Synthesis of some novel bis(pyrazole), bis(pyridine) and bis(pyrazolo[5,1-c]-1,2,4-triazine derivatives

Article abstract of DOI:10.3987/COM-09-11676

Treatment of N,N′-(ethane-1,2-diyl)bis(cyanoacetamide) (1) with hydrazonoyl chlorides 2a,b afforded bis(aminopyrazoles) 5a,b. Heating of compound 1 with arylmethylenepropanedinitrile 9a-c afforded bis(pyridine) derivatives 13a-c. Also, compound 1 coupled

Full text of DOI:10.3987/COM-09-11676

HETEROCYCLES, Vol. 78, No. 7, 2009
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HETEROCYCLES, Vol. 78, No. 7, 2009, pp. 1815 - 1822. © The Japan Institute of Heterocyclic Chemistry
Received, 5th February, 2009, Accepted, 27th March, 2009, Published online, 31st March, 2009
DOI: 10.3987/COM-09-11676
SYNTHESIS OF SOME NOVEL BIS(PYRAZOLE), BIS(PYRIDINE) AND
BIS(PYRAZOLO[5,1-c]-1,2,4-TRIAZINE DERIVATIVES
Nabila A. Kheder*
Department of Chemistry, Faculty of Science, Cairo University, Giza 12613,
Egypt
E-mail: nabila_abdelshafy@yahoo.com
Abstract – Treatment of N,N'-(ethane-1,2-diyl)bis(cyanoacetamide) (1) with
hydrazonoyl chlorides 2a,b afforded bis(aminopyrazoles) 5a,b. Heating of
compound 1 with arylmethylenepropanedinitrile 9a-c afforded bis(pyridine)
derivatives 13a-c. Also, compound 1 coupled smoothly with the arenediazonium
salt generated from 3-chloroaniline or 5-amino-4-methyl-3-phenylpyrazole (16) to
afford the corresponding hydrazones 15 or bis(pyrazolo[5,1-c]-1,2,4-triazine-3-
carboxamide) 19. Refluxing of compound 1 with N,N-dimethylformamide
dimethyl acetal (DMF-DMA) in xylene afforded bis(2-cyano-3-(dimethylamino)-
acrylamide) (20) which reacted with hydrazine hydrate to afford the novel
bis(cyanoopyrazole) 23.
Recently, bis(heterocycles) have received grate deal of attention, not only for being model compounds for
main chain polymers,1-6 but also because many biologically active natural and synthetic products have
molecular symmetry.7 On the other hand, the synthesis of combinatorial libraries of heterocyclic
compounds permits the testing of the biological properties of a vast array of compounds. Routes to novel
skeletons, which could be synthesized using combinatorial methods, are presently a major research
objective. In continuation of our recent work aiming at the synthesis of bis(heterocyclic) systems, 8-12 it
was found that compound 1, is versatile and readily accessible building block for the synthesis of several
new bis(pyrazole)-, bis(pyridine)- and bis(pyrazolo[5,1-c]-1,2,4-triazine) derivatives of expected
biological potency.
Treatment of compound 113 with hydrazonoyl chloride 2a14 in ethanolic sodium ethoxide solution at rt
furnished a single product for which the two possible structures 5a and 8a can be envisaged (Scheme 1).
However, elemental analyses and spectral data were in complete accordance with the bis(aminopyrazole)

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HETEROCYCLES, Vol. 78, No. 7, 2009
structure 5a. The IR spectrum of 5a showed absorption bands at 3439, 3315, 3261, 1675 and 1639 cm-1
due to amino, amide-NH and two carbonyl groups, respectively. Its 1H NMR spectrum showed signals at
δ 2.49, 3.37 and two D2O-exchangeable signals at δ 6.83 and 9.65 due to CH3, NCH2, amino and imino
protons, respectively in addition to an aromatic multiplet in the region δ 7.53-7.62. Prompted by the
foregoing results and to generalize this finding I also studied the reaction of the acetamide 1 with other
hydrazonoyl chloride 2b15 under the same experimental conditions and obtained the respective
aminopyrazole derivative 5b.
CN
H
N
X
NH
H
N
O
CN
R
N
Ar
O
1
2a,b
EtONa EtOH
Ar
Ar
Ar
NH
NH CN
N
N
HN
CN
O
N
R
O
CN
H
N
R
R
N
H
R
HN
N
H
O
O
CN
N
6
3
NH
Ar
Ar
N
N
H
CN
R
HO
HN
NH
H
H
N
Ar
R
N
NH
R
N
O
N
O
N
Ar
R
Ar
NH
OH
N
N
N
H
NC
H
H
7
4
-2H2O
Ar
N N
CN
Ar
H
N
Ar
NH2
N
R
NH2
N
N
R
H
R
N
N
N
N
N
H
N
O
Ar
H
NC
R
O
5a,b
2-8: R / Ar
a: MeCO / Ph
b: Ph / Ph
8
5a (53%), 5b (66%)
Scheme 1
Treatment of compound 1 with arylmethylenepropanedinitrile 9a-c16 furnished 1, 1'-(ethane-1,2-diyl)-
bis(6-amino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile) 13a-c (Scheme 2). The IR spectrum of
compound 13a, taken as a typical example of the prepared series, revealed absorption bands at 1631,
2206, 3317 and 3392 cm-1 corresponding to carbonyl group, nitrile function and amino group,
respectively. Its 1H NMR spectrum showed signals at δ 3.13 and D2O-exchangeable signals at δ 4.18 due

HETEROCYCLES, Vol. 78, No. 7, 2009
1817
to NCH2 and NH2 protons, respectively, in addition to an aromatic multiplet in the region δ 7.44-7.53.
Compounds 13a-c are assumed to be formed via an initial Michael type adducts 10 followed by an
intramolecular cyclization and dehydrogenation to the final products 13a-c (Scheme 2).
CN
CN
NC
NC
NC
NH
CN
CN
H
N
CN
HN
Ar
Ar
NH
+
Ar
O
CN
O
CN
O
O
9a-c
1
10a-c
NC
H
NH
NC
NC
NH2
O
N
CN
O
CN
Ar
N
Ar
N
O
Ar
N
Ar
NC
O
H
HN
CN
H2N
CN
12a-c
11a-c
-2H2
NC
NC
NH2
O
N
CN
CN
Ar
N
O
Ar
9-13: a, Ar = Ph
b, Ar = 4-MeOC6H4
c, Ar = 4-ClC6H4
H2N
13a-c
13a (70%), 13b (72%), 13c (77%)
Scheme 2
Compound 1 coupled smoothly with the diazonium salt 14 generated from 3-chloroaniline in pyridine to
afford N,N'-(ethane-1,2-diyl)bis[2-(N''-(4-chlorophenylhydrazonoyl)-2-cyanoacetamide] (15) (Scheme 3).
The IR spectrum of 15 showed absorption bands at 1651 and 2222 cm-1 corresponding to carbonyl group
1
and nitrile function, respectively. Its H NMR spectrum showed signal at δ 3.39 due to NCH2 and two
D2O-exchangeable signals at δ 8.65 and 14.39 due to two NH protons, in addition to an aromatic
multiplet in the region δ 7.10-7.88.
CN
Ar
NC
O
H
N
NH N NH
+
NH
ArN2Cl
HN N HN
Ar
O
CN
O
CN
O
1
15 (66%)
14
Ar = 3-ClC6H4
Scheme 3

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HETEROCYCLES, Vol. 78, No. 7, 2009
In a similar manner, compound 1 coupled smoothly with the diazonium salt 17 generated from 5-amino-
4-methyl-3-phenylpyrazole (16) in pyridine, at room temperature to afford a single product identified as
N,N'-(ethane-1,2-diyl)bis(4-imino-8-methyl-7-phenyl-1,4-dihydropyrazolo[5,1-c]-1,2,4-triazine-3-carbox-
amide) (19) (Scheme 4).
+
N2
CN
H
N
Me
Ph
NH
NH
+
O
CN
N
O
1
17
Ph
N
NH
Ph
N
HN
H
NC
N
O
O
N
Me
N
HN
NH N NH
NH
Me
Ph
Me
N
Me
Ph
N
HN N HN
O
CN
H
NH
O
N
N
N
HN
18
19 (62%)
Scheme 4
1
The IR spectrum of 19 revealed the absence of a band corresponding to nitrile function. Its H NMR
spectrum showed signals at δ 2.48, 3.59 due to CH3 and NCH2 protons, and three D2O-exchangeable
signals at δ 9.01, 9.12 and 9.2 due to three NH protons, in addition to aromatic multiplet in the region
7.30-7.89.
Treatment of compound 1 with N,N-dimethylformamide-dimethylacetal (DMF-DMA) in refluxing xylene
1
afforded N,N'-(ethane-1,2-diyl)bis[2-cyano-3-(dimethylamino)acrylamide] (20). The H NMR spectrum
of compound 20 showed signals at δ 3.19, 3.22, 3.33, 7.19 and 7.68 due to N,N–dimethylamino, NCH2,
C=CH-N and amide-NH protons, respectively. When compound 20 was treated with hydrazine hydrate in
refluxing EtOH, the novel 3,3'-(ethane-1,2-diyl)bis(azanediyl)bis(1H-pyrazole-4-carbonitrile) (23) was
produced (Scheme 5). The IR spectrum of the isolated product showed absorption bands at 3314 and
2217 cm-1 characteristic for NH and nitrile function, respectively. Its 1H NMR spectrum showed signals at
δ 3.35, 8.40, 10.2 and 11.0 corresponding to NCH2, CH and two D2O-exchangeable signals corresponding
to two NH protons. The foregoing spectral data supported the proposed structure 23 and ruled out the
other possible pyrazole structure 24 (Scheme 5).
In conclusion, the reactivity of N,N'-(ethane-1,2-diyl)bis(cyanoacetamide) (1) was investigated as a
versatile and readily accessible building block for the synthesis of new bis(heterocycles) of biological
and pharmaceutical importance.

HETEROCYCLES, Vol. 78, No. 7, 2009
1819
EXPERIMENTAL
All melting points were measured on a Gallenkamp melting point apparatus. The infrared spectra were
recorded in potassium bromide disks on a Pye Unicam SP 3300 and Shimadzu FT IR 8101 PC infrared
spectrophotometers. The NMR spectra were recorded on a Varian Mercury VX-300 NMR spectrometer.
CN
NC
Me2N
O
H
H
N
NH
O
NMe2
NH
DMF-DMA
HN
O
CN
H
CN
O
20
1
NH2NH2 .H2O
H2N
NH
NC H O
NC H O
Me2N
NH
NH
NMe2
Me2N
H2N
HN
NH
NH2
HN
HN
O H CN
21A
HN NH2
NMe2
O H CN
21
- 2Me2NH
CN
- 2Me2NH
OH
H
N
HN
NH
NH2
O
HN
NH
N
HN
N
H
NH
HO
NC
NH
22
HN
N
O
-2H2O
CN
H2N
24
H
N
HN
N
N
NH
N
H
NC
23 (66%)
Scheme 5
1H spectra were run at 300 MHz and 13C spectra were run at 75.46 MHz in deuterated dimethyl sulfoxide
(DMSO-d6). Chemical shifts were related to that of the solvent. Mass spectra were recorded on a
Shimadzu GCMS-QP 1000 EX mass spectrometer at 70 e.V. Elemental analyses were carried out at the
Microanalytical Center of Cairo University, Giza, Egypt. N, N'-(Ethane-1,2-diyl)bis[cyanoacetamide]
(1),13
hydrazonoyl
halides
2a,14
2b,15
arylmethylenepropanedinitrile
9a-c16
and
5-amino-4-methyl-3-phenyl- pyrazole (16)17 were prepared following the literature procedure.
Reaction of N, N'-(Ethane-1,2-diyl)bis(cyanoacetamide)(1) with hydrazonoyl halides.
General procedure:
Compound 1 (0.194 g, 1 mmol) was added to an ethanolic sodium ethoxide solution [prepared from
sodium metal (46 mg, 2 mmol) and absolute EtOH (20 mL)] with stirring. After stirring the resulting

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HETEROCYCLES, Vol. 78, No. 7, 2009
solution for 15 min., the appropriate hydrazonoyl halide 2a,b (2 mmol) was added portionwise and the
reaction mixture was stirred further for 12 h at rt. The solid product that formed was filtered off, washed
with water and dried. Recrystallization from the proper solvent afforded the corresponding bis(pyrazole)
derivatives 5a,b.
N,N'-(Ethane-1,2-diyl)bis(3-acetyl-5-amino-1-phenyl-1H-pyrazole-4-carboxamide)(5a). Yield (53%),
1
mp > 300 °C (DMF); IR (KBr) ν 1639 (C=O), 1675 (C=O), 3261 and 3315 (NH2), 3439 (NH) cm-1; H
NMR (DMSO-d6) δ 2.49 (s, 6H, 2CH3), 3.37 (s, 4H, 2NCH2), 6.83 (s, 4H, D2O-exchangeable 2NH2),
7.53-7.62 (m, 10H, Ar-H), 9.65 (s, 2H, D2O-exchangeable 2NH); MS m/z (%) 271 (6.91), 258 (1.47), 257
(M+/2, 2.64). Anal. Calcd for C26H26N8O4: C, 60.69; H, 5.09; N, 21.78. Found: C, 60.61; H, 5.02; N,
21.72%.
N, N'-(Ethane-1,2-diyl)bis(5-amino-1,3-diphenyl-1H-pyrazole-4-carboxamide) (5b).
1
Yield (66%), mp > 300 °C (DMF); IR (KBr) ν 1632 (C=O), 3055 (NH), 3314 and 3422 (NH2) cm-1; H
NMR (DMSO-d6) δ 3.20 (s, 4H, 2NCH2), 6.29 (s, 4H, D2O-exchangeable 2NH2), 7.18-7.62 (m, 20H,
Ar-H), 9.57 (s, 2H, D2O-exchangeable 2NH). Anal. Calcd for C34H30N8O2: C, 70.09; H, 5.19; N, 19.23.
Found: C, 70.01; H, 5.24; N, 19.25%.
Synthesis of 1,1'-(ethane-1,2-diyl)bis[6-amino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile]
13a-c.
General procedure:
To a solution of the appropriate arylmethylenepropanedinitrile 9a-c (2 mmol) in EtOH (20 mL) was
added compound 1 (0.194 g, 1 mmol), and few drops of piperidine and the reaction mixture was heated
under reflux for 2 h. The solid product that formed was collected by filtration, washed with EtOH and
then crystallized from a proper solvent to afford the corresponding bis(pyridine) derivatives 13a-c.
1,1'-(Ethane-1,2-diyl)bis(6-amino-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-dicarbonitrile)(13a). Yield
(70%), mp > 300 °C (DMF); IR (KBr) ν 3392 and 3317 (NH2), 2206 (C≡N), 1631 (C=O) cm-1; 1H NMR
(DMSO-d6) δ 3.13 (s, 4H, 2NCH2), 4.18 (s, 4H, D2O-exchangeable 2 NH2), 7.44-7.53 (m, 10H, Ar-H);
13C NMR (DMSO-d6) δ 43.92, 76.92, 83.28, 117.15, 117.49, 127.79, 128.40, 129.72, 135.34, 158.02,
159.33, 160.39. Anal. Calcd for C28H18N8O2: C, 67.46; H, 3.64; N, 22.48. Found: C, 67.41; H, 3.60; N,
22.51%.
1,1'-(Ethane-1,2-diyl)bis(6-amino-4-(4-methoxyphenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile)
(13b). Yield (72%), mp > 300 °C (DMF); IR (KBr) ν 3333 and 3179 (NH2), 2214 (C≡N), 1651 (C=O)
cm-1; 1H NMR (DMSO-d6) δ 3.02 (s, 4H, 2NCH2), 3.83 (s, 6H, 2OCH3), 4.21 (s, 4H, D2O- exchangeable
2 NH2), 7.06 (d, 4H, ArH’s, J = 8.7 Hz), 7.4 (d, 4H, ArH’s, J = 8.7 Hz). Anal. Calcd for C30H22N8O4: C,
64.51; H, 3.97; N, 20.06. Found: C, 64.57; H, 3.92; N, 20.10%.
1,1'-(Ethane-1,2-diyl)bis(6-amino-4-(4-chlorophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile)

HETEROCYCLES, Vol. 78, No. 7, 2009
1821
(13c). Yield (77%), mp > 300 °C (DMF); IR (KBr) ν 3333 and 3179 (NH2), 2214 (C≡N), 1636 (C=O)
1
cm-1; H NMR (DMSO-d6) δ 3.01 (s, 4H, 2NCH2), 4.17 (s, 4H, D2O-exchangeable 2 NH2), 7.48 (d, 4H,
ArH’s, J = 8.4 Hz), 7.62 (d, 4H, ArH’s, J = 8.4 Hz); 13C NMR (DMSO-d6) δ 43.92, 76.93, 89.16, 117.03,
117.39, 128.59, 129.80, 134.19, 134.57, 157.97, 158.09, 160.28. Anal. Calcd for C28H16N8Cl2O2: C,
59.27; H, 2.84; N, 19.75. Found: 59.32; H, 2.80; N, 19.70%.
Synthesis of N,N'-(ethane-1,2-diyl)]bis[2-(N''-(4-chlorophenylhydrazonoyl)-2-cyanoacetamide] (15)
and N,N'-(ethane-1,2-diyl)bis(4-imino-8-methyl-7-phenyl-1,4-dihydropyrazolo[5,1-c]-1,2,4-triazine-3-
carboxamide)(19).
General procedure.
To a cold solution of the compound 1 (0.194 g, 1 mmol) in pyridine (20 mL) was added the appropriate
diazonium salt generated from 3-chloroaniline or 5-amino-4-methyl-3-phenylpyrazole (16) [prepared by
diazotizing the appropriate amine (2 mmol) in hydrochloric acid (6M, 1.2 mL) with sodium nitrite
solution (0.138 g, 2 mmol) in water (1.0 mL)]. The addition was carried out portionwise with stirring at
0-5 ºC over a period of 30 min. After complete addition, the reaction mixture was stirred for further 4 h,
then kept in an ice chest for 12 h, and finally diluted with water. The precipitated solid was collected by
filtration, washed with water, dried and finally recrystallized from a proper solvent to afford the
corresponding products 15 and 19, respectively.
N,N'-(Ethane-1,2-diyl)bis[2-(N''-(4-chlorophenylhydrazonoyl)-2-cyanoacetamide] (15). Yield (66%),
1
mp 270 °C (DMF); IR (KBr) ν 3356 (NH), 3074 (NH), 2222 (C≡N), 1651 (C=O) cm-1; H NMR
(DMSO-d6) δ 3.39 (s, 4H, 2NCH2), 7.10-7.88 (m, 8H, Ar-H), 8.65 (s, 2H, D2O-exchangeable 2NH),
14.39 (s, 2H, D2O-exchangeable 2NH); MS m/z (%) 473 (14.1), 472 (30.6), 470 (M+-1, 30.5), 248 (14.5),
112 (8.4), 111 (64.5). Anal. Calcd for C20H16Cl2N8O2: C, 50.97; H, 3.42; N, 23.78. Found: C, 50.93; H,
3.47; N, 23.72%.
N,N'-(Ethane-1,2-diyl)bis(4-imino-8-methyl-7-phenyl-1,4-dihydropyrazolo[5,1-c]-1,2,4-triazine-3-carb-
oxamide)(19). Yield (62%), mp 283 °C (DMF); IR (KBr) ν 3306 (NH), 3209 (NH), 1659 (C=O) cm-1; 1H
NMR (DMSO-d6) δ 2.48 (s, 6H, 2CH3,), 3.59 (s, 4H, 2NCH2), 7.30 (m, 2H), 7.47 (m, 4H), 7.89 (d, 4H),
9.01 (s, 2H, D2O-exchangeable 2NH), 9.12 (s, 2H, D2O-exchangeable 2NH), 9.20 (s, 2H, D2O-
exchangeable 2NH). Anal. Calcd for C28H26N12O2: C, 59.78; H, 4.66; N, 29.88. Found: C, 59.72; H, 4.63;
N, 29.83%.
Reaction of N,N'-(ethane-1,2-diyl)bis(cyanoacetamide) (1) with DMF-DMA.
A mixture of the compound 1 (1.94 g, 10 mmol) and N,N-dimethylformamide dimethyl acetal
(DMF-DMA) (2.66 ml, 20 mmol) in dry xylene (30 mL) was refluxed for 3 h, then left to cool to rt. The
yellow precipitated product was filtered off, washed with petroleum ether and dried. Crystallization from
EtOH/ DMF gave N,N'-(ethane-1,2-diyl)bis[2-cyano-3-(dimethylamino)acrylamide] (20) in 54 % yield,

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HETEROCYCLES, Vol. 78, No. 7, 2009
1
mp 224 °C; IR (KBr) ν 3348 (NH), 2195 (C≡N), 1655 (C=O) cm-1; H NMR (DMSO-d6) δ 3.19 (s, 6H,
2CH3), 3.22 (s, 6H, 2CH3,), 3.33 (s, 4H, 2NCH2), 7.19 (s, 2H, 2CH), 7.68 (s, 2H, D2O-exchangeable
2NH); 13C NMR (DMSO-d6) δ 37.90, 46.69, 69.90, 119.49, 155.86, 164.81. Anal. Calcd for C14H20N6O2:
C, 55.25; H, 6.62; N, 27.61. Found: C, 55.20; H, 6.67; N, 27.57%.
Reaction of N,N'-(ethane-1,2-diyl)bis[2-cyano-3-(dimethylamino)acrylamide] (20) with hydrazine
hydrate.
To a solution of the compound 20 (0.30 g, 1 mmol) in EtOH (20 mL), hydrazine hydrate (80%, 0.2 mL, 2
mmol) was added and the reaction mixture was refluxed for 4 h, then left to cool. The solid product so
formed was filtered off, washed with EtOH and dried. Recrystallized from DMF afforded
3,3'-(ethane-1,2-diylbis(azanediyl)bis[1H-pyrazole-4-carbonitrile] (23), yield (66%), mp > 300 °C; IR
1
(KBr) ν 3314 (NH), 2217 (C≡N) cm-1; H NMR (DMSO-d6) δ 3.35 (s, 4H, 2NCH2), 8.40 (s, 2H, 2CH),
10.2 (s, 2H, D2O-exchangeable 2NH), 11.0 (s, 2H, D2O-exchangeable 2NH). Anal. Calcd for C10H10N8: C,
49.58; H, 4.16; N, 46.26. Found: C, 49.52; H, 4.20; N, 46.21%.
REFERENCES
1. S. Furuya, H. Matsumoto, Y. Hayase, N. Suzuki, and T. Imada, PCT Int Appl. WO 97 41, 126
[Chem. Abstr., 1998, 128, 13211f].
2. H. Vieweg, S. Leistner, J. Prantz, N. Bohm, and G. Wagner, Pharmazie, 1992, 47, 841.
3. A. G. Griffin and T. R. Britt, J. Am. Chem. Soc., 1981, 103, 4957.
4. G. Galli, M. Laus, and A. S. Angeloni, Makromol. Chem., 1986, 187, 289.
5. H. Ringsdorf, B. Schlarh, and J. Venzmer, Angew. Chem., Int. Ed. Engl., 1988, 27, 115.
6. H. Finkelman, Angew. Chem., Int. Ed. Engl., 1987, 26, 816.
7. C. Aguilera, M. Parra, and G. Fuentes, Z. Naturforsch, 1998, 53B, 367.
8. N. A. Kheder, Y. N. Mabkhot, and A. M. Farag, Heterocycles, 2008, 75, 887.
9. N. A. Kheder, Y. N. Mabkhot, and A. M. Farag, Synth. Commun., 2008, 38, 3170.
10. N. A. Kheder, Y. N. Mabkhot, and A. M. Farag, Arkivoc, 2008, xvii, 107.
11. N. A. Kheder, Y. N. Mabkhot, and A. M. Farag, Heterocycles, 2008, 75, 2937.
12. N. A. Kheder, E. S. Darwish, and K. M. Dawood, Heterocycles, 2009, 78, 177.
13. J. Guareschi, Chem. Ber., 1892, 25, 326.
14. W. Dieckmann and O. Platz, Chem. Ber., 1906, 38, 2989.
15. P. Wolkoff, Can. J. Chem., 1975, 53, 1333.
16. P. Shanthan Rao and R. V. Venkataratnam, Tetrahedron Lett., 1991, 32, 5821.
17. S. Checchi, P. Papini, and M. Ridi, Gazz. Chim. Ital., 1955, 85, 1160.