Synthesis of some new spiro, isolated and fused heterocycles based on 1H-indole-2-one

Article abstract of DOI:10.1002/jccs.200100134

The reaction of 3-benzoylcyanomethylidine-1(H)-indole-2-one (1) with a variety of active methylene compounds, thioglycolic acid, glycine, hydrazine hydrate and phenyl hydrazine led to the formation of compounds 4a-d-10. 3-Thiosemicarbazide-1(H)-indole-2-one 2 on reaction with α-halocarbonyl compounds gave compounds 11a-c, 12a-c. The latter compounds on heating with phosphoryl chloride, cyclization takes place via losing water to give the angular tetracyclic compounds 13a,b and 14a-c. Cyanoacetic hydrazone derivative 3 readily cyclized upon heating in triethyl orthoformate to give the tricyclic system, oxopyridazino indole 15. On the other hand, the reaction of 3 with benzylidine malononitrile and benzylidene ethylcyanoactate gave the pyranyl hydrazone derivatives 16a,b.

Full text of DOI:10.1002/jccs.200100134

JournaloftheChineseChemicalSociety, 2001, 48, 921-927
921
Synthesis of Some New Spiro, Isolated and Fu sed Heterocycles Based on
1H-indole-2-one
T. I. El-Emary*†, R. A. Ahmed and E. A. Bakhite
ChemistryDepartment,FacultyofScience,AssiutUniversity,Assiut71516,Egypt
The re ac tion of 3-benzoylcyanomethylidine-1(H)-indole-2-one (1) with a va ri ety of ac tive meth y lene
com pounds, thioglycolic acid, glycine, hydrazine hy drate and phenyl hydrazine led to the for ma t ion of com-
pounds 4a-d-10. 3-Thiosemicarbazide-1(H)-indole-2-one 2 on re ac tion with -halocarbonyl com pounds
gave com pounds 11a-c, 12a-c. The lat ter com pounds on heat ing with phosphoryl chlo ride, cyclization takes
place via losingwatertogivetheangulartetracycliccompounds13a,b and14a-c. Cyanoacetic hydrazone de-
rivative3 readily cyclized upon heat ing in triethyl orthoformate to give the tricyclic sys tem, oxopyridazino
indole 15.
On the other hand, the re ac tion of 3 with benzylidine malononitrile and benzylidene ethylcyanoactate
gavethepyranylhydrazonederivatives16a,b.
INTRODUCTION
Scheme I
O
A review describing preparations and reactions of
indolin-2(3H)-ones was pub lished few years ago.1 Numerous
isatinderivativesexhibitsignificantbiological,medicinal
andpharmacologicalactivities,2-4 such as antituberculous,
antihypoxing agent, anticonvulsant, antihyperglycemic; ac-
tive against sal mo nella, typhi and against vibrio cholerae.
Be sides, they are used in treat ing and pre vent ing pestvirus.5
Moreovere, they show antifertility ac tiv ity.6
O
N
H
(ii)
(i)
(iii)
CN
C
N-NHCSNH
O
2
COPh
N-NHCOCH CN
2
O
O
N
H
N
H
N
H
From all the men tioned above and in con tin u a tion of
thepreviousworkinthesynthesisofheterocycliccompounds
containingindolemoiety,2c hereinwewishtoreportsynthesis
of some new spiro, iso lated and fused heterocycles based on
1H-indole-2-one.
(1)
(2)
(3)
(i) CH (CN)(COPh)
2
2
(ii) NH NHCSNH2
(iii) NH NHCOCH CN
2
2
azoline-5-oneandthiobarbituricacidinethanolcontaininga
cat a lytic amount of triethyl amine pro duce the spiro pyrano
indolederivatives4a-d-7,respectively.
RESULTSANDDISCUSSION
The re ac tion of thioglycolic acid and/or glycine with
the ylidene 1 in boil ing ace tic acid led to the for ma tion of the
spiro-thieno-indole and the spiro-pyrrolo-indole de riv a tives
8a,b.
1H-Indole-2,3 dione was readily con densed with ben-
zoylacetonitrile7 and with thiosemicarbazide8 inboilingetha-
nol to give 3-benzoylcyanomethylidine-1(H)-indole-2-one 1
and 3-thiosemicarbazide-1(H)-indole-2-one 2,respectively.
Its re ac tion with cyanoacetic hydrazide gave 2-cyano-acetic
acid (2-oxo-1,2-dihydro-indol-3-ylidene)hydrazide 3.9
In this pa per, a se ries of new spiro, iso lated and fused
heterocycles based on 1H- indole-2-one were pre pared us ing
the ylidene 1and a va ri ety of ac tive meth y lene com pounds.
Thus, sub ject ing com pound1 to re act with, malononitrile,
ethyl cyano ac e tate, ethyl acetoacetate, acetylacetone, 1-
phenyl-2 H-3,5-pyrazoline-dione,3-methyl-1-phenyl-2-pyr-
On the other hand, when 1 was treated with hydrazine
hydrateinethanol,thespiropyrazoloindolederivative9 was
pro duced, while when phenyl hydrazine was used in stead,
ylidenic bond cleav age10 takes place to give 3-phenyl hydra-
zone 10.
The thiazolidine and thiazolidinone de riv a tives11a-c
and 12a-c were pro duced when the thiosemicarbazone 2 was
refluxed with -haloketones and/or -haloestresinethanol
andinthepresenceofsodiumacetate.The -haloketones and
† Cur rent Ad dress: Al Jouf Teachers Col lege, P.O. Box: 269, Al Jouf, Saudi Ara bia

922 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
El-Emary et al.
Scheme II
meltingpointapparatusandareuncorrected.Infraredspectra
were recorded on a Perkin-Elmer 297 Infrared Spectro-
photometer (KBr wa fer tech nique). 1H-NMR spec tra were
mea sured on a Varian As so ci ate EM-390 (90 MHz) spec-
trom e ter, chem i cal shifts are re ported in ppm, in ter nal stan-
dard was tetramethylsilane ( scal). Mass spec tra were mea-
sured on a Varian HP Model (MS 5988) at 70 eV with tem per-
a ture 160-400 C.
H
S
N
1
R
O
O
Ph
NH
2
H N
(iv)
(i)
2
R
O
CN
COPh
O
O
N
H
N
H
(7)
1
2
(4a) R = NH ,
R
= CN
2
O
1
2
(4b) R = NH , R = COOEt
2
CN
1
2
(4c) R = CH , R = COOEt
3
PhCO
1
2
3-Benzoylcyanomethylidine-1(H)-indole-2-one (1),
indoline-2,3-dione-3-thiosemicarbazone (2), and
indoline-2,3-dione-3-cyanoacetic acid (3a)
Werepreparedaccordingtomethodsreportedinthelit-
erature.7-9
(4d) R = CH , R = COCH
3
3
Ph
X
(v)
N
O
O
N
NH
2
N
H
Me
(1)
(8a) X= S
(8b) X= NH
COPh
(ii)
O
N
Ph
N
H
H N
(5)
Indoline-2,3-dione-3-phenylhydrazone (10)
Was found to be iden ti cal to that re ported in the lit er a-
ture.7
CN
Ph
N
O
(vi)
N
O
H N
O
(9)
H
NH
2
NNHPh
O
Reactions of compound (1) with, malononitrile,
ethylcyanoacetate, ethylacetoacetate, acetylacetone, 1-
phenyl-2 H-3,5-pyrazoline-dione,3-methyl-1-phenyl-2-
pyrazoline-5-one, thiobarbituric acid: For ma tion of com-
pounds 4a-d-7
COPh
O
N
H
(vii)
(iii)
N
H
(10)
(6)
(i) = CH (X )(X )
2
1
2
Me
=
N
O
a) X = X = CN
O
=
O
1
2
(ii)
(iii) =
HN
(iv)
b) X = CN, X = COOEt
1
2
O
O
c) X = COCH , X = COOEt
HN
N H
1
3
3
2
2
N
N
d) X = COCH , X = COCH
1
3
Ph
(vi) = NH NH .H O
Ph
S
General procedure
(v) = CH (X)COOH
2
vii) = PhNHNH
2
2
2
2
A mix ture of com pound 1 (0.002 mole) and the pre vi-
ouslymentionedcompoundsinethanolcontainingacatalytic
amount of triethyl amine was heated un der re flux for 1-3 h.
The pre cip i tate that formed was col lected by fil tra tion and
crystallized from the proper solvent to give compounds
4a-d-7,respectively.Thephysicalandspectraldataaregiven
inTable1.
a) X = SH
b) X = NH
-haloesters used were: phenacyl bro mide, chloroacetone,
chloroacetyl ethylacetoacetate, 2-bromo methylpropiopante,
chloroaceticacidandbromodiethylmalonate.
On heat ing com pounds 11a,b and 12a-d with phos-
phoryl chlo ride, cyclization takes place via los ing wa ter to
give the an gu lar tetracyclic com pounds, thiazolo- triazino-
indole and thiazolo-triazino-indole-2-one 13a,b and 14a-c.
Cyanoacetichydrazonederivative3 ob tained from con-
densationof1(H) indolin-2,3-dione with cyanoacetic hydra-
zide readily cyclized upon heat ing in triethyl orthformate to
give the tricyclic sys tem, oxopyridazino indole 15.
2-Amino-3,5-dicyano-6-phenyl-spiro[indoline-3,4-
1 (H)pyran]-2 -one (4a)
Was separated from ethanol as colourless crystals
(74%).
2-Amino-3-carboethoxy-5-cyano-6-phenyl-spiro[indolin-
3,4-1 (H)pyran]-2 -one (4b)
On the other hand, the re ac tion of 3 with benzylidine
malononitrile and benzylidene ethylcyanoacetate gave the
pyranylhydrazoneindolonederivatives16a,b.
Was separated from ethanol as colourless crystals
(57%).
3-Carboethoxy-5-cyano-3-methyl-6-phenyl-spiro[indolin-
3,4-1 (H)pyran]-2 -one (4c)
EXPERIMENTALSECTION
Was separated from ethanol as colourless crystals
(42%).
The melt ing points were de ter mined with a Buchi 500

SynthesisofSpiroHeterocycles
J. Chin. Chem. Soc., Vol. 48, No. 5, 2001 923
Scheme III
N
N
S
S
N
N
N-N=
N-N=
S
Me
(iv)
(v)
(i)
S
POCl
3
POCl
N
O
H
3
N
O
H
N
N
Me
O
Ph
S
N
H
N
N
H
N
Ph
O
(11a)
(13a)
(14a)
(12a)
N
N
S
N
N
N-N=
N-N=
S
(ii)
POCl
S
3
POCl
N
H
N
N
3
O
O
N
H
O
N
Me
N
N
Me
N
O
(2)
H
H
(11b)
(13b)
(14b)
(12b)
S
N-N=
S
N-N=
COOEt
(vi)
(iii)
COOEt
N
O
H
N
O
H
O
N
Me
N
H
(12c)
(14c)
POCl
3
(11c)
POCl
3
H
N
N
N
N
S
S
N
N
COOEt
COOEt
N
O
N
Me
(13c)
(i) PhCOCH Br
(ii) CH COCH Cl
(iii) ClCH(COCH )(COOEt)
3
2
3
2
(iv) CH CH(Br)(COOMe) (v) ClCH COOH
(vi) BrCH(COOEt)
3
2
2
5-Benzoyl-6-cyano-3-methyl-2 -oxo-phenyl-spiro[pyrano-
[2,3-c]pyrazole-4(1H)-3 -[2]indoline] (5)
Was separated from ethanol as colourless crystals
(52%).
Scheme IV
(3)
(ii)
(i)
H
NH
5-Benzoyl-6-cyano-3,2 -dioxo-phenyl-spiro[pyrano[2,3-c]-
pyrazole-4(1H)-3 -[2]indoline] (6)
Was sep a rated from ben zene-petroleum ether (60/80
C)(1:1)ascolourlesscrystals(38%).
2
O
N
N
N-N=
O
X
O
Ph
CN
N
H
CN
N
H
5-Benzoyl-6-cyano-4,2 -dioxo-2-thioxo-spiro[pyrano[2,3-c]-
pyrimidine-4(1H)-3 -[2]indoline] (7)
(16a) X = CN
(16b) X = COOEt
(15)
Was sep a rated from di ox an-water (3:1) as colour less
crystals(43%).
(i) = CH(EtO)
(ii) = PhCH=C(X)(CN)
a) X = CN
3
b) X = COOEt
Reaction of compound (1) with thioglycolic acid and
glycine: For ma tion of Com pounds (8a,b)
3-Acetyl-5-cyano-2-methyl-5-phenyl-spiro[indolin-3,4-
1 (H)pyran]-2 -one (4d)
General procedure
Wasseparatedfromdilutedethanolascolourlesscrys-
tals (36%).
A mixture of com pound 1 (0.001 mole) and thio-
glycolic acid/or glycine (0.001 mole) in ace tic acid (20 mL)

924 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
El-Emary et al.
Table 1.
Compd.
No
Mp C
(Yield%)
Mol. Formula
(M.Wt)
IR/Cm-1
1H NMR/
MS
m/z (%)
(d6-DMSO): 3.3 (s,2H,NH2), 6.85-7.85,
(m,9H,Ar-H), 11.8 (NH)
4a
264-265
(74)
226-227
(57)
C20H12N4O2
(340.3)
C22H17N3O4
(387.3)
3300-3180 (NH2 + NH),
2200 (CN), 1650 (CO)
3300-3180 (NH2 + NH),
2210 (CN), 1720, 1650
(2CO)
340
(20)
387
(18)
4b
(CF3COOD): 0.8-1.0 (t,3H,CH3CH2),
3.85-4.0 (q,2H,CH2CH3), 7.0-7.85
(m,9H,Ar-H)
4c
227-228
(42)
C23H18N2O4
(386.3)
3300 (NH), 2200 (CN),
1780, 1650 (2CO)
(d6-DMSO): 0.9-1.1 (t,3H,CH3CH2),
2.5 (s,3H,CH3), 3.85-4.0
386
(22)
(q,2H,CH2CH3), 7.1-7.9
(m,9H,Ar-H), 11.5 (s,1H,NH)
(d6-DMSO): 2.4 (s,3H,CH3),
3.2 (s,3H,COCH3), 7.1-7.9
(m,9H,Ar-H), 11.8 (s,1H,NH)
(CF3COOD): 2.8 (s,3H,CH3),
7.8-8.0 (m,14H,Ar-H)
4d
216-218
(36)
C22H16N2O3
(356.3)
3250 (NH), 2220 (CN),
1760, 1720, 1650 (3CO)
5
268-270
(52)
C27H20N4O3
(448.4)
3400-3300 (NH2 + NH),
1720, 1650 (2CO)
247-248
(38)
196-197
(43)
143-145
(27)
160-162
(34)
C26H18N4O4
(450.3)
C21H14N4O4S
(418.3)
C19H12N2O3S
(348.2)
C19H13N3O3
(331.2)
3380-3220 (NH2 + 2NH),
1700, 1660, 1640 (3CO)
3360-3200 (NH2 + 3NH),
1720, 1660, 1640 (3CO)
3300 (NH), 2210 (CN),
1720, 1700, 1650 (3CO)
3400-3200 (2NH), 2200
(CN), 1720, 1690, 1640
(3CO)
(CF3COOD): 7.9-8.1 (m,14H,Ar-H)
6
7
(CF3COOD): 7.8-8.0 (m,9H,Ar-H)
(d6-DMSO): 4.1 (s,2H,CH2),
7.1-7.7 (m,9H,Ar-H), 11.5 (s,1H,NH)
(d6-DMSO): 4.2 (s,2H, CH2),
7.2-7.8 (m,9H,Ar-H), 11.5, 11.8
(2s,2H,2NH)
8a
8b
9
176-178
(62)
C17H11N4O
(287.2)
3300-3150 (2NH), 2200
(CN), 1650 (CO)
(d6-DMSO): 6.8 (s,1H,NH),
7.1-7.8 (m,9H,Ar-H), 11.2,
12.5 (2s,2H,2NH)
287
(18)
273-275
(78)
256-258
(61)
C17H12N4OS
(320.4)
C12H10N4OS
(258.3)
3300-3250 (2NH), 1660
(CO)
3400-3300 (2NH), 1650
(CO)
(d6-DMSO): 6.5-7.6 (m,10H,
Ar-H,-CH=), 10.9, 11.8 (2s,2H,2NH)
(d6-DMSO): 2.5 (s,3H,CH3),
6.7-7.8 (m,10H,Ar-H,-CH=), 11.2, 11.8 (2s,
2H,2NH)
320
(28)
258
11a
11b
(11)
11c
216-218
(48)
C15H14N4O3S
(330.4)
3400-3150 (2NH), 1690,
1650 (2CO)
(d6-DMSO): 1.2-1.3 (t,3H, CH2CH3),
2.5 (s,3H,CH3), 3.5-3.7 (q,3H,CH2CH3),
6.8-7.8 (m,4H,Ar-H), 11.5, 12.6 (2s, 2H,2NH)
(d6-DMSO): 2.5 (s,3H,CH3) 6.7-7.8
(m,5H,Ar-H,-CH), 10.8, 11.6 (2s,2H,2NH)
(d6-DMSO): 4.2 (s,3H,CH2), 6.9-7.8
(m,4H,Ar-H), 10.2, 11.5 (2s, 2H,2NH).
(d6-DMSO): 1.1-1.2 (t,3H,-CH2-CH3), 4.0-4.2
(q,2H,CH2-CH3), 7.0-7.8 (m,4H,Ar-H).
(CF3COOD): 7.8-8.1 (m,10H,Ar-H+ -CH=)
12a
12b
12c
13a
13b
13c
273-275
(52)
290-292
(66)
223-225
(58)
> 300
(62)
> 300
(52)
> 300
(41)
C12H10N4O2S
(274.3)
C11H8N4O2S
(260.3)
C14H12N4O4S
(332.4)
C17H10N4S
(302.3)
C12H8N4S
(240.3)
C15H12N4O2S
(312.4)
3250-3150 (2NH), 1690,
1640 (2CO)
3300-3150 (2NH), 1680,
1650 (2CO)
3380, 3250 (2NH), 1720,
1680, 1640 (3CO)
3050 (CH,aliph.),
2900 (CH,arom.)
3020 (CH,aliph.),
2930 (CH,arom.)
3010 (CH,aliph.),
2920 (CH,arom.),
1730 (CO)
260
(24)
302
(18)
(CF3COOD): 2.8 (s,3H,CH3), 7.8-8.1
(m,4H,Ar-H).
(CF3COOD): 1.2-1.3 (t,3H,CH2-CH3),
3.0 (s,3H,CH3), 3.6-3.8 (q,2H,CH2-CH3),
7.7-7.9 (m,4H,Ar-H)
14a
> 300
(48)
C12H8N4OS
(256.3)
3010 (CH,aliph.),
2920 (CH,arom.),
1670 (CO)
(CF3COOD): 2.7 (s,3H,CH3),
7.8-8.0 (m,4H,Ar-H)

SynthesisofSpiroHeterocycles
J. Chin. Chem. Soc., Vol. 48, No. 5, 2001 925
242
(18)
14b
14c
> 300
(57)
C11H6N4OS
(242.3)
3050 (CH,aliph.),
2920 (CH,arom.),
1690 (CO)
3040 (CH,aliph.),
2910 (CH,arom.),
1680 (CO)
(CF3COOD): 4.3 (s,2H,CH2),
7.7-7.9 (m,4H,Ar-H)
> 300
(42)
C14H10N4O3S
(314.4)
(CF3COOD): 1.2-1.3 (q,2H,CH2-CH3), 2.1
(s,1H,CH), 3.8-3.9 (t,2H,CH2CH3), 7.8-8.0
(m,4H,Ar-H)
15
> 300
(38)
C11H6N4O
(210.2)
3300 (NH), 2220 (CN),
1660 (CO)
(CF3COOD): 7.7-7.9 (m,4H,Ar-H)
16a
16b
> 300
(59)
> 300
(36)
C21H12N6O2
(380.4)
C23H17N5O4
(427.4)
3400-3250 (NH2 + NH),
2220 (CN), 1660 (CO)
3400-3200 (NH2 + NH),
2210 (CN), 1650 (CO)
(CF3COOD): 7.8-8.1 (m,9H,Ar-H)
(CF3COOD): 1.3-1.4 (t,3H,CH2-CH3), 3.8-4.0
(q,2H,CH2CH3), 7.8-8.0 (m,4H,Ar-H)
was heated un der re flux over night; the sol vent was re moved
un der re duced pres sure and the res i due was triturated with
hot wa ter. The solid prod uct was col lected and crys tal lized
from the proper sol vent to give com pounds 8a,b, re spec-
tively. The phys i cal and spec tral data are given in Ta ble 1.
(0.01 mole) in eth a nol (30 mL) was heated un der re flux for
1-4h. Thesolidproductwasfilteredoffandcrystallizedfrom
the proper sol vent to give com pounds 11a,b and 12a-d. The
phys i cal and spec tral data are given in Ta ble 1. The - halo-
ketones and -haloesters used were: phenacyl bro mide, chlo-
ro acetone, chloroacetyl ethylacetoacetate, 2-bromo methyl-
propiopante,chloroaceticacidandbromodiethylmalonate.
3-Benzoyl-3-cyano-4,2 -dioxo-spiro[indolin-3,2-1 (H)tetra-
hydrothiophine] (8a)
Was sep a rated from di ox an-water (1:1) as colour less
crystals(27%).
1(H)-3-hydrazono-4 -phenyl-3 (H)thiazolyl-indolin-2-one
(11a)
Wasseparatedfromethanolasorangecrystals(78%).
3-Benzoyl-3-cyano-4,2 -dioxo-spiro[indolin-3,2-1 (H)pyrrol]
(8b)
1(H)-3-hydrazono-4 -methyl-3 (H)thiazolyl-indolin-2-one
Was sep a rated from di ox an-water (1:1) as colour less
crystals(34%).
(11b)
Wasseparatedfromethanolasorangish-browncrystals
(61%).
Reaction of compound (1) with hydrazine hydrate: For-
mation of compound (9)
5 -Ethyl-3-hydrazono-4 -methyl-3 (H)thiazolyl-indolin-2-
one-carboxylate (11c)
A mix ture of com pound1 (0.001 mole) and hydrazine
hy drate (1 mL) was heated in eth a nol (20 mL) un der re flux
for 1 h. The so lu tion was con cen trated and the prod uct ob-
tained was fil tered, washed with wa ter, dried. The phys i cal
and spec tral data are given in Ta ble 1.
Was sep a rated from eth a nol as orangish-red crys tals
(48%).
1(H)-3-hydrazono-5 -methyl-4 -oxo-3 (H)thiazolyl-indolin-
2-one (12a)
4-Cyano-3-phenyl-2 -oxo-spiro[indolin-3,2-1 (H)-1(H)-
pyrazol] (9)
Wasseparatedfromethanolasyellowish-orangecrys-
tals (52%).
Was sep a rated from eth a nol-water (1:1) as colour less
crystals(62%).
1(H)-3-hydrazono-5 -oxo-3 (H)thiazolyl-indolin-2-one
(12b)
Reaction of compound (3) with -halocarbonyl com-
pounds: formation of com pounds (11a,b) and (12a-d)
Was sep a rated from eth a nol as brown ish-orange crys-
tals (66%).
General procedure
A mix ture of com pound 2 (0.005 mole) and -halocar-
bonyl com pound (0.005 mole) and fused so dium ac e tate
5 -Ethyl-3-hydrazono-4 -oxo-3 (H)thiazolyl-indolin-2-one-
carboxylate (12c)
Wasseparatedfromethanolasreddish-orangecrystals

926 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
El-Emary et al.
(58%).
Reaction of compound (3) with benzylidinemalononitrile,
benzylidine ethylcyanoacetate: Formation of compounds
(16a,b)
Heating of compounds (11a,b) and (12a-d) in phosphoryl
chlo ride. For ma tion of com pounds (13a,c) and (14a-c)
A mix ture of com pound 11a-c or 12a-c and POCl3 was
heated on a wa ter bath for 1 h. Af ter cool ing, the re ac tion
mix ture was poured into ice-water; the solid prod uct formed
was fil tered off, washed with wa ter, dried and crys tal lized
from the proper sol vent to give com pounds 13a-c and 14a-c.
The phys i cal and spec tral data are given in Ta ble 1.
General procedure
A mix ture of com pound 3 (0.002 mole) and benzyl-
idinemalononitrile or benzylidine ethylcyanoacetate (0.002
mole) in eth a nol (30 mL) was heated un der re flux for 3-5 h.
The solid prod uct ob tained was fil tered, washed with wa ter,
dried and cryslallized from the proper sol vent to give com-
pounds 16a,b. The phys i cal and spec tral data are given in Ta-
ble 1.
3-Phenyl-thiazolo[2 ,3 :3,4]-1,2,4-triazino[5,6-b]indole
(13a)
Was sep a rated from di ox an-water (1:1) as brown ish-
violetcrystals(62%).
3-(2 -amino-3 ,5 -dicyano-4 -phenyl-pyran-6 -yl)hydrazono-
2,3-dihydroindoline-2-one (16a)
Was sep a rated from di ox an-water (1:1) as brown crys-
tals (59%).
3-Methyl-thiazolo[2 ,3 :3,4]-1,2,4-triazino[5,6-b]indole
(13b)
Was separated from dioxan-water (1:1) as reddish-
browncrystals(52%).
3-(2 -amino-3 -carboethoxy-5 -cyano-4 -phenyl-pyran-6 -
yl)hydrazono-2,3-dihydroindoline-2-one (16b)
Was sep a rated from di ox an-water (1:1) as brown crys-
tals (37%).
2-Ethoxycarbonyl-3-methyl-thiazolo[2 ,3 :3,4]-1,2,4-triazino -
[5,6-b]indole (13c)
Was sep a rated from di ox an-water (1:1) as brown crys-
tals (41%).
Received Feb ru ary 2, 2001.
2-Methyl-thiazolo[2 ,3 :3,4]-1,2,4-triazino[5,6-b]indole-
3(2H)-one (14a)
Key Words
Synthesis; Indole derivatives.
Was sep a rated from di ox an-water (1:1) as brown crys-
tals (48%).
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[2 ,3 :3,4]-1,2,4-triazino[5,6-b]indole-3(2H)-one (14b)
Was separated from DMF-water (1:1) as brownish-
violetcrystals(57%).
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Heating of compound (3) in triethyl orthoformate. For-
mation of 4-cyano-2,3,5-trihydro-3-oxopyridazino[4,3-b]-
indole (15)
A mix ture of com pound 3 (0.002 mole) and triethyl
orthoformate (10 mL) was heated on a wa ter bath for 6 h. Af-
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