Synthesis of novel bis-2-(1,3,4-thiadiazolin-3-ylphenoxy) alkane derivatives

Article abstract of DOI:10.1080/10426500307823

A novel synthesis of bis(thiadiazolin-3-yl)ethers 6a-f and bis(thiadiazolin-2-on-3-yl)ethers 10a-f via the reaction of the bis (diazonium) salts 2a-c with the appropriate ω-thiocyanatoacetophenone derivatives 4a-c.

Full text of DOI:10.1080/10426500307823

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis of Novel Bis-2-(1,3,4-thiadiazolin-3-
ylphenoxy) Alkane Derivatives
Mohamed A. A. Elneairy a , Ashraf A. Abbas a & Yehia N. Mabkhout a
a Cairo University, Giza, Egypt
Version of record first published: 27 Oct 2010.
To cite this article: Mohamed A. A. Elneairy , Ashraf A. Abbas & Yehia N. Mabkhout (2003): Synthesis of Novel Bis-2-(1,3,4-
thiadiazolin-3-ylphenoxy) Alkane Derivatives, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:8, 1747-1757
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Phosphorus, Sulfur, and Silicon, 178:1747–1757, 2003
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Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print
DOI: 10.1080/10426500390220989
SYNTHESIS OF NOVEL
BIS-2-(1,3,4-THIADIAZOLIN-3-YLPHENOXY)
ALKANE DERIVATIVES
Mohamed A. A. Elneairy, Ashraf A. Abbas,
and Yehia N. Mabkhout
Cairo University, Giza, Egypt
(Received December 2, 2002; accepted February 24, 2003)
A novel synthesis of bis(thiadiazolin-3-yl)ethers 6a–f and bis(thia-
diazolin-2-on-3-yl)ethers 10a–f via the reaction of the bis (diazonium)
salts 2a–c with the appropriate ω-thiocyanatoacetophenone derivatives
4a–c.
Keywords: Bis(diazonium) salts; thiadiazoline
In the last decades much attention have been devoted to the con-
struction of new derivatives of thiadiazole and thiadiazolone on ac-
count of their reported biological activities. Various series of thiadia-
zoles, thiadiazolones and their annelated derivatives are reported to
have diverse biological activities as antibacterial,1−4 antimicrobial,5,6
antifirinolytic and antiinflammatory,7 antihistamines, and muscarinic
agonists.8 Some thiadiazole derivatives also were used as inhibitors of
the neutral endopeptidase9 carbonic anhydrase,10 anticarcenogenic.11
Recently, bis(compounds) have received great attention not only for be-
ing model compounds for main chain polymers12−17 but also because
many biologically active natural and synthetic products have molecular
symmetry.18 We recently19 have described the synthesis of some new bis
(activated styrene) derivatives and studied their synthetic potential as
starting materials for novel bis(pyridin-4-yl) ethers and bis(thieno[2,3-
b]-pyridine) derivatives. In continuation of our interest in this field,
we report here on the synthesis of some new bis(hydrazones) to ex-
plore their synthetic utility as intermediates in the synthesis of novel
bis(thiadiazolyl) ethers of expected biological activities.
Address correspondence to Mohamed A. A. Elneairy, Chemistry Department, Faculty
of Science, Cairo University, Giza, Egypt. E-mail: elneairy@hotmail.com
1747

1748
M. A. A. Elneairy et al.
RESULT AND DISCUSSION
The synthetic route described for the synthesis of the bis(2-imino-
thiadiazolin-3-yl)ethers 6a–f is outlined in Scheme 1. Thus, the diamine
dihydrochloride 1a–c were diazotized with sodium nitrite in hydrochlo-
ric acid to give the corresponding bis(diazonium) salts 2a–c. The dia-
zonium salts 2a,b were then reacted with ω-thiocyanatoacetophenone
(4a) to give the corresponding bis(iminothiadiazole) derivatives 6a,d.
SCHEME 1

Synthesis of Novel Bis(thiadiazolin-3-yl) Alkane Derivatives
1749
The reaction proceed via initial formation of the bis(hydrazone) deriva-
tives 5a,d followed by the addition of the hydrazone NH to the ni-
trile function to afford the target molecules 6a,d. The IR(cm−1) spec-
tra of the latter products showed absorption bands of NH and C O
groups near ν = 3290 cm−1 and ν = 1640 cm−1, respectively. The struc-
tures of compounds 6a,d were further supported via their reactions
with acetic anhydride and benzoyl chloride to give the correspond-
ing bis-N-(acetylimino) and bis-N-(benzoylimino) derivatives 7a,d and
8a,d respectively, (Scheme 2). The IR spectra of compounds 7a,d and
SCHEME 2

1750
M. A. A. Elneairy et al.
8a,d revealed the absence of bands characteristic for the NH ab-
sorption. Moreover, their 1H-NMR did not reveal any signal corre-
sponding to NH proton. The structures 6a,d were further confirmed
by their reaction with nitrous acid to give the corresponding bis-N-
(nitrosoimino-1,3,4-thiadiazolyl) derivatives 9a,d (Scheme 2). Heat-
ing of compounds 9a,d in refluxing ethylene glycol afforded 60% of
the corresponding bis(thiadiazolone) derivatives 10a,d via the loss of
one molecule of nitrogen. The IR (cm−1) of compounds 10a,d showed
C O absorption band near 1650 cm−1. In the same manner, com-
pounds 2a,b were reacted with p-methyl-ω-thiocyanatoacetophenone
(4b) andp-chloro-ω-thiocyanatoacetophenone (4c) to give the corre-
sponding bis(iminothiadiazole) derivatives 6b,c,e,f in a respective
manner. The latter products reacted with acetic anhydride and ben-
zoyl chloride to yield 45–60% of the corresponding bis-N-(acetylimino)
and bis-N-(benzoylimino) derivatives 7b,c,e,f and 8b,c,e,f respectively.
Compounds 6b,c,e,f also reacted with nitrous acid to afford the cor-
responding bis-N-(nitrosoimino-1,3,4-thiadiazole) derivatives 9b,c,e,f.
Heating of the latter compounds in boiling ethylene glycol afforded
the corresponding bis(thiadiazolone) derivatives 10b,c,e,f respectively,
SCHEME 3

Synthesis of Novel Bis(thiadiazolin-3-yl) Alkane Derivatives
1751
(Scheme 2). The structures of compounds 6a–f, 7a–f, 8a–f, 9a–f, and
10a–f were established on the basis of their elemental analyses and
spectral data.
Our studies have also extended to include the synthesis of the new
bis(hydrazones) 13a,b and 14a–d as outlined in Scheme 3. Thus, cou-
pling of the diazonium salts 2a–c with a series of active methylene com-
pounds namely, 2-cyanothioacetamide (3)20 benzothiazol-2-ylacetamide
(4a)21 and benzothiazol-2-yl-acetonitrile (4b)22 in ethanolic solution
containing sodium acetate afforded 13a,b and 14a–d in 60–75% yield
(cf. Scheme 3). The existance of compounds 13a,b, 14a–d in the hy-
drazone form was confirmed by the following facts: a) the absence of
1
signals characteristic for the methine protons in their H NMR spec-
tra, b) the presence of NH absorption near ν = 3275 cm−1 in their IR
spectra, and c) the fact that the hydrazone is the most stable form
whenever condensation occur at a methylene group.23 Unfortunately,
attempts to react 13a,b and 14a–d with a series of amino nucleophiles
to give the corresponding bis(heterocycles) were unsuccessful. This may
be attributed to the inherent insolubility of the new bis(hydrazones) in
the reaction media.
EXPERIMENTAL
All melting points were measured on a Gallenkamp electrothermal
melting point apparatus and are uncorrected. The infrared spectra were
recorded in potassium bromide on a Pye Unicam SP 3-300 infrared and
FT-IR 8101PC Schimadzu spectrophotometers.
The 1H NMR spectra were recorded in deuterated chloroform or
dimethyl sulphoxide on a Varian Gemini 200 NMR and varian Mercury
300 MHz spectrometer using tetramethysilane(TMS) as an internal ref-
erence; mass spectra were recorded on a GCMS-QP 1000 EX Shimadzu
mass spectrumeter at 70 eV. Elemental analysis were carried out at the
Microanalytical Center of Cairo University, Giza, Egypt.
Compounds 1a, b,24 1c,23 11,20 12a,21 12b,22 and 4a–c25 were pre-
pared according to the literature procedure.
Synthesis of Compounds 13a,c, 14a--d, and 6a--f
General procedure: A stirred cold solution (0–5◦C) of the appro-
priate diamine dihydrochloride 1a–c (1 mmol) in water (10 ml) and
concentrated hydrochloric acid (5 ml) was added a solution of sodium
nitrite (0.23 g in 5 ml of water) over 30 min. Stirring was continued for
40 min at 0–5◦C. The solution was then added dropwise with stirring
to a solution containing the appropriate active methylene compounds

1752
M. A. A. Elneairy et al.
TABLE I Characterization Data of the Newly Synthesized Compounds
Elemental analyses
calc./found
Mol. formula
colour
Yield %
m.p.◦C
Solvent
of cryst.
Comp.
C
H
N
S
Cl
6a
C33H26N6O4S2
Yellow
C35H30N6O4S2
Yellow
C33H24N6O4S2Cl2
Yellow
C34H28N6O4S2
Yellow
75
125–127
60
95–97
50
215–217
60
145–147
66
90–92
70
Semisolid
60
238–240
60
255–257
55
275–277
60
205–207
60
165–167
50
110–112
65
245–246
55
305–307
65
302–304
60
210–212
70
Ethanol
Ethanol
Ethanol
Ethanol
62.45 4.13 13.24 10.10
62.20 3.90 13.50 10.40
6b
6c
6d
6e
6f
63.43 4.56 12.68
63.70 4.70 12.90
56.33 3.44 11.94
56.60 3.20 12.10
62.95 4.35 12.95
63.10 4.50 13.10
9.68
9.90
9.11 10.08
8.90 10.30
9.89
9.60
C
36H32N6O4S2
Yellow
34H26N6O4S2Cl2
Acetic acid 63.89 4.77 12.42
64.00 4.50 12.20
Ethanol
9.48
9.60
C
56.90 3.65 11.71
57.20 3.90 11.40
8.94
8.70 10.0
8.92
9.88
Yellow
C37H30N6O6S2
Yellowish-white
7a
7b
7c
7d
7e
7f
Acetic acid 61.83 4.21 11.69
62.00 4.50 11.40
Acetic acid 62.72 4.59 11.25
63.00 4.30 11.50
Acetic acid 56.42 3.58 10.67
56.20 3.30 10.90
Acetic acid 62.28 4.40 11.47
62.00 4.70 11.70
Acetic acid 63.14 4.77 11.04
63.40 4.90 10.90
Acetic acid 56.93 3.77 10.48
57.10 4.00 10.20
DMF
DMF
DMF
9.10
8.59
8.30
C
39H34N6O6S2
Yellowish-white
37H28N6O6S2Cl2
Yellowish-white
38H32N6O6S2
Yellowish-white
40H36N6O6S2
Yellowish-white
38H30N6O6S2Cl2
C
8.14
8.40
8.75
9.00
8.43
8.20
8.00
8.30
7.61
7.40
7.36
7.10
7.03
7.30
7.48
7.20
7.25
7.50
6.93
7.10
9.26
9.50
8.90
9.10
8.42
8.20
9.07
9.30
9.0
8.7
C
C
C
8.84
8.60
Yellowish-white
C47H34N6O6S2
White
8a
8b
8c
8d
8e
8f
66.97 4.07
67.10 3.90 10.10
67.57 4.40
67.30 4.70
61.91 3.54
62.10 3.80
9.97
C49H38N6O6S2
9.65
9.80
9.22
9.00
9.81
White
C47H32N6O6S2Cl2
7.78
8.0
White
C48H36N6O6S2
Acetic acid 67.27 4.23
Yellow
67.50 4.50 10.00
C50H40N6O6S2
Acetic acid 67.86 4.56
9.50
9.20
9.08
9.30
Reddish-brown
C48H34N6O6S2Cl2
Yellowish-white
C33H24N8O6S2
Reddish-brown
C35H28N8O6S2
Reddish-brown
C33H22N8O6S2Cl2
Reddish-brown
140–142
55
230–232
70
140–142
60
154–156
65
68.00 4.80
Acetic acid 62.27 3.70
62.00 3.40
Acetic acid 57.22 3.49 16.18
57.50 3.20 16.40
7.66
7.90
9a
9b
9c
9d
Acetic acid 58.32 3.92 15.55
58.50 3.70
5.80
Acetic acid 52.04 2.91 14.71
51.80 2.70 15.00
Acetic acid 57.78 3.71 15.85
58.00 3.90 15.60
9.31
9.10
138–140
60
250–252
C34H26N8O6S2
Reddish-brown
(Continued on next page)

Synthesis of Novel Bis(thiadiazolin-3-yl) Alkane Derivatives
1753
TABLE I Characterization Data of the Newly Synthesized Compounds
(Continued)
Elemental analyses
calc./found
Mol. formula
colour
Yield %
m.p.◦C
Solvent
of cryst.
Comp.
C
H
N
S
Cl
9e
C36H30N8O6S2
Reddish-brown
70
140–142
60
140–142
55
80–82
40
145–147
40
95–97
40
166–168
50
145–147
40
218–220
75
225–227
75
215–217
80
240–242
75
255–257
80
Acetic acid 58.84 4.11 15.25
59.00 4.40 15.50
Acetic acid 52.65 3.12 14.45
52.40 3.40 14.20
8.73
8.40
8.27
8.50
9f
C34H24N8O6S2Cl2
9.14
8.90
Reddish-brown
C33H24N4O6S2
Yellowish-white
10a
10b
10c
10d
10e
10f
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
62.25 3.80
62.40 3.90
63.24 4.25
63.50 4.00
56.17 3.14
55.90 3.40
62.76 4.03
63.00 4.30
63.70 4.45
64.00 4.20
56.75 3.36
57.00 3.10
8.80 10.07
9.00
8.43
8.20
7.94
7.10
8.61
8.80
8.25
8.50
7.79
8.80
9.90
9.65
9.90
9.09 10.05
8.80 10.30
9.86
9.60
9.45
9.70
8.91
C
35H28N4O6S2
Yellowish-white
33H22N4O6S2Cl2
Yellow
34H26N4O6S2
Yellow
36H30N4O6S2
C
C
C
Yellowish-white
C34H24N4O6S2Cl2
Yellow
9.85
9.10 10.1
13a
13b
14a
14b
14c
14d
C
21H20N8O2S2
Yellow
21H20N8S4
Yellow
33H28N8O4S2
Yellow
33H24N8O2S2
Acetic acid 52.49 4.19 23.32 13.34
52.10 4.00 23.10 13.60
Acetic acid 49.20 3.93 21.86 25.02
49.50 3.70 22.00 25.3
C
C
DMF
DMF
DMF
DMF
59.62 4.25 16.86
59.40 4.11 16.75
63.04 3.85 17.82 10.20
62.80 4.00 17.50
60.16 4.45 16.51
59.80 4.19 16.65
63.53 4.08 17.43
9.65
9.70
C
Yellow
C34H30N8O4S2
Yellow
9.90
9.45
9.30
9.98
290–292
75
C34H26N8O2S2
Yellow
265–267
63.30 3.80 17.70 10.20
namely; 2-cyanothioacetamide (11) benzothiazol-2-ylacetamide (12a),
benzothiazol-2-ylacetonitrile (12b), and ω-thiocyanatoacetophenone
derivatives 4a–c (2 mmol), in ethanol (20 ml) and dimethylformamide
(10 ml) containing sodium acetate (3 g) over a period of 50 min. The re-
action mixture was then allowed to stand at 0◦C for 3 h. The solid
obtained was collected by filtration and crystallized from the proper
solvent.
Synthesis of 7a--f
General procedure: The appropriate of bis imino-1,3,4-thiadiazole
derivative of 6a–f (10 mmol) and acetic anhydride (20 ml) was heated

1754
M. A. A. Elneairy et al.
TABLE II IR and 1H-NMR Data
Comp.
IR(cm−1
)
H-NMR(δ)
6a
3290, (NH), 1640 (C O)
3205, (NH), 1697 (C O)
3320, (NH), 1635 (C O)
3288, (NH), 1635 (C O)
3270, (NH), 1690 (C O)
3292, (NH), 1635 (C O)
1705, 1628 (two C O)
1703, 1659 (two C O)
1702, 1661 (two C O)
1710, 1665 (two C O)
1705, 1627 (two C O)
1701, 1658 (two C O)
2.32 (quintet, 2H, J = 5.8 Hz, OCH2CH2),
4.16 (t, 4H, J = 5.8 Hz, OCH2), 6.98–8.22
(m, 20H, ArH’s, NH)
2.17 (quintet, 2H, J = 5.6 Hz, OCH2CH2),
2.37 (s, 6H, CH3), 4.16 (t, 4H, J = 5.8 Hz,
OCH2), 6.99–8.16 (m, 18H, ArH’s and NH)
2.09 (brs, 2H, OCH2CH2), 3.4 (brs, 2H, NH),
4.20 (t, 4H, J = 4 Hz, OCH2), 7.17–8.19 (m,
16H, ArH’s)
1.81 (brs, 4H, OCH2CH2), 2.71 (brs, 2H, NH),
3.95 (brs, 4H, OCH2), 6.95–8.24 (m, 18H,
ArH’s)
1.81 (brs, 4H, OCH2CH2), 2.38 (s, 6H, CH3),
3.94 (brs, 4H, OCH2), 6.98–8.16 (m, 18H,
ArH’s and NH)
1.82 (brs, 4H, OCH2CH2), 3.6 (brs, 2H, NH),
3.94 (brs, 4H, OCH2), 6.97–8.21 (m, 16H,
ArH’s)
1.92 (quintet, 2H, J = 5.6 Hz, OCH2CH2),
1.9 (s, 6H, CH3), 3.86 (t, 4H, J = 5.8 Hz,
OCH2), 6.85–8.28 (m, 18H, ArH’s)
1.91 (m, 2H, OCH2CH2), 1.95 (s, 6H, CH3),
2.34 (t, 4H, J = 5.2 Hz, OCH2), 7.02–8.09
(m, 16H, ArH’s)
1.86 (brs, 2H, OCH2CH2), 1.92 (s, 6H, CH3),
3.94 (brs, 4H, OCH2), 7.03–8.16 (m, 16H,
ArH’s)
1.53 (brs, 4H, OCH2CH2), 2.21 (s, 6H, CH3),
3.84 (brs, 4H, OCH2), 6.95–8.32 (m, 18H,
ArH’s)
6b
6c
6d
6e
6f
7a
7b
7c
7d
7e
7f
1.49 (brs, 4H, OCH2CH2), 2.1 (s, 6H, CH3),
2.36 (s, 6H, Ar-CH3), 3.92 (brs, 4H, OCH2),
7.1–8.1 (m, 16H, ArH’s)
1.53 (brs, 4H, OCH2CH2), 2.51 (s, 6H, CH3),
3.86 (brs, 4H, OCH2), 6.99–8.28 (m, 16H,
ArH’s)
8a
8b
8c
8d
8e
1676, 1641 (two C O)
1657, 1620 (two C O)
1663, 1615 (two C O)
1645, 1618 (two C O)
1650, 1620 (two C O)
1.80 (brs, 2H, OCH2CH2), 3.91 (t, 4H, J = 4.4
Hz, OCH2), 6.85–8.22 (m, 28H, ArH’s)
2.34 (m, 8H, CH3-Ar, OCH2CH2), 3.92 (brs,
4H, OCH2), 6.8–8.15 (m, 26H, ArH’s)
1.79 (brs, 2H, OCH2CH2), 3.92 (t, 4H, J = 5
Hz, OCH2), 6.9–8.20 (m, 26H, ArH’s)
1.36 (brs, 4H, OCH2CH2), 3.53 (brs, 4H,
J = 5.8 Hz, OCH2), 6.5–8.34 (m, 28H, ArH’s)
1.33 (brs, 4H, OCH2CH2), 2.73 (s, 6H, CH3),
3.67 (brs, 4H, OCH2), 6.8–8.13 (m, 26H,
ArH’s)
(Continued on next page)

Synthesis of Novel Bis(thiadiazolin-3-yl) Alkane Derivatives
TABLE II IR and 1H-NMR Data (Continued)
1755
Comp.
IR(cm−1
)
H-NMR(δ)
8f
1645 1620 (two C O)
1.31 (brs, 4H, OCH2CH2), 3.65 (brs, 4H,
OCH2), 6.71–8.23 (m, 26H, ArH’s)
—
9a
9b
9c
1663 (C O)
1643 (C O)
1651 (C O)
—
—
9d
9e
1643 (C O)
1643 (C O)
—
—
9f
1651 (C O)
—
10a
1697, 1651 (two C O)
2.17 (quintet, 2H, J = 5.5 Hz,
OCH2CH2), 4.2 (t, 4H, J = 7.3 Hz,
OCH2), 6.8–8.2 (m, 18H, ArH’s)
2.15 (quintet, 2H, J = 5.8 Hz,
OCH2CH2), 2.37 (s, 6H, CH3), 4.14
(t, 4H, J = 6 Hz, OCH2), 6.94–8.18
(m, 16H, ArH’s)
10b
1697, 1643 (two C O)
10c
10d
10e
1695, 1643 (two C O)
1697, 1651 (two C O)
1720, 1643 (two C O)
2.05 (brs, 2H, OCH2CH2), 4.12 (brs, 4H,
OCH2), 7.01–8.41 (m, 16H, ArH’s)
1.68 (brs, 4H, OCH2CH2), 3.99 (brs, 4H,
OCH2), 7.05–8.14 (m, 18H, ArH’s)
1.72 (brs, 4H, OCH2CH2), 2.37 (s, 6H,
CH3), 4.08 (brs, 4H, OCH2), 7.20–8.09
(m, 16H, ArH’s)
10f
1697, 1651 (two C O)
1.69 (brs, 4H, OCH2CH2), 4.23 (brs, 4H,
OCH2), 7.2–8.15 (m, 16H, ArH’s)
2.32 (quintet, 2H, J = 5.2 Hz, O
CH2CH2), 4.39 (t, 4H, J = 5.4 Hz,
OCH2), 6.98–7.97 (m, 8H, ArH’s), 9.56
(brs, 2H, NH2), 9.64 (s, 2H, NH), 9.81
(brs, 2H, NH2)
13a
3420, 3273, 3144 (NH2 and NH),
2221 (CN), 1537 (C S)
13b
14a
3410, 3290, 3200 (NH2 and NH),
2206 (CN), 1520 (C S)
1.66 (quintet, 2H, J = 7 Hz, SCH2CH2),
2.96 (t, 4H, J = 7 Hz, SCH2), 7.1–8.01
(m, 8H, ArH’s), 9.567 (brs, 2H, NH2),
9.87 (brs, 2H, NH2), 10.13 (s, 2H, NH)
2.7 (brs, 2H, OCH2CH2), 4.55 (brs, 4H,
OCH2), 6.92–8.17 (m, 16H, ArH’s),
9.55 (brs, 4H, NH2), 14.65 (brs, 2H,
NH)
3468, 3330, 3192 (NH2 and NH),
1665 (C O)
14b
14c
14d
3449, (NH), 2216 (CN)
2.65 (brs, 2H, OCH2CH2), 4.54 (brs, 4H,
OCH2), 6.92–8.16 (m, 16H, ArH’s),
14.14 (brs, 2H, NH)
2.17 (brs, 4H, OCH2CH2), 4.35 (brs, 4H,
OCH2), 6.8–8.3 (m, 16H, ArH’s), 9.2
(brs, 4H, 2NH2), 14.7 (brs, 2H, NH).
2.2 (brs, 4H, OCH2CH2), 4.21 (brs, 4H,
OCH2), 6.70–8.0 (m, 16H, ArH’s),
14.44 (brs, 2H, NH)
3464, 3248, 3171 (NH2 and NH),
1659(C O)
3420, (NH), 2208 (CN)

1756
M. A. A. Elneairy et al.
under reflux for 3 h. The excess of the acetic anhydride was evaporated
in vacuo. The solid product was collected by filtration, washed with
water, and crystallized from the acetic acid as yellowish white crystals
to give 7a–f respectively.
Synthesis of 8a--f
General procedure: A solution of the appropriate bis-imino-1,3,4-
thiadiazole derivative each of 6a–f (10 mmol) and benzoyl chloride
(20 ml), in pyridine was stirred at room temperature for 1 h. The reac-
tion mixture was then poured onto ice and acidified with hydrochloric
acid. The solid product was collected by filtration, washed with water,
and crystallized from the proper solvent to give 8a–f respectively.
Synthesis of 9a--f
General procedure: A cold solution of the appropriate 6a–f (0.5 g) in
acetic acid (25 ml) was treated with a saturated aqueous solution of
sodium nitrite with stirring for 30 min. The solid product that formed
was collected by filtration and crystallized from acetic acid as reddish
brown crystal to give 9a–f respectively.
Synthesis of 10a--f
General procedure: The appropriate nitroso derivative 9a–f was re-
fluxed in ethylene glycol (20 ml) for 40 min. The solvent was then diluted
with water. The solid product that formed was collected by filtration,
washed with water, and crystallized from the proper solvent to give
10a–f respectively.
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