), 352 (24), 290 (18), 286 (16), 284
(24), 244 (20), 242 (22), 112 (34), 76 (50); C24H16ClN3O2S (445.92): Calcd: C, 64.64; H, 3.62;
Cl, 7.95; N, 9.42; S, 7.19. Found: C, 64.50; H, 3.60; Cl, 8.04; N, 9.54; S, 7.04%.
Acknowledgement
Professor Aly thanks DAAD foundation for providing him with the postdoctoral grant that enabled him to do analyses.
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