Synthesis and biological activity of new selected different heterocyclic nitrogen compounds incorporating 1,4-naphthquinone

Article abstract of DOI:10.1002/jccs.200100114

Condensation of 1-phenylnaphthcyclopentan-2,4,9-trione (II) with aromatic aldehydes yielded the corresponding 3-benzylidene deivatives (III_a-f). Interaction of III_a-f with hydrazines, hydroxylamine, urea and thiourea afforded some new (pyrazoline IV_a-f, V_a-f, Isoxazolino VI_a-f pyrimidinone and/or pyrimidinethione, VII_a-f, VIII_a-f) derivatives, respectively. Also, a series of some spiro compounds covering β-lactams and thiazolidinones (Xg-j, XIg-j) incorporating 1-phenylnaphthcyclopentan-2,4,9-trione were prepared.

Full text of DOI:10.1002/jccs.200100114

JournaloftheChineseChemicalSociety, 2001, 48, 801-806
801
Synthesis and Biological Activity of New Selected DifferentHeterocyclic
Nitrogen Compounds Incorporating1,4-naphthquinone
Ali Kamel Khalafallah
DepartmentofChemistry,AswanFacultyofScience,Aswan,Egypt
Condensationof1-phenylnaphthcyclopentan-2,4,9-trione(II)witharomaticaldehydesyieldedthecorre-
spond ing 3-benzylidene deivatives (IIIa-f). Interactionof IIIa-f with hydrazines, hydroxylamine, urea and
thiourea af forded some new (pyrazoline IVa-f, Va-f, Isoxazolino VIa-f pyrimidinone and/or pyrimidinethione,
VIIa-f, VIIIa-f) de riv a tives, re spec tively. Also, a se ries of some spiro com pounds cov er ing -lactamsand
thiazolidinones (Xg-j, XIg-j)incorporating1-phenylnaphthcyclopentan-2,4,9-trionewereprepared.
INTRODUCTION
An ef fi cient strat egy was de vel oped for syn the sis of
compoundsIIIa-f ledtotheirreactionwithhydrazinesaccord-
ing to the re ported method.4 Thus, the in ter ac tion ofIIIa-f
with hydrazinehydrate in dry al co hol in the pres ence of gla-
cial ace tic acid af forded the cor re spond ing 1-phenyl naphth-
cyclopentan(2,3-c)-N-acetylpyrazolino-4,9-dione (IVa-f).
How ever, the re ac tion ofIIIa-f with phenyl hydrazine gave
N-phenylpyrazolinoanalogues(Va-f) un der the in flu ence of
piperidinecatalysis.
Also, the ac ti va tion ex erted by the car bonyl group on
the exocyclic dou ble bond in IIIa-f rendersthemavailablefor
theadditionofthevariousaminocompounds, e.g., hydroxyl-
aminehydrochloride,ureaandthiourea.Thus,interactionof
IIIa-f with one mole equiv a lent of hydroxylamine hy dro chlo-
ride in ethanolic so dium hy drox ide so lu tion gave the cor re-
sponding 1-phenylnaphthcyclopentan(2,3-c)isoxazolino-
4,9-dione (VIa-f ), whereas the interaction of IIIa-f with
equimolarratiosofureaand/orthioureainethanolcontaining
hydrochloricacidgavethecorresponding1-phenylnaphth-
cyclopentan(2,3-c)pyrimidine(pyrimidinethione)-4,9-dione
(VIIa-f and VIIIa-f),respectively(SchemeI).
new heterocyclics via cyclocondensation re ac tion be tween
dif fer ent types of , -unsaturatedketonecompoundswith
hydrazines, hydroxylamine, urea and thiourea. Also, this an
ef fi cient strat egy ex tended to in clude a syn the sis of some
spiro com pounds via cycloaddition re ac tion of mono chloro-
acetyl chlo ride and thioglycolic acid to the newly syn the sised
Schiff bases (IXg-j) which were the sub ject of our pre vi ous
studies.1-7 Incontinuationofourpreviousworkonthehetero-
cyclic ni tro gen com pounds and in view of their var i ous uses
asbiologicalandsyntheticdrugs,8-12 pyrazolines, isoxazo-
lines, py rimi dines, pyrimidinethiones, -lac tams and thiazo-
lidinones (IVa-f-VIIIa-f, Xg-j, XIg-j) in con junc tion with
1-phenylnaphthcyclopenan-4,9-dionewereprepared.
RESULTSANDDISCUSSION
1-Phenylnaphthcyclopentan-2,4,9-trione (II) was pre-
pared through the re ac tion of 1,4-naphthquinone with benzyl
chlorideinthepresenceofethyleneglycolassolventandso-
dium bi car bon ate as cat a lyst to give 2-benzyl-1,4- naph th-
quinone (I), thenthecyclocondensationreactionoftheprevi-
ously pre pared com pound (1) with monochloroacetic acid
proceededinthepresenceoftriethylamineascatalystafford-
ing 1-phenylnaphthcyclopentan-2,4,9-trione (II) (Scheme I).
The struc tures ofI andIIwereconfirmedbyelementalanaly-
sis, IR and 1H NMR spec tral data (Ta bles 1, 2).
StructureofcompoundsI-VIIIa-f were con firmed by el-
ementalanalysis,IRand1HNMRspectraldata13-14 (Ta bles 1,
2).
Also 1-phenylnaphthcyclopentan-2,4,9-trione (II)
undergoes condensation reaction with different aromatic
nitroso com pounds such as -nitrosophenol, -nitroso-N-
dimethylaniline, -nitroso- -naphthol and -nitroso- -
naphthol in the pres ence of piperidine af forded the cor re-
spondingschiffbasescompounds(IXg-i).Itsstructureswere
con firmed by el e men tal anal y sis, IR and1H NMR spec tra
(c.f. Ta bles 1, 2). These schiff bases (IXg-i) re act ing with
chloroacetylchloride in the pres ence of triethylamine in DMF
affordedthecorrespondingsoiro -lactams(Xg-i). Its struc-
tureswereconfirmedbyelementalanalysis, IRand1H NMR
spec tra (c.f. Ta bles 1, 2).
Con den sa tion of II with appropriate aromaticalde-
hydes pro ceeded smoothly in ab so lute al co hol us ing piper-
idine as cat a lyst to yield the cor re spond ing 3-arylideno-1-
phenylnaphthcyclopentan-2,4,9-trione(IIIa-f).
The pres ence of , -unsaturated Ketonic sys tem in

802 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Khalafallah
Scheme I
On the other hand the cycloaddition re ac tion of thio-
glycolic acid to the schiff bases ( IXg-j) in DMF gave the cor-
respondingthiazolidinone(XIg-j). Its struc tures were con-
firmed by el e men tal anal y sis, IR and 1H NMR spec tra (c.f.
Ta bles 1, 2).
Theantibacterialandantifungalactivitiesofsomese-
lectedcompounds, i.e., III-VIIIa,c,f dissolvedinethylenegly-
col were de ter mined us ing fil ter pa per disc method15 against
bacteria Bacillus stearetherophil and Serratia and fungi
Aspergillus and Penicillium spe cies. The in hi bi tion zones of
all the com pounds were found in the range of 6-14 mm.
Structure-biologicalactivityrelationshipofthefused
pyrazolines, isoxazolines and py rimi dines (IVa,c,f-VIIIa,c,f
)
wasdemonstratedrelativetotheparentcompoundIII. Thus,
theparentcompoundsIIIa,c,f are slightly po tent against bac te-
ria and fungi. It is quite ob vi ous that the pres ence of elec-
tron-donating or with draw ing groups (IIIc or IIIf)increases
the ac tiv ity more than the unsubstitutedIIIa.Also,insertinga
pyrazolino moi ety to the par ent IIIa to give IVa causes, to
some ex tent, an in crease in the bi o log i cal ac tiv ity. Thus, N-
acetylpyrazolinoderivatives(IVa,c,f) slightly in crease the bi-
ologicalactivity,butthoseofN-phenylpyrazolinoanalogues

HeterocyclicNitrogenCompoundsIncorporating1,4-naphthquinone
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 803
Table 1. Physical Data of Compounds I-XI
Comp.
No.
Mol. Formula
(m. wt.)
m.p.*
( C)
Yield
(%)
Elemental analysis;
Found (Calc.) %
C
H
N
-
I
C17H12O2
(248)
C19H12O3
(288)
C26H16O3
(376)
C27H18O4
(406)
C28H11O3N
(419)
C26H16O4
(392)
C26H16O4
(392)
C26H15NO5
(421)
C28H20N2O3
(432)
C29H22N2O4
(462)
C30H25N3O3
(475)
C28H20N2O4
(448)
C28H19N2O4
(448)
C28H19N3O5
(477)
C32H22N2O2
(466)
C33H24N2O3
(496)
C34H27NO2
(509)
C32H22N2O3
(482)
C32H22N2O3
(482)
C32H21N3O4
(511)
C32H22NO3
(468)
C33H24NO4
(498)
C34H27N2O3
(511)
C32H22NO4
(484)
140 a
160 a
185 a
205 b
195 b
180 b
230 a
170 a
190 b
180 b
195 a
175 b
215 a
170 a
185 a
205 b
205 b
165 b
220 a
185 a
170 b
160 b
185 a
155 b
230 a
60
65
55
50
45
52
40
70
60
50
55
45
35
65
50
40
35
40
30
60
55
45
35
40
30
82.30
(82.26)
79.21
(79.17)
83.10
6.90
(6.85)
4.20
(4.17)
4.40
II
-
-
-
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IVa
IVb
IVc
IVd
IVe
IVf
Va
(82.98)
79.90
(4.26)
4.49
(79.80)
80.20
(80.19)
79.61
(4.43)
5.09
(5.01)
4.10
3.39
(3.34)
-
(79.59)
80.10
(4.08)
4.48
-
(79.59)
74.20
(74.11)
77.80
(4.08)
3.61
(3.56)
4.68
3.40
(3.33)
6.50
(77.78)
75.40
(4.63)
4.80
(6.48)
6.10
(75.32)
75.80
(4.76)
5.30
(6.06)
8.89
(75.79)
75.12
(5.26)
4.50
(8.84)
6.30
(75.00)
75.45
(4.46)
4.62
(6.25)
6.45
(75.00)
70.49
(4.46)
4.10
(6.25)
8.85
(70.44)
82.52
(3.98)
4.83
(8.81)
6.08
(82.40)
79.60
(4.72)
4.98
(6.01)
5.60
Vb
(79.84)
80.27
(4.84)
5.42
(5.65)
8.31
Vc
(80.16)
79.71
(5.30)
4.61
(8.25)
5.86
Vd
(79.67)
79.59
(4.56)
4.48
(5.81)
5.92
Ve
(79.67)
75.20
(4.56)
4.00
(5.81)
8.32
Vf
(75.15)
82.09
(4.11)
5.10
(8.22)
3.30
VIa
VIb
VIc
VId
VIe
(82.05)
79.61
(4.70)
4.91
(2.99)
2.90
(79.52)
79.75
(4.82)
5.19
(2.81)
5.59
(79.84)
79.20
(5.28)
4.41
(5.48)
2.92
(79.34)
79.56
(4.55)
4.67
(2.89)
2.94
C32H22NO4
(484)
(79.34)
(4.55)
(2.89)

804 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Khalafallah
Table 1. Physical Data of Compounds I-XI (continued)
Comp.
No.
Mol. Formula
(m. wt.)
m.p.*
( C)
Yield
(%)
Elemental analysis;
Found (Calc.) %
C
H
N
S
-
VIf
C32H21N2O5
(513)
C27H18N2O3
(418)
C28H20N2O4
(448)
C29H23N3O3
(461)
C27H18N2O4
(434)
C27H18N2O4
(434)
C27H17N3O5
(463)
C27H18N2O2S
(434)
C28H20N2O3S
(464)
C29H23N3O2S
(477)
C27H18N2O3S
(450)
C27H18N2O3S
(450)
C27H17N3O4S
(479)
C25H15NO4
(393.40)
C27H20N2O3
(420.47)
C29H17NO3
(427.46)
C29H17NO3
(427.46)
C27H16NO5Cl
(469.89)
C29H21N2O4Cl
(496.96)
C31H18NO4Cl
(503.95)
C31H18NO4Cl
(503.95)
C27H17NO5S
(467.50)
C29H22N2O4S
(494.56)
C31H19NO4S
(501.56)
150 a
185 a
175 a
190 b
180 b
225 a
195 b
170 a
185 a
165 a
170 a
230 b
150 b
215
70
50
40
35
30
45
60
50
40
30
45
30
70
60
65
67
69
68
60
55
67
69
70
65
60
74.90
(74.85)
77.60
4.14
(4.09)
4.41
5.51
(5.46)
6.72
VIIa
VIIb
VIIc
VIId
VIIe
VIIf
VIIIa
VIIIb
VIIIc
VIIId
VIIIe
VIIIf
IXg
IXh
IXi
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
(77.51)
75.10
(75.00)
75.39
(75.49)
74.76
(74.65)
74.70
(74.65)
70.10
(69.98)
74.85
(74.65)
72.51
(72.41)
73.10
(72.96)
72.10
(72.00)
72.50
(72.00)
67.68
(67.64)
76.35
(76.33)
77.14
(77.13)
81.50
(81.49)
81.51
(81.49)
69.03
(4.31)
4.56
(4.46)
4.87
(4.98)
4.20
(4.15)
4.21
(4.15)
3.80
(3.67)
4.35
(4.15)
4.42
(4.31)
5.10
(4.82)
4.14
(4.00)
4.53
(4.00)
3.59
(3.55)
3.85
(3.84)
4.80
(4.79)
4.03
(4.01)
4.02
(4.01)
3.45
(6.69)
6.45
(6.25)
9.21
(9.11)
6.51
(6.45)
6.57
(6.45)
9.08
(9.07)
6.59
(6.45)
6.07
(6.03)
9.10
(8.81)
6.31
(6.22)
6.50
(6.22)
8.91
(8.77)
3.58
(3.56)
6.86
(6.66)
3.29
(3.28)
3.20
(3.28)
2.99
225
240
IXj
250
Xg
230
(69.02)
70.10
(70.09)
73.89
(73.88)
73.90
(3.43)
4.27
(4.26)
3.62
(3.60)
3.63
(2.98)
5.66
(5.64)
2.79
(2.78)
2.80
Xh
245
Xi
260
Xj
280
(73.88)
69.39
(69.37)
70.45
(3.60)
3.68
(3.67)
4.49
(2.78)
3.00
(2.96)
5.67
XIg
XIh
XIi
265
6.88
(6.86)
6.49
255
(70.43)
74.25
(4.48)
3.83
(5.66)
3.00
(6.48)
6.41
270
(74.24)
74.26
(3.82)
3.84
(2.79)
3.01
(6.39)
6.41
XIj
C31H19NO4S
(501.56)
285
(74.24)
(3.82)
(2.79)
(6.39)
Solvent for crystallisation: a = ethanol; b = methanol.

HeterocyclicNitrogenCompoundsIncorporating1,4-naphthquinone
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 805
Table 2. IR and 1H NMR Spectral Data of Some Selected Heterocyclic Compounds I-XI
Comp.
No.
IR (KBr max cm-1)
1H NMR (DMSO) ppm
I
II
1720 (C=O)
1735 (C=O)
7.06-8.0 (m, 9H, aromatic), 3.22 (s, 2H, -CH2 joined to phenyl).
7.06-8.0 (m, 9H, aromatic), 4.32 (s, 1H, -CH joined to phenyl), 3.12 (s, 2H,
-CH2 cyclopentanone).
IIIa
IVa
Va
1735 (C=O),
1610 (C=C)
1745 (C=O),
1575-1520 (C=N)
1775 (C=O),
1575 (C=N)
1745 (C=O),
1575 (C=N)
1735 (C=O),
1575 (C=N),
3400-3300 (N-H)
1700 (C=O),
1575 (C=N),
3400 (N-H)
7.06-8.0 (m, 14H, aromatic), 4.8 (s, 1H, ylidene),
4.32 (s, 1H, CH joined to phenyl).
7.06-8.0 (m, 14H, aromatic), 2.2 (s, 3H, -CH-CH3), 7.1-7.3 (d, 2H,
pyrazoline), 4.32 (s, 1H, -CH joined to phenyl).
7.06-8.0 (m, 14H, aromatic),7.2-7.5 (d, 2H, pyrazoline protons), 4.32 (s, 1H,
-CH, -CH joined to phenyl).
7.06-8.0 (m, 14H, aromatic), 6.6-6.8 (d, 2H, isoxazoline protons), 4.32 (s,
1H, -CH joined to phenyl).
7.06-8.0 (m,14H, aromatic), 3.1 (b, 1H, -NH),
6.4-6.6 (m, 2H, pyrimidine protons),
VIa
VIIa
4.32 (s, 1H, -CH joined to phenyl).
VIIIa
IXg
7.06-8.0 (m, 14H, aromatic), 3.1 (b, 1H, -NH),
5.4-5.6 (m, 2H, pyrimidine thiono protons),
4.32 (s, 1H, -CH joined to phenyl).
7.01-8.2 (m, 14H, aromatic),
4.32 (s, 1H, -CH joined to phenyl).
1735 (C=O),
1580 (C=N)
1745 (C=O)
1735 (C=O)
Xg
XIg
7.02-8.1 (m, 14H, aromatic), 1.4 (s, 1H)
7.03-8.1 (m, 14H, aromatic), 1.2 (s, CH of thiazolidinone).
(Va,c,f) in crease the ac tiv ity. On the other hand, in ser tion of
isoxazolino and/or pyrimidino moi eties (VIa,c,f-VIIIa,c,f) to
theparentcompound( IIIa,c.f) causes a high in crease in the bi-
ologicalactivity,especially those containing -N-(CH3)2
substituent.
ac tion mix ture was fil tered, con cen trated and boil ing wa ter
was added. The prod uct ( II)precipitatedoutandwasfiltered
off, washed sev eral times with wa ter, dried and crys tal lised
from the proper sol vent (cf. Ta ble 1).
Synthesis of 3-arylideno-1-phenylnaphthcyclopentan-
2,4,9-trione (IIIa-f)
EXPERIMENTAL
Amixture of II (0.01 mol) and the aromaric al de hyde
(0.01 mol) was dissolved in ethanol (20 mL) containing
piperidine (1 mL) and refluxed for 25-30 h. The re ac tion mix-
ture was then fil tered while hot, con cen trated and al lowed to
coolatroomtemperatureforovernight.Onadditionofpetro-
leum ether 60-80 C, aresinousmaterialwasseparatedand
trituratedwithwater.Theresultingsolidwasfiltered,washed
sev eral times with wa ter, dried and crys tal lised from the
proper sol vent (cf. Ta ble 1).
Allmeltingpointsareuncorrected.TheIRspectrawere
re corded on a Perkin-Elmer 127 B spectrophotometer and 1H
NMRspectraonanEM390(90MHz)spectrometer.
Synthesis of 2-benzyl-1,4-naphthquinone (I)
A mix ture of 1,4-naphthquinone (0.01 mol) and benzyl
chloride(0.01mol)inethyleneglicol30mLcontaining5mL
so dium bi car bon ate 20%, was refluxed for 8 h. The hot re ac-
tion mix ture was fil tered; to the fil trate were added 10 mL
eth a nol and a few moles of ace tic acid; refluxed again for 2 h.,
thentothehotreactionmixturecoldwaterwasadded,where-
by the prod uctIsep a rated out; it was fil tered off, washed sev-
eral times with wa ter, dried and crys tal lised from the proper
solvent(cf. Table1).
Synthesis of 1-phenylnaphthcyclopentan(2,3-c)-N-
acetylpyrazolino-4,9-dione (IV a-f
)
A mix ture of IIIa-f (0.01 mol) and hydrazinhydrate
(0.01 mol) in eth a nol (20 mL) con tain ing ace tic acid (1 mL)
was pre pared. The re ac tion mix ture was then fil tered while
hot, concentrated to one-third of its volume, poured in
ice-watermixturewithvigorousstirringandleftovernightat
room tem per a ture. The re sult ing solid was fil tered, washed
sev eral times with wa ter, dried and crys tal lised from the
proper sol vent (cf. Ta ble 1).
Synthesis of 1-phenylnaphthcyclopentan-2,4,9-trione (II)
Amixtureof 2-benzyl-1,4-naphthquinone I (0.01 mol)
and monochloroacetic acid (0.01 mol) in 30 mL eth a nol con-
tain ing 2 mL triethylamine was refluxed for 10 h. The hot re-

806 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Khalafallah
Synthesis of 1-phenylnaphthcyclopentan(2,3-c)-N-
phenylpyrazolino-4,9-dione (Va-f)
chloride or mercaptoacetic acid in DMF (30 mL) in the pres-
ence of a cat a lytic amount of triethylamine (0.1 mL). The re-
ac tion mix ture was heated un der re flux for 8-10 hr. (mon i-
tored by TLC). The sol vent was then evap o rated un der re-
duced pres sure and the res i due was treated with ice/wa ter.
The solid prod uct was col lected and crys tal lized from DMF.
A mix ture of IIIa-f (0.01 mol) and phenylhydrazine
(0.01 mol) was dis solved in eth a nol (20 mL) con tain ing
piperidine (1 mL) and refluxed for 18-26 h. The re ac tion mix-
ture was then fil tered while hot, con cen trated to one-third of
its vol ume, poured in ice-water mix ture with stir ring for 40
min. and left over night at room tem per a ture. The re sult ing
solidwasfiltered,washedseveraltimeswithwater,driedand
crystallisedfromthepropersolvent(cf. Table1).
Received December 26, 2000.
Key Words
Synthesis of 1-phenylnaphthcyclopentan(2,3-c)-
isoxazolino-4,9-dione derivatives(VIa-f)
1,4-naphthquinone.
A mix ture of IIIa-f (0.01 mol) and hydroxylamine hy-
drochloride(0.01mol)inethanol(20mL)containing2%so-
dium hy drox ide (1 mL) was refluxed for 20-25 h. The re ac-
tion mix ture was then fil tered while hot, the fil trate con cen-
trated to one-third of its vol ume, poured in ice-water mix ture
with stir ring for 20 min. and left over night at room tem per a-
ture. The re sult ing solid was fil tered, washed sev eral times
withwater, driedandcrystallisedfromthepropersolvent(cf.
Table1).
REFERENCES
1. Khalafallah, A. K.; El-Latif, F. M. Abd; Salim, M. A.;
El-Maghraby, M. A. Asian J. Chem. 1993, 5, 988.
2. Khalafallah, A. K.; Koraiem, A. I. M.; El-Maghraby, M.
A.; Shindy, H. A. J. In dian Chem. Soc. 1989, 66, 398.
3. El-Maghraby, M. A.; Khalafallah, A. K.; Hassan, M. E.;
Soliman, H. A. J. In dian Chem. Soc. 1986, 63, 910.
4. Khalafallah, A. K.; El-Ela, A. Abou; Elshami, E.;
El-Maghraby, M. A. J. In dian Chem. Soc. 1985, 62, 676.
5. El-Maghraby, M. A.; Koraiem, A. I. M.; Khalafallah, A.
K. Asw. Sci. Tech. Bull. 1984, 5, 1.
Synthesis of 1-phenylnaphthcyclopentan(2,3-c)pyrimidine
and/or pyrimidinethione-4,9-dione derivatives (VIIa-f and
VIIIa-f)
A mix ture of an ethanolic so lu tion of IIIa-f (0.01 mol),
ureaand/orthiourea(4g)andconcentratedhydrochloricacid
(20 mL) was refluxed for 15-22 h. The re ac tion mix ture was
then fil tered while hot, al lowed to cool and neu tral ised with
5NaOH. The re sult ing solid was fil tered, washed sev eral
times with wa ter, dried and crys tal lised from the proper sol-
vent (cf. Ta ble 1).
6. Khalafallah, A. K.; Selim, M. A.; El-hamd, R. M. Abu;
El-Maghraby, M. A.; Soleiman, H. A.; Raslan, M. A. In-
dian J. of Chem. 1995, 34B, 1066-1070.
7. Soleiman, H. A.; Khalafallah, A. K.; El-zaher, H. M. Abd
J. Chin. Chem. Soc. 2000, 47, 1267-1272.
8. Gill man, P. P.; Belly, R. J.; Kosselok, T. K.; Zigman, S.,
U. S. 4, 1980, 323, 121.; Chem. Abstr. 1981, 94, 97109.
9. Makisoumi, Y. Japan 1960, 13, 641.; Chem. Abstr. 1964,
60, 531.
10. Takamizowa, A.; Mamoshima, Y. Japan 1963, 14423.;
Chem. Abstr. 1966, 65, 20144.
11. Ito, I. Japan 1970, 7030, 10.; Chem. Abstr. 1971, 74,
22827.
12. Takamizowa, A.; Sato, ?. Japan 1972, 72, 45353.; Chem.
Abstr. 1973, 78, 58454.
Synthesis of 3-azoarylmethylene-1-phenyl-2,4,9-trione
derivatives (IXg-j)
A so lu tion of (II) (0.01 mole) in eth a nol (30 mL) was
treated with ar o matic nitroso com pounds (0.01 mole) in the
presenceofacatalyticamountofpiperidine(0.5mL). There-
actionmixturewasheatedunderrefluxfor7-9hr.(monitored
by TLC). The sol vent was then evap o rated un der re duced
pressureandtheresiduewastreatedwithice/water. Thesolid
productwascollectedandcrystallizedfromethanol.
13. Bellamy, L. J. The In fra red Spec tra of Com plex Mol e-
cules; 2nd Edn., Methuen, Lon don, 1964.
14. Scheimann, F. NuclearMagneticResonanceandInfra-
redSpectroscopy; 1970, Vol. 1, pp 41-70.
15. Loo, Y. H.; Skell, P. S.; Thorabrry, H. H.; Megurire, J. L.;
Sav age, G. M.; Sylvester, J. C. J. Bact. 1945, 50, 701.
Synthesis of 3-spiro(chloro-N-substituted- -lactam)-1-
phenyl-2,4,9-trione derivatives (Xg-j) and 3-spyro-
Nsubstituted thiazolidinone-1-phenyl-2,4,9-trione deriva-
tives (XIg-j)
A so lu tion of (IXg-j) was treated with chloroacetyl-