Novel synthesis of 4,5-dihydrospiropyrazole-5,2′-indane-1′,3′-diones

Article abstract of DOI:10.1081/SCC-120012997

A novel synthesis of 4,5-dihydrospiropyrazole-5,2′-indane-1′,3′-diones 7a-n, 8a-c,e,f and 12a-f via the treatment of hydrazonoyl halides 1-3 with 2-arylidene indane-1,3-diones 6a-e respectively, is reported.

Full text of DOI:10.1081/SCC-120012997

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NOVEL SYNTHESIS OF 4,5-DIHYDROSPIROPYRAZOLE-
5,2′-INDANE-1′,3′-DIONES
Hamdi M. Hassaneen a , Nehal M. Elwan a & Huwaida M. Hassaneen a
a Chemistry Department, Faculty of Science, Cairo University, Giza, Egypt
Published online: 16 Aug 2006.
To cite this article: Hamdi M. Hassaneen , Nehal M. Elwan & Huwaida M. Hassaneen (2002) NOVEL SYNTHESIS OF 4,5-
DIHYDROSPIROPYRAZOLE- 5,2′-INDANE-1′,3′-DIONES, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 32:19, 3047-3055, DOI: 10.1081/SCC-120012997
To link to this article: http://dx.doi.org/10.1081/SCC-120012997
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 19, pp. 3047–3055, 2002
NOVEL SYNTHESIS OF
4,5-DIHYDROSPIROPYRAZOLE-
5,20-INDANE-10,30-DIONES
*
Hamdi M. Hassaneen, Nehal M. Elwan,
and Huwaida M. Hassaneen
Chemistry Department, Faculty of Science,
Cairo University, Giza, Egypt
ABSTRACT
A novel synthesis of 4,5-dihydrospiropyrazole-5,20-indane-
10,30-diones 7a–n, 8a–c,e,f and 12a–f via the treatment of
hydrazonoyl halides 1–3 with 2-arylidene indane-1,3-diones
6a–e respectively, is reported.
Due to their reactivity and their ease of preparation hydrazonoyl
halides[1–8] 1–3 have been used as starting material for the formation of
various heterocyclic systems.[9] Now, we report on the reaction of hydrazo-
noyl halides 1–3 with 2-arylidene indane-1,3-diones 6a–e prepared as
previously described by refluxing of indane-1,3-dione 5 with the aromatic
aldehydes in ethanol in the presence of piperidine (Sch. 1). The
physical constants obtained for 6a–e are in agreement with those reported
in literature.[10–12]
*Corresponding author. E-mail: hamdi251@hotmail.com
3047
DOI: 10.1081/SCC-120012997
Copyright & 2002 by Marcel Dekker, Inc.
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3048
HASSANEEN, ELWAN, AND HASSANEEN
Scheme 1.
Scheme 2.
Reaction of 2-arylidene indane-1,3-diones 6a–e with C,N-diarylnitri-
limines 4a–c, generated in situ by action of triethylamine on the corre-
sponding C,N-diarylhydrazonoyl halides 1a–c, was investigated. Thus,
refluxing equimolar amounts of the 2-arylidene indane-1,3-diones 6a–e,
hydrazonoyl halides 1a–c and triethylamine for 6 h in chloroform gave
after work up in each case, only one spirocycloadduct (Sch. 2). All cycload-
ducts 7 gave satisfactory elemental analyses and the spectral data
(IR, 1H NMR, MS) supported the proposed structures. For example,

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4,5-DIHYDROSPIROPYRAZOLE-5,20-INDANE-10,30-DIONES
3049
the 1H NMR spectrum of each compound showed a singlet signal at
ꢀ ꢀ 5.20 ppm assignable to the proton at position 4. This chemical shift
agreed with values reported in literature.[13]
Also, we studied the reaction of 2-arylidene indane-1,3-diones 6a–c,e
with a-alkoxycarbonylmethanohydrazonoyl halides 3a,b to investigate
the effect of the presence of a-alkoxycarbonyl group on the course of
cycloaddition reaction.
Treatment of 6a with ethyl a-phenylhydrazonochloroacetate 3a in
refluxing chloroform in the presence of triethylamine afforded one product,
the spirodione 8a (Sch. 3). Similarly, reaction of 6a with methyl a-phenyl-
hydrazonochloroacetate 3b under similar conditions yielded the respective
spirocycloadduct 8f (Sch. 3).
The structures of the products 8a,f were established on the basis of
spectral data and elemental analyses. Also, 2-arylidene indane-1,3-diones
Scheme 3.

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3050
HASSANEEN, ELWAN, AND HASSANEEN
Scheme 4.
6b,c,e react with hydrazonoyl halides 3a to give the corresponding spiro-
cycloadducts 8b,c,e respectively (Sch. 4).
Refluxing of either 8a or 8f in sodium methoxide in absolute methanol
yielded 9. Similarly 8a or 8f gave 10 on boiling in ethanolic sodium ethoxide
solution. Further evidence in support of the assigned structure 10
is provided by the alternate synthesis of 10 from indane-1,3-dione 5
and ethyl-3-oxo-2-phenylhydrazono-3-phenylpropanoate[14] 11 (see experi-
mental) (Sch. 3).
Next, the reaction of 2-arylidene indane-1,3-diones 6a–d with a-keto-
hydrazonoyl halides namely a-benzoyl and a-acetylmethano-hydrazonoyl
halides 2a and 2b respectively, gives the corresponding spirocycloadducts
12a–d, 12e,f respectively (Sch. 5). The structures of the products were
inferred from elemental analyses and spectral data, (see experimental).
Treatment of 12a with sodium methoxide in methanol leads to open chain
compound 13, which also obtained by independent synthesis according
to Sch. 5.
EXPERIMENTAL
Melting points were determined on a Gallenkamp electrothermal
apparatus and are uncorrected. IR spectra (KBr) were recorded on a Pye
Unicam SP-300 IR spectrophotometer and Testscan Shimadzu FTIR 8000
1
series. H NMR spectra were recorded on a Varian Gemini 200 and Varian
EM 390 spectrometer using solution in deuterated chloroform and TMS
as internal standard. Mass spectra were recorded on a GCMS-QP
1000-EX shimadzu, Japan. Elemental analyses were carried out at the
Microanalytical Center, University of Cairo, Giza, Egypt.

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4,5-DIHYDROSPIROPYRAZOLE-5,20-INDANE-10,30-DIONES
3051
Scheme 5.
4,5-Dihydrospiropyrazole-5,20-indane-10,30-diones 7a–n, 8a–c,e,f, 12a–f:
General procedure: To a mixture of hydrazonoyl halides 1–3 (5 mmol) and
2-arylidene indane-1,3-diones 6a–e (5 mmol) in chloroform (40 mL),
triethylamine (0.7 mL) was added. The reaction mixture was refluxed for
6 h. Then, the solvent was evaporated under reduced pressure and the resi-
due was triturated with methanol (10 mL) and solidified. The crude product
was collected and crystallized from suitable solvent. 7a: m.p. 170ꢁC (acetic
acid); 77% yield; ꢁmax/cmÀ1 (KBr); 1746 (C¼O), 1714 (C¼O); ꢀH (CDCl3)
5.2 (s, 1H, pyrazole H-4); 6.7–8.2 (m, 19H, aromatic protons). (Found:
C, 81.2; H, 4.5; N, 6.4. C29H20N2O2 requires C, 81.3; H, 4.7; N, 6.5%).
7b: m.p. 162ꢁC (ethanol); 87% yield; ꢁmax/cmÀ1 (KBr) 1750 (C¼O), 1716
(C¼O); ꢀH (CDCl3) 2.3 (s, 3H, CH3); 5.2 (s, 1H, pyrazole H-4); 6.6–8.2 (m,
18H, aromatic protons). (Found: C, 81.3; H, 5.0; N, 6.4. C30H22N2O2
requires C, 81.4; H, 5.0; N, 6.3%). 7c: m.p. 178ꢁC (acetic acid); 80%
yield; ꢁmax/cmÀ1 (KBr) 1748 (C¼O), 1714 (C¼O); ꢀH (CDCl3) 5.2 (s, 1H,
pyrazole H-4); 6.8–8.2 (m, 18H, aromatic protons) (Found: C, 75.2; H, 3.9;
Cl, 7.8; N, 6.2. C29H19ClN2O2 requires C, 75.2; H, 4.1; Cl, 7.7; N, 6.1%). 7d:
m.p. 250ꢁC (acetic acid); 77% yield; ꢁmax/cmÀ1 (KBr) 1753 (C¼O), 1714
(C¼O); ꢀH (CDCl3) 5.2 (s, 1H, pyrazole H-4); 6.8–8.2 (m, 18H, aromatic
protons); m/z 473 (Found: C, 73.4; H, 4.1; N, 8.9. C29H19N3O4 requires C,
73.6; H, 4.0; N, 8.9%). 7e: m.p. 205ꢁC (acetic acid); 72% yield; ꢁmax/cmÀ1
(KBr) 1744 (C¼O), 1712 (C¼O); ꢀH (CDCl3) 5.4 (s, 1H, pyrazole H-4);

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3052
HASSANEEN, ELWAN, AND HASSANEEN
6.6–8.2 (m, 17H, aromatic protons); m/z 434 (Found: C, 74.4; H, 3.9; N, 6.4;
S, 7.4. C27H18N2O2S requires C, 74.6; H, 4.2; N, 6.5; S, 7.4%). 7f: m.p.
155ꢁC (acetic acid); 80% yield; ꢁmax/cmÀ1 (KBr) 1748 (C¼O), 1713 (C¼O);
ꢀH (CDCl3) 5.0 (s, 1H, pyrazole H-4); 6.1–8.2 (m, 21H, aromatic protons).
(Found: C, 81.7; H, 4.7; N, 6.4. C31H22N2O2 requires C, 81.9; H, 4.9;
N, 6.2%). 7g: m.p. 211ꢁC (acetic acid); 68% yield; ꢁmax/cmÀ1 (KBr) 1750
(C¼O), 1714 (C¼O); (CDCl3) 2.3 (s, 3H, CH3); 5.0 (s, 1H, pyrazole H-4);
6.2–8.2 (m, 20H, aromatic protons); m/z 468 (Found: C, 82.2; H, 5.0; N, 5.8.
C32H24N2O2 requires C, 82.0; H, 5.1; N, 6.0%). 7h: m.p. 195ꢁC (acetic acid);
80% yield; ꢁmax/cmÀ1 (KBr) 1750 (C¼O), 1713 (C¼O); ꢀH (CDCl3) 5.0
(s, 1H, pyrazole H-4); 6.1–8.1 (m, 20H, aromatic protons); m/z 488
(Found: C, 76.1; H, 4.5; Cl, 7.3; N, 5.6. C31H21ClN2O2 requires C, 76.1;
H, 4.3; Cl, 7.3; N, 5.7%). 7i: m.p. 195ꢁC (acetic acid); 79% yield; ꢁmax/cmÀ1
(KBr) 1750 (C¼O), 1715 (C¼O); ꢀH (CDCl3) 5.3 (s, 1H, pyrazole H-4),
6.3–8.2 (m, 19H, aromatic protons); m/z 460 (Found: C, 75.3; H, 4.4; N,
6.2; S, 6.9. C29H20N2O2S requires C, 75.6; H, 4.4; N, 6.1; S, 7.0%). 7j: m.p.
160ꢁC (acetic acid); 77% yield; ꢁmax/cmÀ1 (KBr) 1749 (C¼O), 1714 (C¼O);
ꢀH (CDCl3) 5.1 (s, 1H, pyrazole H-4), 6.6–8.7 (m, 16H, aromatic protons).
(Found: C, 67.5; H, 3.7; N, 8.7; S, 6.8. C27H17N3O4S requires C, 67.6; H,
3.6; N, 8.8; S, 6.7%). 7k: m.p. 273ꢁC (acetic acid); 83% yield; ꢁmax/cmÀ1
(KBr) 1750 (C¼O), 1716 (C¼O); ꢀH (CDCl3) 2.3 (s, 3H, CH3), 5.2 (s, 1H,
pyrazole H-4), 6.7–8.2 (m, 15H, aromatic protons). (Found: C, 68.4; H, 3.9;
N, 8.4; S, 6.3. C28H19N3O4S requires C, 68.1; H, 3.9; N, 8.5; S, 6.5%). 7l:
m.p. 210ꢁC (acetic acid); 66% yield; ꢁmax/cmÀ1 (KBr) 1752 (C¼O), 1717
(C¼O); ꢀH (CDCl3) 5.2 (s, 1H, pyrazole H-4), 6.6–8.2 (m, 15H, aromatic
protons); m/z 513 (Found: C, 63.1; H, 3.2; Cl, 6.8; N, 8.2; S, 6.3.
C27H16ClN3O4S requires C, 63.1; H, 3.1; Cl, 6.9; N, 8.2; S, 6.2%).
7m: m.p. 263ꢁC (acetic acid); 76% yield; ꢁmax/cmÀ1 (KBr) 1752 (C¼O),
1712 (C¼O); ꢀH (CDCl3) 5.3 (s, 1H, pyrazole H-4), 6.6–8.3 (m, 15H, aro-
matic protons); m/z 525 (Found: C, 61.8; H, 3.2; N, 10.6; S, 6.2.
C27H16N4O6S requires C, 61.8; H, 3.1; N, 10.7; S, 6.1%). 7n: m.p. 200ꢁC
(acetic acid); 80% yield; ꢁmax/cmÀ1 (KBr) 1752 (C¼O), 1718 (C¼O); ꢀH
(CDCl3) 5.2 (s, 1H, pyrazole H-4), 6.5–8.0 (m, 14H, aromatic protons).
(Found: C, 61.6; H, 2.9; N, 8.7; S, 13.1. C25H15N3O4S2 requires C, 61.8;
H, 3.1; N, 8.7; S, 13.2%). 8a: m.p. 178ꢁC (acetic acid); 80% yield; ꢁmax/cmÀ1
(KBr) 1752 (C¼O), 1719 (C¼O); ꢀH (CDCl3) 1.2 (t, 3H, CH3), 4.2 (q, 2H,
CH2), 5.1 (s, 1H, pyrazole H-4), 6.8–8.2 (m, 14H, aromatic protons); m/z
424 (Found: C, 73.4; H, 4.5; N, 6.4. C26H20N2O4 requires C, 73.6; H, 4.8; N,
6.6%). 8b: m.p. 175ꢁC (acetic acid); 70% yield; ꢁmax/cmÀ1 (KBr) 1752
(C¼O), 1717 (C¼O); ꢀH (CDCl3) 1.2 (t, 3H, CH3), 2.3 (s, 3H, CH3), 4.2
(q, 2H, CH2), 5.0 (s, 1H, pyrazole H-4), 6.6–8.2 (m, 13H, aromatic protons).
(Found: C, 73.8; H, 5.3; N, 6.3. C27H22N2O4 requires C, 74.0; H, 5.0;

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4,5-DIHYDROSPIROPYRAZOLE-5,20-INDANE-10,30-DIONES
3053
N, 6.4%). 8c: m.p. 275ꢁC (acetic acid); 76% yield; ꢁmax/cmÀ1 (KBr) 1752
(C¼O), 1717 (C¼O); ꢀH (CDCl3) 1.2 (t, 3H, CH3), 4.2 (q, 2H, CH2), 5.0 (s,
1H, pyrazole H-4), 6.8–8.2 (m, 13H, aromatic protons). (Found: C, 68.3; H,
4.3; Cl, 7.8; N, 6.4. C26H19ClN2O4 requires C, 68.1; H, 4.2; Cl, 7.7; N,
6.1%). 8e: m.p. 159ꢁC (ethanol); 82% yield; ꢁmax/cmÀ1 (KBr) 1752
(C¼O), 1720 (C¼O), 1695 (C¼O); ꢀH (CDCl3) 1.2 (t, 3H, CH3), 4.3
(q, 2H, CH2), 5.3 (s, 1H, pyrazole H-4), 6.6–8.2 (m, 12H, aromatic protons).
(Found: C, 67.3; H, 4.1; N, 6.4; S, 7.3. C24H18N2O4S requires C, 67.0; H,
4.2; N, 6.5; S, 7.5%). 8f: m.p. 132ꢁC (ethanol); 82% yield; ꢁmax/cmÀ1 (KBr)
1751 (C¼O), 1716 (C¼O); ꢀH (CDCl3) ꢀ 3.7 (s, 3H, CH3), 5.0 (s, 1H, pyr-
azole H-4), 6.7–8.1 (m, 14H, aromatic protons). (Found: C, 73.2; H, 4.3; N,
6.6. C25H18N2O4 requires C, 73.2; H, 4.4; N, 6.8%). 12a: m.p. 152ꢁC (acetic
acid); 75% yield; ꢁmax/cmÀ1 (KBr) 1750 (C¼O), 1713 (C¼O), 1628 (C¼O);
ꢀH (CDCl3) 5.3 (s, 1H, pyrazole H-4), 6.8–8.8 (m, 19H, aromatic protons).
(Found: C, 78.7; H, 4.6; N, 6.3. C30H20N2O3 requires C, 78.9; H, 4.4; N,
6.1%). 12b: m.p. 180ꢁC (ethanol); 79% yield; ꢁmax/cmÀ1 (KBr) 1746 (C¼O),
1712 (C¼O); ꢀH (CDCl3) 2.3 (s, 3H, CH3), 5.3 (s, 1H, pyrazole H-4), 6.6–8.4
(m, 18H, aromatic protons). (Found: C, 79.2; H, 4.5; N, 6.2. C31H22N2O3
requires C, 79.1; H, 4.7; N, 6.0%). 12c: m.p. 172ꢁC (acetic acid); 76% yield;
ꢁ
max/cmÀ1 (KBr) 1743 (C¼O), 1711 (C¼O), 1637 (C¼O); ꢀH (CDCl3) 5.3 (s,
1H, pyrazole H-4), 6.6–8.4 (m, 18H, aromatic protons). (Found: C, 73.4; H,
3.9; Cl, 7.3; N, 6.0. C30H19ClN2O3 requires C, 73.4; H, 3.9; Cl, 7.2; N,
5.7%). 12d: m.p. 160ꢁC (acetic acid); 80% yield; ꢁmax/cmÀ1 (KBr) 1753
(C¼O), 1713 (C¼O), 1630 (C¼O); ꢀH (CDCl3) 5.1 (s, 1H, pyrazole H-4),
6.6–8.1 (m, 18H, aromatic protons). (Found: C, 71.8; H 3.7; N, 8.4.
C30H19N3O5 requires C, 71.9; H, 3.8; N, 8.4%). 12e: m.p. 160ꢁC (acetic
acid); 65% yield; ꢁmax/cmÀ1 (KBr) 1750 (C¼O), 1711 (C¼O); ꢀH (CDCl3)
2.6 (s, 3H, CH3); 5.0 (s, 1H, pyrazole H-4), 6.7–8.2 (m, 13H, aromatic
protons). (Found: C, 70.1; H, 4.2; Cl, 8.2; N, 6.4. C25H17ClN2O3 requires
C, 70.0; H, 4.0; Cl, 8.3; N, 6.5%). 12f: m.p. 177ꢁC (acetic acid); 72% yield;
ꢁ
max/cmÀ1 (KBr) 1754 (C¼O), 1711 (C¼O); ꢀH (CDCl3) 2.6 (s, 3H, CH3),
5.1 (s, 1H, pyrazole H-4), 6.9–8.3 (m, 13H, aromatic protons). (Found: C,
68.4; H, 4.2; N, 9.7. C25H17N3O5 requires C, 68.3; H, 3.9; N, 9.6%).
a[(Phenylhydrazono)methoxycarbonyl]methylbenzylideneindane-1,3-dione
9: To a solution of 4,5-dihydrospiro[1,4-diphenyl-3-ethoxy-carbonyl] pyra-
zole-5,20-indane-10,30-dione 8a or 4,5-dihydrospiro[1,4-diphenyl-3-methoxy-
carbonyl]pyrazole-5,20-indane-10,30-dione 8f (1.2 mmol) in methanol (2 mL)
was added sodium methoxide (1.2 mmol) and the mixture was boiled for 2 h.
The solvent was evaporated and the residue extracted with ether (25 mL)
and water (10 mL). The organic layer was dried over anhydrous sodium
sulfate and the solvent was evaporated. The residue was recrystallized
from acetic acid to give compound 9: m.p. 235ꢁC (acetic acid); 59% yield;

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3054
HASSANEEN, ELWAN, AND HASSANEEN
ꢁ
max/cmÀ1 (KBr) 1780 (C¼O), 1720 (C¼O), 3290 (NH); ꢀH (CDCl3) 3.3
(s, 3H, CH3), 6.5 (s, 1H, NH), 7.0–7.4 (m, 14H, aromatic protons). (Found:
C, 73.4; H, 4.3; N, 6.6. C25H18N2O4 requires C, 73.2; H, 4.4; N, 6.8%).
a-[(Phenylhydrazono)ethoxycarbonyl]methylbenzylideneindane-1,3-dione
10: Method (A). This compound was prepared using the same procedure
described for the synthesis of 9 using sodium ethoxide in absolute ethanol in
place of sodium methoxide to give compound 10. Method (B).[14] A mixture
of indanedione 5 (1.02 g, 0.7 mmol) and ethylbenzoylacetatephenylhydra-
zone 11 (2.07 g, 0.7 mmol) was refluxed in ethanol in the presence of
sodium ethoxide. The excess solvent was evaporated and the residue was
recrystallized from acetic acid to give compound identical in all respects
(m.p., mmp, IR, 1H NMR, MS) with 10. 10: m.p. 290ꢁC (acetic acid);
60% yield; ꢁmax/cmÀ1 (KBr) 1780 (C¼O), 1719 (C¼O), 3417 (NH); ꢀH
(CDCl3) 0.99 (t, 3H, CH3), 4.1 (q, 2H, CH2), 6.2 (s, 1H, NH), 6.9–7.3
(m, 14H, aromatic protons); m/z 424 (Found: C, 73.4; H, 4.7; N, 6.5.
C26H20N2O4 requires C, 73.6; H, 4.8; N, 6.6%).
a[(Phenylhydrazono)benzoyl]methylbenzylideneindane-1,3-dione13:
Method (A). This compound was prepared using the same procedure
described for the synthesis of 9 using 4,5-dihydrospiro(1,4-diphenyl-3-
benzoylpyrazole-5,20-indane-10,30-dione) 12a in place of 8a or 8f.
Method (B).[15] Compound 13 was prepared by the same method described
for synthesis of 10 using dibenzoylmethanephenylhydrazone 14 in place of
11. The product was identical in all respects with compound 13 (m.p., mmp,
IR, 1H NMR, MS). 13: m.p. 179ꢁC (acetic acid); 75% yield; ꢁmax/cmÀ1
(KBr) 1773 (C¼O), 1655 (C¼O), 3296 (NH); ꢀH (CDCl3) 6.3 (s, 1H, NH),
6.9–8.9 (m, 19H, aromatic protons). (Found: C, 78.8; H, 4.3; N, 6.2.
C30H20N2O3 requires C, 78.9; H, 4.4; N, 6.1%).
REFERENCES
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Received in the USA September 24, 2001

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