Reaction of N,N '-disubstituted hydrazinecarbothioamides with 2-bromo-2-substituted acetophenones

Article abstract of DOI:10.24820/ark.5550190.p010.385

Reaction of hydrazinecarbothioamides with 2-bromoacetophenones furnished the formation of thiazole-, bisthiazole-, pyrazole- and 1,3,4-thiadiazole- derivatives in good yields. The mechanism was discussed. The structures of products were proved by MS, IR,

Full text of DOI:10.24820/ark.5550190.p010.385

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Paper
Archive for
Organic Chemistry
Arkivoc 2018, part iii, 102-111
Reaction of N,N ’-disubstituted hydrazinecarbothioamides with 2-bromo-2-
substituted acetophenones
*
a
b
a
a
Ashraf A Aly, Alaa A. Hassan, El-Shimaa S. M. AbdAl-Latif, Mahmoud A. A. Ibrahim,
b
c
Stefan Bräse, and Martin Nieger
a
Chemistry Department, Faculty of Science, Minia University, 61519-El-Minia, Egypt
Institute of Organic Chemistry, Karlsruhe Institute of Technology,76131Karlsruhe, Germany
Department of Chemistry, University of Helsinki, PO Box 55, 00014 University of Helsinki, Finland
E-mail: ashrafaly63@yahoo.com
b
c
Received 11-06-2017
Accepted 12-15-2017
Published on line 12-23-2017
Abstract
Reaction of hydrazinecarbothioamides with 2-bromoacetophenones furnished the formation of thiazole-, bis-
thiazole-, pyrazole- and 1,3,4-thiadiazole- derivatives in good yields. The mechanism was discussed. The
structures of products were proved by MS, IR, NMR, elemental analyses and X-ray structure analyses.
Keywords: Hydrazinecarbothioamides, 2-bromoacetophenones, thiazoles, bis-thiazole, pyrazole
DOI: https://doi.org/10.24820/ark.5550190.p010.385
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Aly, A. A. et al.
Introduction
1
-3
4
Substituted hydrazinecarbothioamides were found to exhibit antifungal,
antiviral and antioxidant
5
activities . Free radicals and reactive sulfur species such as thiol radicals are frequently synthesized through
many biological processes and may be considered as indicators of biological inadequacy. In recent times, the
applications of thiazoles have found in drug development for the treatment of allergies , hypertension,
inflammation, schizophrenia, bacterial, HIV infections, and hypnotics . Moreover, thiazoles have been
used for the treatment of pain, as fibrinogen receptor antagonists with antithrombotic activity and as new
inhibitors of bacterial DNA gyrase B. Mukhija it was reported that thiourea reacted quantitatively with
various 2-halocarbonyl compounds to form 2-amino salts of thiazoles. Many classes of thiadiazole have been
known to possess interesting widespread biological properties such as antimicrobial, and anticancer.
Previously, we utilized by N,N’-disubstituted-hydrazinecarbothioamides in heterocyclic synthesis, such as 1,3-
thiazin-2-ylidene-substituted hydrazides and 1,2,4-triazolo[3,4-b]-1,3-thiazine-5-carboxylates . Continuation
6
7
8
9
10
11
12
13
14
15
16
17
18,19
20
21-26
of our research program included the synthesis of various thiazoles,
investigation on the reactions of symmetrical hydrazinecarbothioamides 1a-d with 2-bromoacetophenones
a,b.
we herein report the results of our
2
Results and Discussion
Pleasingly, treatment of N,N’-disubstituted-hydrazinecarbothioamides 1a-d with 2-bromoacetophenones 2a,b
at room temperature afforded the corresponding thiazoles 3cb (80%), 4bb (82%), 5ba (90%), and 6db (87%)
(Scheme 1). (1E,2E)-1,2-Bis(5-methyl-4-phenyl-3-(p-tolyl)thiazol-2(3H)-ylidene)-hydrazine (7da) was also
obtained in 74% yield (Scheme 1), during the reaction of 1d with 2a. Reaction of allyl hydrazinecarbothioamide
derivative 1a with 2b, gave pyrazole 8ab in 75% yield (Scheme 1). Finally, and on reacting 1c with 2a, the
known 1,3,4-thiadiazole 9c was obtained in 72% yield (Scheme 1).
The structures of thiazoles 3cb, 4bb, 5ba, and 6db were elucidated by IR, NMR, mass spectra and
elemental analyses. For 3cb, its molecular formula was proved from elemental analysis and mass spectrometry
-
1
22
as C28H N
4
S
2
(Experimental section). The IR spectrum of 3cb showed absorption band at = 3330-3320 cm
1
for the NH group. No absorption was noted for carbonyl or hydroxyl groups in the IR spectrum. The H NMR
spectrum of 3cb showed two broad singlets; each for one proton at 
protons of thiourea. In C NMR spectrum of 3cb, it was observed carbon signals at  = 181.0 for C=S, 154.0

= 11.45 and 11.30 assigned to the two
13
C
(
thiazole-C-2), and 118.4 ppm for C-5 of thiazole moiety (Experimental Section).
For compound 4bb, its molecular formula was proved by mass spectrometry and elemental analysis as
(Experimental Section). Mass spectrum showed also the molecular ion peak at m/z = 506 (55%),
C
30 26
H N
S
4 2
whereas the basic ion peak at m/z = 91, which related to the prescence of benzylic fragment pattern. The IR
-1
1
spectra of 4bb showed the NH groups at = 3220-3215 cm . In the H NMR spectral data of 4bb
Experimental Section), it can be seen two broad singlets appeared at  = 10.25 and 10.08 ppm, which
assigned to the two NH thiourea protons. Moreover, the two-dissimilar benzylic-CH protons resonated at 
.86 and 5.02 ppm, respectively. The C NMR spectra was also in accordance to the proposed structure and
showed the functional groups of carbon signals  = 181.0 for the thioamide carbon and the two benzylic
carbons at  = 48.9 and 46.9 (Experimental section). The thiazole carbon signals were also resonated at 
56.8 (C-2), 145.0 (C-4) and 118.3 (thiazole-C-5).
(
H
2
H
=
13
4
C
C
C
=
1
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Scheme 1. Reactions of hydrazinecarbothioamides 1a-d with 2-bromoacetophenones 2a,b.
When, the derivative 1b reacted with 2-bromo-1-phenylpropan-1-one (2a), the reaction gave thiazole 5ba
1
(
Scheme 1). Mass spectrum of 5ba showed the molecular peak at m/z = 444. The H NMR spectrum of
compound 5ba gave two broad singlets at 
Section). Moreover, the asymmetrical structure was corroborated via appearance of three singlets at 
H
= 10.20 and 8.20 for the two NH thiourea protons (Experimental
= 4.8,
and thiol-H, respectively. The 13C NMR spectrum
H
5
.0, 2.3 and 2.1 of the two benzylic-CH
2
protons, CH
3
1
supported the H NMR spectroscopic data due to the prescence of the thione-C, thiazole-C-2 and the two
benzylic carbons at 
db, the two NH protons absorbed as two broad singlets at 
spectrum of 6db elucidated the asymmetric structure of 6db via the appearance the two carbon signals of the
p-toyl-methyl groups at  = 21.2 and 21.4 (see Experimental Section).
C
=179.7, 156.6, 48.9, and 46.4, respectively. (Experimental Section). Again, and in case of
13
6
H
=11.00 and 10.20. Most indicative that C NMR
C
Under the condition mentioned above, 1d reacted with 2a to give the bis-thiazole 7da in 74% yield
Scheme 1). The IR spectrum of 7da didn’t reveal any absorption corresponding to NH, OH and C=S groups
Experimental Section). Mass and elemental analysis revealed that the molecular weight of 7da equals to the
(
(
sum of 1d with two moles of 2a accompanied with elimination of two molecules of hydrogen bromide. In the
13
meanwhile, C NMR spectrum reveal carbon signals of an asymmetric molecule. Disappearance of the thione
13
carbon in C NMR spectrum, indicated that it was involved in cyclization process. The structure of E-
configuration in 7da was ultimately proved by X-ray structural analysis (Figure 1).
The suggested mechanism described the formation of thiazoles 3cb, 4bb, 5ba and 6db was based upon
attacking of thione-lone pair to the -bromo-C in 2a,b (Scheme 2). That was followed by salt formation as in
intermediate 10. Subsequently, salt 10 would be neutralized and nitrogen lone-pair would attack to the
carbonyl-C to form intermediate 11. Elimination of water and HBr from 11 would give the thiazoles 3cb, 4bb,
5ba and 6db (Scheme 2). Ultimately, addition of a second molecule of 2a to 11 along with extrusion of two
molecules of water and HBr, would produce 7da (Scheme 2).
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Figure 1. Molecular structure of 7da (displacement parameters are drawn at 50% probability level).
Scheme 2. Suggested mechanism describing the formation of thiazoles 3cb, 4bb, 5ba, 6bb and free bis-
thiazole 7da.
In different manner, reaction of equal equivalents of both 1a with 2-bromo-1,2-diphenylethan-1-one (2b)
gave pyrazole 8ab (Scheme 1). The IR spectrum of 8ab showed the NH and aliphatic groups at  = 3425-3400
-1
and 2933-2974 cm , respectively. The mass and elemental analysis elucidated the gross molecular formula of
8
ab as C18
H
17
N
3
. Mass spectrum showed the molecular ion peak at m/z = 275 (51%), whereas the base peak at
1
m/z = 102. The H NMR spectrum proved the prescence of allyl group and its protons. The NH-pyrazole was
absorbed in H NMR at  =12.00 (Experimental Section). The C NMR spectrum supported the H NMR
1
13
1
H
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spectroscopic data via the appearance of the allylic-carbons at 
C
= 45.7, 114.8 and 133.3. The structure of 8ab
was corroborated by X-ray structure analysis (Figure 2).
Scheme 3. Suggested mechanism describing the formation of compound 8ab.
The suggested mechanism for the formation of 8ab starts also from the salt 10 (Scheme 3). Neutralization
accompanied by elimination of HBr molecule, then addition of nitrogen-lone pair of the N-2 of the hydrazine
group to the carbonyl-C would give intermediate 13 (Scheme 3). Elimination of water molecule from 13 would,
thus, give 14. Rearrangement was then occurred via amidine-like reaction to C-6 of the formed thiadiazine
would led to salt 15. Elimination of allyl isothiocyanate and extrusion of sulfur from 15 would, finally give 8ab
(Scheme 3).
Finally, on reacting hydrazinecarbothioamide derivative 1c with 2a, the reaction yielded the known
27
product 9c , Scheme 1). Heating the compound 1c alone under the same condition didn’t proceed to give 9c,
therefore we concluded that the presence of 2a would enhance the formation of thiadiazole 9c. Starting from
the previous formed intermediate 10, the other thione-lone pair would attack to the positively charged
thiamido-C to form salt 16 (Scheme 4). Rearrangement and neutralization process in 16 and recombination of
the eliminated Br anion would form 10 and recycled compound 2a together with extrusion of H S (Scheme 4).
2
27
Based upon TLC analysis with authentic sample of known N,N’-diphenyl-1,3,4-thiadiazole-2,5-diamine and its
1
IR and H NMR, the structure compound 9c was proved.
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Scheme 4. Suggested mechanism describing formation of compound 9c during reaction of 1c with 2a.
Figure 2. Molecular of 8ab (displacement parameters are drawn at 50% probability level).
Conclusions
Our paper describes the synthesis of different types of heterocycles during the reactions of
hydrazinecarbothioamides with electrophilic reagents. Therefore, much work will be done in our lab to
investigate further reactions of hydrazinecarbothioamides.
Experimental Section
General. Melting points were determined on Stuart electrothermal melting point apparatus and were
uncorrected. TLC analysis was performed on analytical Merck 9385 silica aluminum sheets (Kiselgel 60) with
PF254 indicator. The IR spectra were recorded as KBr disks on Shimadzu-408 infrared spectrophotometer,
Faculty of Science, Minia University. The NMR spectra were measured using a Bruker AV-400 spectrometer at
the Karlsruhe Institut für Technologie (KIT), Institute of Organic Chemistry, Karlsruhe, Germany. Chemical
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shifts were expressed as δ (ppm) with tetramethylsilane as internal reference. The samples were dissolved in
DMSO-d , s = singlet, d = doublet, dd = doublet of doublet and t = triplet. Mass spectrometry were recorded on
6
a Varian MAT 312 instrument in EI mode (70 eV), at the Karlsruhe Institut für Technologie (KIT), Institute of
Organic Chemistry, Karlsruhe, Germany. Elemental analyses were carried out using Varian Elementary device
in National Research Center, Giza, Egypt.
Starting materials. N,N’-Disubstituted-hydrazinecarbothioamides were prepared according to published
27
procedures as were N,N’-diallylhydrazine-1,2-dicarbothioamide (1a) , N,N’-bis(benzyl)hydrazine-1,2-
27
dicarbothioamide (1b), N,N’-diphenylhydrazine-1,2-dicarbothioamide (1c) , N,N’-bis(4’-methylphenyl)-
28
hydrazine-1,2-dicarbothioamide (1d). 2-Bromoacetophenones 2a,b were bought from Aldrich.
General Procedure: reaction of hydrazinecarbothioamides 1a-d with 2-bromoacetophenones 1a,b. A mixture
of hydrazinecarbothioamides (1a-d, 1 mmol) and 2-bromoacetophenones (2a,b, 1 mmol) in 30 mL dry EtOH
together 0.5 mL of triethyl amine were stirred at room temperature for 10-12 h (the reaction was followed up
by TLC analysis). In case of reaction between 1a and 2b, the reaction was completed after refluxing the
reaction mixture for 3h. The formed precipitates were allowed to stand overnight and they were collected by
suction filtration. The precipitates were then washed with cyclohexane, and dried at room temperature.
Compounds 3cb, 4bb, 5ba, 6db, free bis-thiazole 7da, pyrazole 8ab and thiadiazole 9c were obtained and were
recrystallized from the stated solvents.
N-Phenyl-2-(3,4,5-triphenylthiazol-2(3H)-ylidene)hydrazine-1-carbothioamide (3cb). Yellow crystals (EtOH),
o
yield: 0.38 g (80%), M.p.: 235 -7 C (decomp.). IR (KBr):  = 3330-3320 (NH), 3030 (Ar-CH), 1620 (C=N), 1590
-1 1
(
C=C), 1366 (C=S) cm ; H NMR (400 MHz, DMSO-d
): 
6 H
= 11.45 (bs, 1H, NH), 11.30 (bs, 1H, NH), 7.80-7.75 (m,
2
6
4
1
H, Ph-H), 7.70-7.65 (m, 2H, Ph-H), 7.56-7.46 (m, 5H, Ph-H), 7.30-7.15 (m, 5H, Ph-H), 7.00-6.85 (m, 4H, Ph-H),
13
.80-6.75 (m, 2H) ppm. C NMR (100 MHz, DMSO-d
6
):  = 181.0 (C=S), 154.0 (thiazole-C-2), 144.4 (thiazole-C-
C
), 138.3, 136.4 (Ar-N-C), 130.2, 130.0 (Ph-C), 128.4, 128.2, 127.8, 127.6, 127.4, 127.2, 127.0 (Ar-2CH), 126.8,
26.6, 126.4, 126.0 (Ar-CH), 125.8 (Ar-2CH), 118.4 (thiazole-C-5) ppm. MS (70 eV, Fab mass, %): m/z = 478
(92%), 385 (17), 328 (32), 268 (38), 152 (100). C28
22
H N
4
S (478.18): Calcd. C, 70.26; H, 4.63; N, 11.71. Found: C,
2
70.16; H, 4.60; N, 11.60.
N-Benzyl-2-(3-benzyl-4,5-diphenylthiazol-2(3H)-ylidene)hydrazine-1-carbothioamide (4bb). Orange crystals
°
(
(
DMF/EtOH), yield: 0.41 g (82%), M.p.: 200-2 C (decomp.).IR (KBr):  = 3220-3215 (NH), 3030 (Ar-CH), 2777
-1 1
Aliph.-CH), 1581 (C=N), 1560 (C=C), 1370 (C=S) cm ; H NMR (400 MHz, DMSO-d
): 
6 H
=10.25 (bs, 1H, NH),
1
0.08 (bs, 1H, NH), 7.80-7.76 (m, 2H, Ar-H), 7.70-7.50 (m, 5H, Ar-H), 7.30-7.15 (m, 4H, Ar-H), 7.00-6.86 (m, 2H,
13
Ar-H), 6.80-6.50 (m, 7H, Ar-H), 5.02 (bs, 2H, CH
DMSO-d ):  = 181.0 (C=S), 156.8 (thiazole-C-2), 145.0 (thiazole-C-4), 138.3, 136.4 (Ar-N-C), 131.6, 131.0 (Ph-
C), 128.5, 128.3, 128.0, 127.9, 127.8, 127.6, 127.5, 127.2 (Ar-2CH), 126.4, 126.0, 125.8, 125.4 (Ar-CH), 118.3
2
-benzyl), 4.86 (bs, 2H, CH
2
-benzyl) ppm. C NMR (100 MHz,
6
C
2
(thiazole-C-5), 48.90, 46.9 (benzylic-CH ) ppm. MS (70 eV, Fab mass, %): m/z = 506 (55%), 91 (100). C30
26
H N
S
4 2
(506.16): Calcd. C, 71.12; H, 5.17; N, 11.06. Found: C, 71.00; H, 5.08; N, 11.10.
N-Benzyl-2-(3-benzyl-5-methyl-4-phenylthiazol-2(3H)-ylidene)hydrazine-1-carbothioamide (5ba). Brown
°
crystals (DMF/EtOH), 0.40 g (90%), M.p.: 260-2 C (decomp.). IR (KBr):  = 3330-3260 (NH), 3060-3030 (Ar-CH),
-1 1
2
900-2820 (Aliph.-CH), 1630, 1610 (C=N), 1560 (C=C) cm ; H NMR (400 MHz, DMSO-d
6
):  =10.20 (s, 1H, NH-
H
thiourea), 8.20 (bs, 1H, NH-thiourea), 7.60-7.50 (m, 5H, Ar-H), 7.35-7.10 (m, 5H, Ar-H), 6.94-6.86 (m, 5H, Ar-H),
1
3
5
1
2
.00 (bs, 2H, CH
2
-benzyl), 4.80 (bs, 2H, CH
2
-benzyl), 2.30 (s, 3H, CH
3
) ppm. C NMR (100 MHz, DMSO-d
6
): 
C
=
79.7 (C=S), 169.7 (C-2), 144.7 (C-5), 139.1 (C-4), 133.2, 132.1, 131.3 (Ar-C), 129.2, 128.8, 128.6, 127.8 (Ar-
CH), 126.8, 126.6, 126.2 (Ar-CH-p), 124.8, 124.4 (Ar-2CH), 48.9, 46.4 (benzyl-CH
2 3
), 22.0 (CH ) ppm. MS (70 eV,
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Aly, A. A. et al.
+
Fab mass, %): m/z = 444 ([M , 100). C25
24
H N
4
S
2
(444.62): Calcd. C, 67.54; H, 5.44; N, 12.60. Found: C, 67.40; H,
5.58; N, 12.70.
2
-(4,5-Diphenyl-3-(p-tolyl)thiazol-2(3H)-ylidene-N-(p-tolyl)hydrazine-1-carbothioamide (6db). Brown crystals
°
(DMF/EtOH), 0.45 g (87%), M.p. 282-4 C (decomp.). IR (KBr):  = 3340-3210 (NH), 3090 (Ar-CH), 2900-2820
-1 1
(
1
Aliph.-CH), 1630, 1620 (C=N), 1570 (C=C) cm ; H NMR (400 MHz, DMSO-d
0.20 (bs, 1H, NH-thiourea), 7.60-7.57 (dd, 2H, J = 7.8, 0.7 Hz, Ar-H), 7.40-7.15 (m, 5H, Ar-H), 7.20-7.00 (m, 5H,
Ar-H), 6.80-6.65 (m, 4H, Ar-H), 6.56-6.52 (dd, 2H, J = 7.8, 1.0 Hz, Ar-H), 2.40 (s, 3H, CH -Ar-C), 2.20 (s, 3H, CH
= 180.0 (C=S), 168.0 (C=N), 144.5 (C-5), 139.2 (C-4), 138.2, 138.0
6
):  =11.00 (s, 1H, NH-thiourea),
H
3
3
-
13
Ar-C) ppm. C NMR (100 MHz, DMSO-d
6
): 
C
(
1
Ar-N-C), 136.2, 135.4 (Ar-C-CH
26.6, 126.4 (Ar-CH-p), 124.8 (Ar-2CH), 22.3, 22.1 (CH
3
), 132.3, 130.1 (Ar-C), 128.8, 128.7, 128.6, 128.0, 127.8, 127.6, 127.2 (Ar-2CH),
+
3
-Ar) ppm. MS (70 eV, Fab mass, %): m/z = 506 ([M ],
26
100). C30H N
S
4 2
(506.68): Calcd. C, 71.11; H, 5.17; N, 11.06. Found: C, 71.20; H, 5.10; N, 11.28.
(
1E,2E)-1,2-Bis(5-methyl-4-phenyl-3-(p-tolyl)thiazol-2(3H)-ylidene)hydrazine
(7da).
Yellow
crystals
o
(DMF/EtOH), yield: 0.41 g (74%), M.p. = 230-232 C. IR (KBr):  = 3030-3009 (Ar-CH), 2960, 2940 (Aliph-CH),
−
1 1
1
7
630-1610 (C=N), 1560 (C=C) cm ; H NMR (400 MHz, DMSO-d
.40-7.20 (m, 6H, Ar-H), 7.10-6.80 (m, 8H, Ar-H), 2.26 (s, 6H, CH
):  = 163.2 (2C-2, thiazole), 147.8 (2C-4, thiazole), 139.8 (Ar-2C-N), 136.8, 131.0 (Ph-2C), 128.6,
6
): 
H
= 7.75-7.70 (dd, 4H, J = 8.0, 0.9 Hz, Ar-H),
1
3
3
), 2.20 (s, 6H, Ar-CH
3
) ppm. C NMR (100 MHz,
DMSO-d
6
C
1
28.5, 127.8 (Ar-4CH), 126.5 (Ph-2CH-p), 120.4 (Ar-4CH), 90.6 (2C-5, thiazole), 22.0, 18.9 (2CH
3
) ppm. MS (70
+
eV, Fab mass, %): m/z = 559 (M + 1, 22), 558 (M , 34), 250 (100), 101 (30). C34
30
H N
4
S (558.76): Calcd. C, 73.09;
2
H, 5.41; N, 10.03. Found: C, 73.30; H, 5.30; N, 10.0.
N-Allyl-4,5-diphenyl-1H-pyrazole-3-amine (8ab). Buff crystals (EtOH), yield: 0.20 g (75%), M.p.: 140-142 °C. IR
−
1 1
(
KBr):  = 3425-3400 (NH), 2933, 2974 (Aliph-CH), 1641-1601 (C=N), 1533 (C=C) cm ; H NMR (400 MHz,
DMSO-d ):  = 12.00 (bs, 1H, Pyrazole- NH pyrazole), 7.80-7.60 (m, 6H, Ph-H), 7.45-7.30 (m, 5H, Ph-H, allyl-
NH), 5.80 (m, 1H, allyl-CH= ), 5.30-5.40 (m, 2H, allyl-CH
DMSO-d ):  = 143.0 (pyrazole-C-3), 139.8 (pyrazole-C-5), 136.0, 133.4 (Ph-C), 133.3 (allyl-CH=), 129.0, 128.6,
Ar-2CH), 127.8, 127.8 (Ar-CH-p), 127.8, 127.4 (Ar-2CH), 114.8 (allyl-CH=0), 112.0 ( pyrazole-C4), 45.7 (allyl-
CH ) ppm. MS (70 eV, Fab mass, %): m/z = 275 (51), 102 (100). C18 (275.36): Calcd. C, 78.52; H, 6.22; N,
5.26. Found: C, 78.40; H, 6.10; N, 15.12.
N,N’-Diphenyl-1,3,4-thiadiazole-2,5-diamine (9c). Colorless crystals (MeOH), yield: 0.19 g (72%), M.p.: 240 °C
6
H
13
2
), 3.90 (m, 2H, CH -allyl) ppm. C NMR (100 MHz,
2
6
C
(
2
H N
17 3
1
2
7
(lit. 239–240°C).
Crystal Structure Determinations. The single-crystal X-ray diffraction study were carried out on a Bruker D8
Venture diffractometer with Photon100 detector at 123(2) K using Cu-Kradiation (= 1.54178 Å. Direct
29
Methods (SHELXS-97) were used for structure solution and refinement was carried out using SHELXL-2014
30
(
full-matrix least-squares on F2) . Hydrogen atoms were localized by difference electron density
determination and refined using a riding model (H(N) free). Semi-empirical absorption corrections were
applied. For 8ab an extinction correction was applied.
7
P2
=
da: orange crystals, C34
H
30
N
4
S
2
, Mr = 558.74, crystal size 0.12 × 0.08 × 0.06 mm, monoclinic, space group
3
1
/c (No. 14), a = 9.7213(3) Å, b = 13.9974(4) Å, c = 10.8289(3) Å, β = 103.137(2)°, V = 1434.96(7) Å , Z = 2, ρ
-3
-1
1.293 Mg/m , µ(Cu-K) = 1.911 mm , F(000) = 588, 2max = 144.4°, 21286 reflections, of which 2822 were
independent (Rint = 0.054), 183 parameters, R1 = 0.040 (for 2354 I > 2σ(I)), wR2 = 0.102 (all data), S = 1.05,
largest diff. peak / hole = 0.322 / -0.211 e Å-3.
8
ab: yellow crystals, C18
H
17
N
3
, Mr = 275.34, crystal size 0.36 × 0.30 × 0.06 mm, monoclinic, space group C2/c
3
(No. 15), a = 29.1406(8) Å, b = 11.0744(3) Å, c = 9.2494(2) Å, β = 104.998(1)°, V = 2883.23(13) Å , Z = 8, ρ =
-
3
-1
1.269 Mg/m , µ(Cu-K) = 0.596 mm , F(000) = 1168, 2max = 144.4°, 18490 reflections, of which 2847 were
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Arkivoc 2018, iii, 102-111
Aly, A. A. et al.
independent (Rint = 0.031), 197 parameters, 2 restraints, R1 = 0.034 (for 2572 I > 2σ(I)), wR2 = 0.084 (all data),
S = 1.04, largest diff. peak / hole = 0.217 / -0.201 e Å-3.
The CCDC 1553071 (7da), and CCDC 1553072 (8ab) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
We thank the DFG (BR 1750) for its financial supported to the stay of Professor Aly at the Karlsruhe Institute of
Technology, Institute of Organic Chemistry, Germany.
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