The syntheses of 4-arylamino-1,2,3-triazoles and stable 6-sydnonyl verdazyls from sydnone derivatives and their fragments

Article abstract of DOI:10.1002/jccs.200100110

α-Chloroformylarylhydrazones 1 and α-chloroformylarylhydrazones of sydnonecarbaldehydes 3 have been prepared by a new synthetic route: α-chloroformylarylhydrazines hydrochlorides 2 reacted with corresponding carbonyl compounds. Reactions of compounds 3 with various hydrazines to give 6-sydnonyl-1,2,4,5-tetrazinan-3-ones 7 and/or carbazones 8 were also investigated. By oxidization with lead dioxide, compounds 7 were transformed to stable 6-sydnonyl-3,4-dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl radical derivatives 9 (sydnonyl verdazyls). Furthermore, sydnonecarbaldehydes arylhydrazones 5 through acidic conditions could be transferred to 4-arylamino-1,2,3-triazoles 6 which were also obtained by means of acidic decompositions of 4-formylsydnones 10.

Full text of DOI:10.1002/jccs.200100110

JournaloftheChineseChemicalSociety, 2001, 48, 769-782
769
The Syn the ses of 4-Arylamino-1,2,3-triazoles and Sta ble 6-Sydnonyl
verdazyls from Sydnone DerivativesandTheirFragments
Wen-Fa Kuo (
), I-Tzu Lin (
),
Shiaw-Wen Sun (
) and Mou-Yung Yeh* (
)
DepartmentofChemistry,NationalChengKungUniversity,Tainan,Taiwan70101,R.O.C.
-Chloroformylarylhydrazones 1 and -chloroformylarylhydrazones of sydnonecarbaldehydes 3 have
been pre pared by a new syn thetic route: -chloroformylarylhydrazineshydrochlorides2 re acted with cor re-
spond ing car bonyl com pounds. Re ac tions of com pounds 3 with var i ous hydrazines to give 6-sydnonyl-
1,2,4,5-tetrazinan-3-ones7 and/or carbazones 8 werealsoinvestigated. Byoxidizationwithleaddioxide,
compounds7were trans formed to sta ble 6-sydnonyl-3,4-dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-ylradicalde-
rivatives9 (sydnonyl verdazyls). Fur ther more, sydnonecarbaldehydes arylhydrazones 5 through acidic con-
ditionscouldbetransferredto4-arylamino-1,2,3-triazoles6 which were also ob tained by means of acidic de-
compositionsof4-formylsydnones10.
INTRODUCTION
Scheme II
-Chloroformylarylhydrazones 1 are potent pre cur-
sors1-2 of antiinflammatory drugs and many heterocyclic
com pounds. In this study, com pounds 1 were pre pared with
O
C
R1
O
C
R1
O
C
N
N
Cl
THF
R4
N
H
C
+
N
Cl
R4
N
C
N
C C
H
NH2 HCl
2
O
O
C
N
good yields (Scheme I, path 1) by treatment of the
-
O
O
chloroformylarylhydrazineshydrochlorides 2 with cor re-
spondingaromaticaldehydesandketones.Sydnonecarbal-
dehyde -chloroformylarylhydrazones 3 were also pre pared
(SchemeII)inhighyields.Bothcondensationreactionswere
fast (within 40 min.) and pro ceeded at room tem per a ture. In
addition,theacidicdecompositionofsydnonecarbaldehydes
arylhydrazones 5to ob tain 4-arylamino-1,2,3-triazoles 6 is a
new syn thetic route for prep a ra tion of com pounds 6 and is
quitedifferentfromtraditionalmethods.3-5 Theexamination
ofacidicdecompositionof4-formylsydnone10 which would
producecompounds6has also been stud ied in this re port.
3
by Milcent et al.2 Intheirmethod, however, thereagent, phos-
gene,isanexpensiveanddangerouscontraband,andreaction
conditionsrequireheatingandanhydrousconditions.Hence
we de vel oped a new syn thetic method (path 1) to pre pare
-chloroformylarylhydrazones 1.
Accordingtotheliterature, 1,2,4,5-tetrazinan-3-ones
andtheiroxidizedproducts,verdazyls, possessliquid-crystal
properties6 andarenuclearmagneticresonancetomography
contrastagents.7 Also, sydnone com pounds are well-known
intheirbiological,pharmacologicalactivitiesandtheirex-
tremelyspecialelectronicstructure.However,syntheticreac-
tionsusingsydnonesareexperimentallydemandingasthese
compoundsareunstabletowardbothacidicandbasicmedia.
As a con se quence, the syn the sis must be car ried out with
carefulconsiderationoftemperature,reactionpath,reagents,
etc.8
Scheme I
O
C
1
R
O
2
N
Cl
3
Path 1
O
C
R
C R
1
+
R
NH2 HCl
2
2-propanol
Cl
N
N
3
R
C
For reasons mentioned above, we employed only
sydnonecarbaldehyde -chloroformylarylhydrazones 3 to
pre pare 6-sydnonyl-1,2,4,5-tetrazinan-3-ones7 which were
oxidizedtogivecorresponding6-sydnonyl-3,4-dihydro-3-
oxo-1,2,4,5-tetrazin-1(2H)-ylradicalderivatives,sydnonyl
verdazyls 9.Thesecompoundsarenewmoleculespossessing
3
1
O
C
R
R
NH N C
Path 2
2
+
2
R
Cl
Cl
1
R
4
Phosgene reacted with hydrazones 4 to give com -
pounds 1 (Scheme I, path 2) had been re ported in good yield

770 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Kuo et al.
si mul ta neously a mesoionic group (sydnone) and a rad i cal
group (verdazyls) as dis played in Scheme IV.
(b)) in the pres ence of HCl (in EtOAc at 60 C); some mol e-
cules of 4-formylsydnones trans ferred to arylhydrazine by
acidic de com po si tion and con densed with other 4-formyl-
sydnone mol e cules to form com pounds5 , which would be
fur ther de com posed in the acidic con di tions to give com-
pounds 6 (Ta ble 3, 6h-6k). It is note wor thy that the same
prod ucts (Ta ble 3, 6j-6k) could be ob tained through acidic
decompositionofsydnonecarbaldehydealkylhydrazones 11
(R6 = CH3, H). When com pounds 11 (Scheme III, (c)) were
adoptedasstartingmaterials, acidicdecompositiondidnot
give the ex pected prod ucts, 4-arkylamino-1,2,3-triazoles 12,
but 4-arylamino-1,2,3-triazoles 6 were produced in low
yields. These ob ser va tions can ac count for the hy dro ly sis of
compounds 11 that would give com pounds 10. Acidic de-
compositionandcondensationofcompound10 gave com-
RESULTSANDDISCUSSION
In the re ac tion of com pounds 2with al de hydes or ke-
tones,theselectionofsolventisextremelyimportantbecause
com pounds2 pos sess both nucleophilc (-NH2) and electro-
philc (-COCl) groups and hence it easily undergoesself-
dimerization in sol vent.9 THF and 2-propanol were suit able
solventstopreparecompounds 1afterasequenceofvarious
solvent studies. The former would dissolve the products
(compounds 1), andresultedininconvenientisolationand
unsatisfyingyields. Using2-propanolassolvent, ontheother
hand,theproductsprecipitatedandwereconsiderablypureas pound 5 , which was trans ferred to com pound 6 afterfurther
con firmed by el e ment anal y sis. Pres ented in Ta ble 1 are the
syntheticresults.
acidicdecomposition.
Milcent2 and Neugebauer10obtained1,2,4,5-tetrazinan-
Con trary to the above re sults, sydnonecarbaldehydes
were quite in sol u ble in 2-propanol and did not re act with
compounds 2, sydnonecarbaldehyde -chloroformyl aryl-
hydrazones 3 were prepared in THF at acid condition
(SchemeII).Purificationofeachproductwasalsoeasilyper-
formed by sim ple fil tra tion from the re ac tion so lu tion and
recrystallization from THF (Ta ble 2).
In view of the poor sta bil ity of sydnone ring, 4- aryl-
amino-1,2,3-triazoles 6 might be ob tained by means of the
acidicdecompositionofcompounds5 (Scheme III, (a)). Af-
ter add ing HCl(aq) to the so lu tions of com pounds5 in EtOAc
and heat ing to 60 C; the sydnone ring open ing and decar-
boxylation pro ceeded se quen tially to pro duce 4-arylamino-
1,2,3-triazoles6 (Ta ble 3, 6a-6i). Thereactionmechanism
pro posed in Scheme III is re ferred to as a photolysis mech a-
nism of sydnone ring re ported by Marky5 and the struc tures
of com pounds 6 were iden ti fied by var i ous spec tral data and
X-raydiffractionanalysis(Fig.1,Tables6,7,8).Analterna-
tivemethodtosynthesizecompounds6wasaccomplishedby
acidicdecompositionof4-formylsydnones 10 (Scheme III,
3-ones by the reaction of com pounds 1 with substituted
hydrazinesandfollowedbyoxidizationtogiveverdazylsde-
riv a tives. We have also un der taken re ac tion stud ies of com-
pounds 3 with hydrazine hy drate, methylhydrazine and var i-
ous arylhydrazines hy dro chlor ides in the pres ence of tri-
ethylamine. It was found that the com pounds 7 and/or
sydnonecarbaldehyde carbazones 8 (Scheme IV) can be pro-
vided. Thereactionsofcompounds3 with hydrazine hy drate
inethanolwereconvertedexclusivelyintothecorresponding
Table 2. Preparation of Compound 3 from Compound 2 in THF
Compound
R1
R4
Yield ( )
3a
3b
3c
3d
3e
3f
H
CH3
H
CH3
Cl
H
Cl
CH3O
H
H
CH3
CH3
78
80
88
90
81
76
80
85
CH3
CH3O
CH3O
CH3O
3g
3h
Table 1. Preparation of Compound 1 from Compound 2 in 2-Propanol
Compound
R1
R2
R3
Yield ( )
Mp ( C)
Mp ( C, liter.)
1a
1b
1c
1d
1e
1f
H
H
H
H
CN
CH3O
CH3O
H
H
H
H
78
80
77
82
92
91
88
101-102
126.5-127.5
91.5-92.5
112-113
129-130
123-124
101-1022
-
922
Cl
H
-
-
-
-
CH3
CH3O
Cl
CH3
CH3
CH3
H
H
1g
108-109

1,2,3-Triazoles and 6-Sydnonyl-verdazyls
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 771
carbazones 8, whereas only cy clic prod ucts 7 were ob tained
by the re ac tion with methylhydrazine.
Scheme III
(a)
In ad di tion, when arylhydrazines were em ployed to re-
act with com pounds3, the re ac tions pro ceeded via 1-N and/
or 2-N-acylations of arylhydrazines and gave com pounds 7
and/or 8. The yield ra tios of com pounds 7/8weredependent
on the electronic ef fects of the sub stitu ents borne by the
arylhydrazines. Phenyl-, 4-methylphenyl- and 4-ethoxy-
phen yl hydrazines re acted with com pounds 3 to give com-
pounds 7 and 8 in good yields and the yield ra tios of com-
pounds 7/8were1/1, 1/1and8/1, respectively. Forreactionof
4-ethoxycarbonyl-phenylhydrazinehydrochloridewithcom-
pounds 3, 1-N-acylation could not pro ceed and were con-
verted only into the cor re spond ing carbazones 8 since the
elec tron den sity of 1-N de creased due to the -withdrawing
na ture of the ethoxycarbonyl group. How ever, when 4- fluo-
ro phenyl hydrazine re acted with com pounds3, the yield ra-
R1
NHNH2
O
H
H
R4
N
C C H
R4
N
C C N N
R1
N
C
O
N
C
O
O
O
5
10
o
H
C
HCl(aq)
EtOAc / 60 C
R4
N
C
N
N
NH
H
H
R4
N
C
C N
N
R1
N
C
R1
O
O
H
C
H
N
R4
N C
N
N
R1
6a ~ 6i
(b)
H
H
HCl(aq)
4
4
10
R
N
C C N N
R
6h ~ 6k
o
EtOAc / 60 C
N
C
O
O
5'
(c)
H
R6
HCl(aq)
N
N
o
EtOAc
/ 60 C
HCl
NHNH2
6j , 6k
10
5'
R4
N
C C H
6
_
R
N
C
O
O
H
11
C
N
Fig. 1. Molecularstructureof2-(4-methylphenyl)-
4-(4-methylphenylamino)-2H-1,2,3-triazole
(6h).
R4
N C
N
R6
N
H
12
Table 3. Preparation of Compounds 6 from Compounds 5, 10, 11
[2]
Compound
R1
R4
Yield%[1]
Yield%
Yield%[3]
6a
6b
6c
6d
6e
6f
6g
6h
6i
p-CH3
p-CH3
p-CH3
H
H
H
p-Cl
p-CH3
H
p-EtO
p-CH3O
H
p-EtO
p-CH3O
p-CH3
p-CH3O
p-CH3
H
52
81
61
40
59
60
70
61
72
-
-
-
-
-
-
-
-
70
30
62
57
-
-
-
-
-
-
-
-
-
6j
6k
p-EtO
p-CH3O
10*1
10*2
-
Starting material: [1] = compound 5, [2] = compound 10, [3] = compound 11.
*1: R6 = CH3. *2: R6 = H.

772 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Kuo et al.
at 1H NMR spec tra and there was not an N-H stretch ing sig nal
in the IR spec tra. The mo lec u lar weight and com po si tion
anal y sis were iden ti fied by both mass spec tros copy and el e-
mentanalysis.
Scheme IV
1
R
O
C
1
R
H
N
O
C
5
R
H
N
N
N
N
5
1
2
R
N
N
C
N
H
5
R
NHNH
2
H
N
C
3
and / or
H
4
C
R
4
C
N
H
R
C
N
O
O
C
N
CONCLUSION
O
O
7
8
1
R
O
C
5
4-Arylamino-1,2,4-triazoles 6 could be syn the sized by
acidic de com po si tions of ei ther sydnonecarbaldehydes aryl-
hydrazones 5 or 4-formylsydnones 10. Using -Chloro for-
mylarylhydrazines 2 asstartingmaterials, -chloro formyl-
hydrazonesofaldehydes,ketonesandsydnonecarbaldehydes
might be pre pared more eas ily and safely. In the syn thetic
study of sydnonylverdazyls 9, these re sults pre sented that the
methyl- and methoxyphenyl hydrazines were better re agents
to pre pare com pounds7 andthepartitionsofintermediates
7/8wereextremelydependentontheelectroniceffectsofthe
sub stitu ents borne by the arylhydrazines. By ox i di za tion,
com pounds7 were trans formed into sydnonylverdazyls 9,
possessingbothmesoionicandradicalstructureattributes.
R
N
N
N
PbO
2
N
AcOH
C
4
C
N
R
C
N
O
O
9
tios of 7/8 were ap prox i mately 2/1, which were higher than
7/8 ra tios of phenylhydrazine re acted with com pounds 3,
even though the flu o ride is -with draw ing group and would
de mote the charge den sity of 1-N. All the yields of com-
pounds 7 and 8 are pre sented in Ta ble 4.
Ox i da tions of 6-sydnoyl-1,2,4,5-tetrazinan-3-ones7
with lead di ox ide into sta ble sydnonyl-3-oxo-1,2,4,5- tetra-
zinyl rad i cal, sydnonyl-verdazyls 9 (Scheme IV), were per-
formed in CH2Cl2 with acetic acid (Table 5). Sydnonyl
verdazyls 9 arenewmoleculesofradicalwithhighstability,
i.e., decompositionofthesecompoundswasnotobservedaf-
teroneyearatroomtemperature.Structureidentificationof
thesemoleculesisbasedonthefollowingspectroscopicdata.
NoprotonsignalexceptwaterandDMSO-d6 peaks pre sented
EXPERIMENTAL SECTION
General
Melting points (Buchi 535 ap pa ra tus) are un cor rected.
IR spec tra were re corded on a Hitachi 270-30 in fra red spec-
Table 4. Preparation of Compounds 7 and 8 from Compounds 3
R1
R4
R5
Yield (%)
Starting
material
Compound 7
Compound 8
3f
3h
3f
3g
3h
3f
H
CH3O
H
Cl
CH3O
H
H
CH3
CH3
Cl
CH3O
CH3O
CH3O
CH3O
CH3O
CH3O
CH3O
H
CH3
CH3
CH3O
CH3O
CH3O
CH3
H
H
CH3
CH3
CH3
7a
-
-
8a
80
83
-
-
-
10
30
38
41
44
37
37
36
29
30
82
85
7b
7c
7d
7e
7f
7g
7h
7i
7j
7k
7l
7m
7n
7o
7p
7q
8b
8c
8d
8e
8f
8g
8h
8i
8j
8k
8l
8m
8n
8o
8p
8q
76
81
88
79
51
44
48
43
50
51
53
56
54
-
p-CH3OC6H4
p-CH3C6H4
C6H5
3f
3b
3d
3e
3f
3g
3h
3c
3d
3d
3e
C6H5
C6H5
C6H5
C6H5
H
Cl
CH3O
H
CH3
CH3
Cl
C6H5
p-FC6H4
p-FC6H4
p-EtOCOC6H4
p-EtOCOC6H4
CH3
CH3
CH3
-

1,2,3-Triazoles and 6-Sydnonyl-verdazyls
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 773
Table 7. Bond Distances/Å of 6h
Table 5. Preparation of Compound 9 from Compound 7
Compound 9
R1
R4
R5
Yield
C(1)-C(2)
C(1)-N(1)
C(1)-N(4)
C(2)-N(3)
C(2)-H(2)
C(3)-C(4)
C(3)-C(8)
C(3)-N(2)
C(4)-C(5)
C(4)-H(4)
C(5)-C(6)
C(5)-H(5)
C(6)-C(7)
C(6)-C(9)
C(7)-C(8)
C(7)-H(7)
C(8)-H(8)
C(9)-H(9a)
C(9)-H(9b)
1.394(8)
1.319(7)
1.351(7)
1.328(7)
0.952(5)
1.352(7)
1.373(7)
1.434(6)
1.401(8)
0.950
1.380(8)
0.951
1.395(7)
1.469(7)
1.367(7)
0.952
C(9)-H(9c)
C(10)-C(11)
C(10)-C(15)
C(10)-N(4)
C(11)-C(12)
C(11)-H(11)
C(12)-C(13)
C(12)-H(12)
C(13)-C(14)
C(13)-C(16)
C(14)-C(15)
C(14)-H(14)
C(15)-H(15)
C(16)-H(16a)
C(16)-H(16b)
C(16)-H(16c)
N(1)-N(2)
0.951
1.387(7)
1.382(7)
1.409(8)
1.371(8)
0.952
1.388(7)
0.952
1.382(9)
1.505(8)
1.369(9)
0.952
0.951
0.951
0.949
0.950
1.367(6)
1.318(6)
0.952
9a
9b
9c
9d
9e
9f
CH3
CH3
Cl
H
Cl
H
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
65
62
68
70
71
67
CH3
CH3
CH3O
CH3O
CH3O
CH3O
trometer. 1H NMR spec tra were mea sured on a Bruker AMX-
200 NMR spec trom e ter with tetramethylsilane as in ter nal
standard, 13C NMR spec tra were run on a Bruker AC-300 in
DMSO-d6. The mass spec tra were reg is tered on a Finnigan
MATTSQ-46Cspectrometeratanionizingpotential70eV.
El e men tal anal y ses were per formed on Heraeus CHN- O-
RapidandTacusselCoulomax78analyzers.UVspectrawere
taken on a Hitachi U-2000 Spectrophotometer. X-ray in ten-
sity data was col lected with a Nonius CAD-4 diffractometer.
Column chromatography was carried out on silica gel
(Kieselgel 100, 230-400 mesh, E. Merck).
0.952
0.950
0.950
N(2)-N(3)
N(4)-H(N4)
ride 1a (0.828 g, 4 mmol) and benzaldehyde (0.467 g, 4.4
mmol) in 10 mL ofi-PrOH (1 drop of H2SO4 was added for re-
ac tion of1e~1g) was stirred at room tem per a ture for 30 min-
utes. The precipitating solid was collected by filtration,
washed with cold i-PrOH and dried to af ford pure pow der
prod uct1a (0.833 g, 81%).
Preparationof -Chloroformylarylhydrazones of Alde-
hydes 1a~1d and ketones 1e~1g
Asolutionof -chloroformylarylhydrazinehydrochlo-
Benzaldehyde -chloroformylphenylhydrazone (1a)
White pow der, IR (KBr), cm-1: 1728 ( C=O), 1593 (
C=N), 1HNMR(Acetone-d6), = 7.74~7.60 (m,J = 5H), 7.50
(s, 1H), 7.47~7.42 (m, 5H), EIMS (70 eV) m/z (%): 260
(M++2, 8), 258 (M+, 25), 221 (5), 195 (100), 167 (34), 155
(21), 120 (30), 104 (30), 89 (38), 77 (77). Anal. Calcd for
C14H11N2OCl (258.70): C: 65.00, H: 4.29, N: 10.83. found C:
64.97, H: 4.31, N: 10.86.
Table 6. Crystal Data of 6h
Formula
Formula weight
Cryst system
Space group
a/Å
C16H16N4
264.33
Orthorhombic
P-212121
6.224 (7)
7.586 (8)
29.150 (7)
1376.4 (22)
4
b/Å
c/Å
V/Å3
4-Cyanobenzaldehyde -chloroformylphenylhydrazone
(1b)
Z
Dc/g cm3
F000
1.271
Yel low pow der, IR (KBr), cm-1: 2224 ( CN), 1734 (
C=O), 1602 ( C=N), 1HNMR(Acetone-d6), = 7.94 (d, J =
8.5 Hz, 2H), 7.83 (d, J= 8.5 Hz, 2H), 7.73~7.62 (m, 3H), 7.56
(s, 1H), 7.46 (dd,J = 7.9, 2.0 Hz, 2H). EIMS (70 eV) m/z (%):
285 (M++2, 8), 283 (M+, 24), 248 (7), 220 (100), 192 (18),
155 (12), 119 (29), 102 (25), 91 (24), 77 (59). Anal. Calcd for
C15H10N3OCl (283.71): C: 63.50, H: 3.55, N: 14.81. found C:
63.52, H: 3.69, N: 14.72.
556.19
0.70930
0.07
12.64-26.10
2
44.9
3964
1807
1559
182
0.035
0.048
1.41
(Mo-K ) Å
/cm-1
Range/deg
Scan type
2
max/deg.
Reflections measured
Unique reflections
Observed reflections
Refined parameters
Rf for significant reflections
Rw for significant reflections
GoF
4-Methoxybenzaldehyde -chloroformylphenylhydrazone
(1c)
Yel low pow der, IR (KBr), cm-1: 1725 ( C=O), 1611 (
C=N), 1HNMR(Acetone-d6), = 7.68~7.56 (m, 5H), 7.45~

774 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Table 8. Bond Angles/deg of 6h
Kuo et al.
C(2)-C(1)-N(1)
C(2)-C(1)-N(4)
N(1)-C(1)-N(4)
C(1)-C(2)-N(3)
C(1)-C(2)-H(2)
N(3)-C(2)-H(2)
C(4)-C(3)-C(8)
C(4)-C(3)-N(2)
C(8)-C(3)-N(2)
C(3)-C(4)-C(5)
C(3)-C(4)-H(4)
C(5)-C(4)-H(4)
C(4)-C(5)-C(6)
C(4)-C(5)-H(5)
C(6)-C(5)-H(5)
C(5)-C(6)-C(7)
C(5)-C(6)-C(9)
C(7)-C(6)-C(9)
C(6)-C(7)-C(8)
C(6)-C(7)-H(7)
C(8)-C(7)-H(7)
C(3)-C(8)-C(7)
C(3)-C(8)-H(8)
C(7)-C(8)-H(8)
C(6)-C(9)-H(9a)
C(6)-C(9)-H(9b)
C(6)-C(9)-H(9c)
H(9a)-C(9)-H(9b)
H(9a)-C(9)-H(9c)
H(9b)-C(9)-H(9c)
C(11)-C(10)-C(15)
109.1(5)
C(11)-C(10)-N(4)
C(15)-C(10)-N(4)
C(10)-C(11)-C(12)
C(10)-C(11)-H(11)
C(12)-C(11)-H(11)
C(11)-C(12)-C(13)
C(11)-C(12)-H(12)
C(13)-C(12)-H(12)
C(12)-C(13)-C(14)
C(12)-C(13)-C(16)
C(14)-C(13)-C(16)
C(13)-C(14)-C(15)
C(13)-C(14)-H(14)
C(15)-C(14)-H(14)
C(10)-C(15)-C(14)
C(10)-C(15)-H(15)
C(14)-C(15)-H(15)
C(13)-C(16)-H(16a)
C(13)-C(16)-H(16b)
C(13)-C(16)-H(16c)
H(16a)-C(16)-H(16c)
H(16a)-C(16)-H(16c)
H(16b)-C(16)-H(16c)
C(1)-N(1)-N(2)
124.3(4)
117.5(5)
120.2(4)
121.1
118.8
122.1(5)
126.0(5)
124.9(5)
109.3(3)
124.8
125.9
121.0(5)
120.4(5)
118.6(4)
119.5(5)
118.8
117.2
120.6
117.0(5)
121.2(5)
121.8(5)
121.4(5)
120.0
118.6
121.2(5)
119.6
119.2
110.6
112.7
109.9
108.7
105.6
109.2
102.9(4)
123.1(4)
121.8(4)
115.0(4)
103.7(4)
129.3(4)
115.7
121.6
120.9(4)
119.7(6)
119.4(6)
117.2(5)
122.6(5)
120.2(5)
121.9(5)
120.4
117.7
119.4(5)
118.5
122.1
112.5
111.5
109.6
109.7
107.3
105.9
118.2(5)
C(3)-N(2)-N(1)
C(3)-N(2)-N(3)
N(1)-N(2)-N(3)
C(2)-N(3)-N(2)
C(1)-N(4)-C(10)
C(1)-N(4)-H(N4)
C(10)-N(4)-H(N4)
115.0
7.40 (m, 3H), 6.98 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H). EIMS (70
eV) m/z (%): 290 (M++2, 13), 288 (M+, 42), 225 (68), 210
(11), 182 (56), 155 (20), 134 (40), 119 (27), 91 (53), 77 (100),
63 (49). Anal. Calcd for C15H13N2O2Cl (288.73): C: 62.40, H:
4.54, N: 9.70. found C: 62.41, H: 4.59, N: 9.81.
4-Methoxybenzaldehyde -chloroformyl-4-chlorophenyl-
hydrazone (1d)
White pow der, IR (KBr), cm-1: 1713 ( C=O), 1605 (
C=N), 1HNMR(Acetone-d6), = 7.71~7.65 (m, 4H), 7.52 (d,
J = 8.9 Hz, 2H), 7.46 (s, 1H), 6.98 (d, J = 8.9 Hz, 2H), 3.84 (s,
3H). EIMS (70 eV) m/z (%): 326 (M++4, 7), 324 (M++2, 36),
322 (M+, 54), 261 (32), 259 (100), 224 (32), 216 (40), 153
(40), 134 (77), 111 (48), 91 (50), 77 (74). Anal. Calcd for
C15H12N2O2Cl2 (323.18): C: 55.75, H: 3.74, N: 8.67. found C:
55.80, H: 3.83, N: 8.87.
2H), 7.51 (m, 1H), 7.42 (d, J = 7.8 Hz, 2H), 7.27 (d,J = 8.0 Hz,
2H), 2.38 (s, 3H), 2.32 (s, 3H), FABMS (1.13 eV) m/z (%):
287 (M++1, 36), 286 (M+, 24). Anal. Calcd for C16H15N2OCl
(286.76): C: 67.01, H: 5.27, N: 9.76. found C: 66.93, H: 5.29,
N: 9.74.
Acetophenone -chloroformyl-4-methoxyphenyl-
hydrazone (1f)
Pale yel low pow der; IR (KBr), cm-1: 1728 ( C=O), 1H
NMR (DMSO-d6), = 7.85 (d, J = 8.0 Hz, 2H), 7.53-7.41 (m,
5H), 7.00 (d, J = 8.1 Hz, 2H), 3.76 (s, 3H), 2.39 (s, 3H),
FABMS (1.26 eV) m/z (%): 305 (M++3, 34), 304 (M++2, 31),
303 (M++1, 77), 302 (M+, 68). Anal. Calcd for C 16H15N2O2Cl
(302.76): C: 63.47, H: 4.99, N: 9.25. found C: 63.42, H: 5.09,
N: 9.31.
Acetophenone -chloroformyl-4-chlorophenylhydrazone
(1g)
White pow der; IR (KBr), cm-1: 1713 ( C=O), 1H NMR
(DMSO-d6), = 7.77 (d, J = 8.2 Hz, 2H), 7.51-7.48 (m, 5H),
7.23 (d, J = 8.2 Hz, 2H), 2.24 (s, 3H), FABMS (1.26 eV) m/z
Acetophenone -chloroformyl-4-methylphenylhydrazone
(1e)
White pow der, IR (KBr), cm-1: 1722 ( C=O), 1H NMR
(DMSO-d6), = 7.88 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 7.8 Hz,

1,2,3-Triazoles and 6-Sydnonyl-verdazyls
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 775
(%): 309 (M++3, 32), 307 (M++1, 50). Anal. Calcd for
C15H12N2OCl2 (307.18): C: 58.70, H: 4.08, N: 9.46. found C:
58.81, H: 4.07, N: 9.37.
2H), 6.54 (d, J = 8.3 Hz, 2H), 2.07 (s, 3H), 2.06 (s, 3H), EIMS
(70 eV), m/z (%): 372 (M++2, 14), 370 (M+, 40), 312 (100),
249 (10), 133 (28), 118 (44), 105 (16), 91 (44), 77 (69). Anal.
Calcd. for C18H15O3N4Cl: C: 58.31, H: 4.08, N: 15.11. found
C: 58.31, H: 4.15, N: 15.00.
Preparationofsydnonecarbaldehyde -chloroformyl-
arylhydrazones 3a~3h
3-(4-Methylphenyl)sydnon-4-ylformaldehyde
A so lu tion of -chloroformylphenylhydrazine hy dro-
chlo ride (0.327 g, 1.58 mmol) and 0.3 g (1.58 mmol) of
3-phenylsydnonecarbaldehyde in THF (5 mL) was stirred at
roomtemperaturefor30minutes.Theprecipitatingsolidwas
col lected by fil tra tion and the fil trate was re moved un der re-
duced pres sure. 10 mL of i-PrOH was added, stirred and then
filtered. Thesolidproductswerecombinedandrecrystallized
with THF to ob tain 3-phenylsydnonecarbaldehyde -chloro-
formylphenylhydrazone 3a (0.481 g, 78%).
-chloroformyl-4-chlorophenyl-hydrazone (3e)
Yel low nee dles; mp 214-215 C, IR (KBr), cm-1: 1776,
1737 ( C=O), 1HNMR(Acetone-d6), = 7.68 (d, J = 8.3 Hz,
2H), 7.44 (d, J = 8.3 Hz, 2H), 7.40 (s, 1H), 6.88 (d,J = 7.7 Hz,
2H), 6.56 (d, J = 7.7 Hz, 2H), 2.07 (s, 3H), EIMS (70 eV), m/z
(%): 394 (M++4, 5), 392 (M++2, 22), 390 (M+, 33), 322 (100),
269 (6), 153 (33), 118 (95), 91 (36). Anal. Calcd. for
C17H12O3N4Cl2: C: 52.19, H: 3.09, N: 14.32. found C: 52.13,
H: 3.13, N: 14.16.
3-Phenylsydnon-4-ylformaldehyde -chloroformyl-4-
methylphenylhydrazone (3a)
3-(4-Methoxyphenyl)sydnon-4-ylformaldehyde
-chloroformylphenylhydrazone (3f)
Yel low nee dles; mp 201-202 C, IR (KBr), cm-1: 1779,
1716 ( C=O), 1HNMR(Acetone-d6), = 7.81-7.68 (m, 5H),
7.61-7.29 (m, 5H), 7.02 (s, 1H). EIMS (70 eV) m/z (%): 344
(M++2, 8), 342 (M+, 44), 284 (100), 249 (3), 221 (12), 119
(49), 104 (69), 77 (79). Anal. Calcd for C17H13O3N4Cl:
(342.74) C: 56.07, H: 3.23, N: 16.35. found C: 56.07, H: 3.24,
N: 16.31.
Yel low pow der; mp 168-169 C, IR (KBr), cm-1: 1779,
1725 ( C=O), 1HNMR(Acetone-d6), = 7.80-7.52 (m, 5H),
7.55 (d, J = 8.3 Hz, 2H), 7.20 (d,J = 8.3 Hz, 2H), 6.94 (s, 1H),
3.98 (s, 3H), EIMS (70 eV), m/z (%): 374 (M++2, 10), 372
(M+, 20), 314 (100), 251 (7), 134 (633), 119 (24), 77 (35).
Anal. Calcd. for C17H13O4N4Cl: C: 54.78, H: 3.51, N: 15.03.
found C: 54.82, H: 3.50, N: 15.05.
3-Phenylsydnon-4-ylformaldehyde -chloroformyl-4-
methylphenylhydrazone (3b)
3-(4-Methoxyphenyl)sydnon-4-ylformaldehyde
-chloroformyl-4-chlorophenyl-hydrazone (3g)
Yel low nee dles; mp 209-210 C, IR (KBr), cm-1: 1758,
1737 ( C=O), 1HNMR(Acetone-d6), = 7.70-7.51 (m, 5H),
7.42 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.3 Hz, 2H), 7.04 (s, 1H),
2.39 (s, 3H), EIMS (70 eV), m/z (%): 358 (M++2, 12), 356
(M+, 37), 298 (100), 235 (8), 133 (50), 104 (55), 91 (29), 77
(41). Anal. Calcd for C17H13O3N4Cl: (356.76) C: 57.23, H:
3.67, N: 15.70. found C: 57.15, H: 3.71, N: 15.66.
3-(4-Methylphenyl)sydnon-4-ylformaldehyde
Yel low nee dles; mp 200-201 C, IR (KBr), cm-1: 1776,
1740 ( C=O), 1HNMR(Acetone-d6), = 7.42 (d, J = 8.2 Hz,
2H), 7.16 (d, J = 8.2 Hz, 2H), 7.04 (s, 1H), 6.88 (d,J = 7.4 Hz,
2H), 6.54 (d, J = 7.4 Hz, 2H), 4.01 (s, 3H), EIMS (70 eV), m/z
(%): 410 (M++4, 1), 408 (M++2, 5), 406 (M+, 8), 348 (29), 286
(21), 134 (100), 125 (24), 111 (30). Anal. Calcd. for
C17H12O4N4Cl2: C: 50.14, H: 2.97, N: 13.76. found C: 50.05,
H: 2.87, N: 13.67.
-chloroformylphenylhydrazone (3c)
3-(4-Methoxyphenyl)sydnon-4-ylformaldehyde
Yel low pow der; mp 199-200 C, IR (KBr), cm-1: 1773,
1734 ( C=O), 1HNMR(Acetone-d6), = 7.70-7.38 (m, 5H),
7.42 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.3 Hz, 2H), 6.77 (s, 1H),
2.39 (s, 3H), EIMS (70 eV), m/z (%): 358 (M++2, 11), 356
(M+, 33), 298 (100), 235 (7), 119 (34), 105 (4), 91 (51), 77
(28). Anal. Calcd. for C17H13O3N4Cl: C: 57.23, H: 3.67, N:
15.70. found C: 57.17, H: 3.70, N: 15.66.
-chloroformyl-4-methoxyphenyl-hydrazone (3h)
Yel low nee dles; mp 188.5-189.5 C, IR (KBr), cm-1:
1782, 1725 ( C=O), 1HNMR(Acetone-d6), = 7.70 (d, J =
9.0 Hz, 2H), 7.26~7.09 (m, 6H), 7.06 (s, 1H), 3.93 (s, 3H),
3.87 (s, 3H), EIMS (70 eV), m/z (%): 404 (M++2, 10), 402
(M+, 29), 346 (29), 344 (87), 309 (15), 281 (11), 168 (13), 149
(100), 134 (92), 121 (31), 107 (27), 92 (20). Anal. Calcd. for
C18H15O5N4Cl: C: 53.67, H: 3.75, N: 13.91. found C: 53.44,
H: 3.77, N: 13.85.
3-(4-Methylphenyl)sydnon-4-ylformaldehyde
-chloroformyl-4-methylphenyl-hydrazone (3d)
Yel low nee dles; mp 208-209 C, IR (KBr), cm-1: 1755,
1731 ( C=O), 1HNMR(Acetone-d6), = 7.67 (d, J = 8.3 Hz,
2H), 7.51 (d, J = 8.3 Hz, 2H), 7.40 (s, 1H), 6.92 (d,J = 8.3 Hz,
Preparation of 4-Arylamino-1,2,3-triazoles 6a~6k
Asolutionof3-(4-ethoxyphenyl)sydnonecarbaldehyde

776 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Kuo et al.
4-methylphenylhydrazone (0.3 g, 0.9 mmol) in EtOAc (5
mL) and aque ous HCl (0.5 mL, 12 M) was heated at 60 C for
1 hr. The sol vent was re moved un der re duced pres sure. 6 mL
of i-PrOH was added to the vis cous so lu tion, decolorized
with char coal and fil tered. The fil trate was then dropped into
20mLofwater,andcrudeproductwascollectedbyfiltration.
Recrystallization us ing EtOAc-hexane af forded 0.14 g of 6a
(52%).
91 (29), 77 (69). Anal. Calcd. for C16H16N4O: C: 68.55, H:
5.75, N: 19.98. found C: 68.41, H: 5.90, N: 20.00.
4-(4-Methoxyphenylamino)-2-phenyl-2H-1,2,3-triazole
(6e)
Yel low pow der; mp 79.5~80.5 C, IR (KBr), cm-1: 3348
( N-H), 1598 ( C=N), 1H NMR (DMSO-d6), = 8.94 (s,
1H), 7.91 (d,J = 7.8 Hz, 2H), 7.58 (s, 1H), 7.52 (t, J = 7.8 Hz,
2H), 7.41 (d,J = 8.9 Hz, 2H), 7.29 (t,J = 7.8 Hz, 1H), 6.90 (d,
J = 8.9 Hz, 2H), 3.70 (s, 3H), EIMS (70 eV), m/z (%): 266
(M+, 100), 251 (71), 252 (10), 148 (12), 133 (36), 105 (25), 91
(40), 91 (40), 77 (95). Anal. Calcd. for C15H14N4O: C: 67.65,
H: 5.30, N: 21.04. found C: 67.53, H: 5.41, N: 20.97.
4-(4-Methylphenylamino)-2-phenyl-2H-1,2,3-triazole (6f)
Yel low pow der; mp 73.5~75.0 C, IR (KBr), cm-1: 3340
( N-H), 1605 ( C=N), 1H NMR (DMSO-d6), = 9.06 (s,
1H), 7.94 (d,J = 8.3 Hz, 2H), 7.64 (s, 1H), 7.54 (t, J = 8.3 Hz,
2H), 7.39~7.31 (m, J = 3H), 7.11 (t, J = 8.4 Hz, 2H), 2.25 (s,
3H), EIMS (70 eV), m/z (%): 250 (M+, 100), 222 (11), 194
(4), 131 (7), 118 (6), 107 (5), 91 (26). Anal. Calcd. for
C15H14N4: C: 71.98, H: 5.64, N: 22.38. found C: 71.95, H:
5.68, N: 22.17.
Preparation of compounds 6i-6k from 4-formyl -
sydnones 10 or sydnonecarbaldehydes alkylhydrazones was
accordingtotheaboveprocedure.
2-(4-Methylphenyl)-4-(4-ethoxyphenylamino)-2H-1,2,3-
triazole (6a)
Yellowpowder;mp96.5~97.5 C, IR (KBr), cm-1: 3328
( N-H), 1596 ( C=N), 1H NMR (DMSO-d6), = 8.89 (s,
1H), 7.79 (d, J = 8.4 Hz, 2H), 7.54 (s, 1H), 7.37 (d,J = 8.9 Hz,
2H), 7.31 (d,J = 8.4 Hz, 2H), 6.87 (d,J = 8.9 Hz, 2H), 3.95 (q,
J = 6.9 Hz, 2H), 1.29 (s, 3H), 1.29 (t, J = 6.9 Hz, 3H), EIMS
(70 eV), m/z (%): 294 (M+, 100), 265 (77), 149 (3), 134 (7),
105 (15), 91 (18), 69 (7), 65 (7). Anal. Calcd. for C17H18N4O:
C: 69.37, H: 6.16, N: 19.03. found C: 69.25, H: 6.18, N:
19.17.
2-(4-Chlorophenyl)-4-(4-methoxyphenylamino)-2H-1,2,3-
triazole (6g)
2-(4-Methylphenyl)-4-(4-methoxyphenylamino)-2H-1,2,3-
triazole (6b)
Yel low pow der; mp 96.5~97.5 C, IR (KBr), cm-1: 3328
( N-H), 1605 ( C=N), 1H NMR (DMSO-d6), = 9.01 (s,
1H), 7.91 (d, J = 9.0 Hz, 2H), 7.61 (s, 1H), 7.57 (d,J = 9.1 Hz,
2H), 7.41 (d, J = 9.0 Hz, 2H), 6.90 (d,J = 9.1 Hz, 2H), 3.70 (s,
3H), EIMS (70 eV), m/z (%): 302 (M++2, 37), 300 (M+, 100),
285 (48), 148 (8), 133 (15), 125 (12), 111 (16), 90 (10). Anal.
Calcd. for C15H13N4OCl: C: 59.91, H: 4.36, N: 18.63. found
C: 59.77, H: 4.50, N: 18.64.
Yellowpowder;mp75.5~76.5 C, IR (KBr), cm-1: 3352
( N-H), 1596 ( C=N), 1H NMR (DMSO-d6), = 8.89 (s,
1H), 7.79 (d, J = 8.4 Hz, 2H), 7.54 (s, 1H), 7.39 (d,J = 8.9 Hz,
2H), 7.31 (d, J = 8.4 Hz, 2H), 6.89 (d,J = 8.9 Hz, 2H), 3.70 (s,
3H), 2.33 (s, 3H), EIMS (70 eV), m/z (%): 280 (M+, 100), 265
(45), 188 (3), 165 (4), 133 (11), 105 (32), 91 (22), 77 (16).
Anal. Calcd. for C 16H16N4: C: 72.70, H: 6.10, N: 21.20. found
C: 72.56, H: 6.18, N: 21.23.
4-(4-Methylphenylamino)-2-(4-methylphenyl)-2H-1,2,3-
triazole (6h)
2-(4-Methylphenyl)-4-phenylamino-2H-1,2,3-triazole (6c)
Yellowpowder;mp97.5~98.8 C, IR (KBr), cm-1: 3322
( N-H), 1605 ( C=N), 1H NMR (DMSO-d6), = 9.15 (s,
1H), 7.82 (d, J = 8.4 Hz, 2H), 7.63 (s, 1H), 7.46 (d,J = 7.7 Hz,
2H), 7.35~7.24 (m, J = 4H), 6.86 (t, J = 7.3 Hz, 1H), 2.34 (s,
3H), EIMS (70 eV), m/z (%): 250 (M+, 100), 222 (4), 118 (7),
105 (29), 104 (14), 91 (17), 77 (13). Anal. Calcd. for
C15H14N4: C: 71.98, H: 5.64, N: 22.38. found C: 71.98, H:
5.65, N: 22.38.
Yel low pow der; mp 149.5~150.0 C, IR (KBr), cm-1:
3406 ( N-H), 1614 ( C=N), 1H NMR (DMSO-d6), = 9.00
(s, 1H), 7.80 (d, J = 8.5 Hz, 2H), 7.58 (s, 1H), 7.36~7.29 (m,
4H), 7.09 (d, J = 8.4 Hz, 2H), 2.34 (s, 3H), 2.23 (s, 3H). EIMS
(70 eV), m/z (%): 264 (M+, 100), 131 (9), 118 (6), 106 (14),
105 (31), 91 (35), 78 (12). Anal. Calcd. for C H16N4: C:
16
72.70, H: 6.10, N: 21.20. found C: 72.55, H: 6.19, N: 21.24.
4-Phenylamino-2-phenyl-2H-1,2,3-triazole (6i)
4-(4-Ethoxyphenylamino)-2-phenyl-2H-1,2,3-triazole (6d)
Yellowpowder;mp70.5~71.5 C, IR (KBr), cm-1: 3348
( N-H), 1598 ( C=N), 1H NMR (DMSO-d6), = 8.96 (s,
1H), 7.92 (d,J = 8.2 Hz, 2H), 7.59 (s, 1H), 7.56~7.38 (m, 4H),
7.28 (t, J = 7.4 Hz, 1H), 6.88 (d, J = 9.0 Hz, 2H), 3.94 (q,J =
6.9 Hz, 2H), 1.28 (t,J = 6.9 Hz, 3H), EIMS (70 eV), m/z (%):
280 (M+, 100), 264 (12), 252 (29), 251 (88), 134 (11), 92 (21),
Yel low pow der; mp 85~86 C, IR (KBr), cm-1: 3328 (
N-H), 1605 ( C=N), 1H NMR (DMSO-d6), = 9.20 (s, 1H),
7.94 (d, J = 8.0 Hz, 2H), 7.67 (s, 1H), 7.58~7.25 (m, 7H), 6.86
(t, J = 7.6 Hz, 1H). EIMS (70 eV), m/z (%): 236 (M+, 100),
208 (13), 180 (6), 118 (7), 104 (8), 91 (48), 77 (57). Anal.
Calcd. for C14H12N4: C: 71.17, H: 5.12, N: 23.71. found C:
71.10, H: 5.16, N: 23.70.

1,2,3-Triazoles and 6-Sydnonyl-verdazyls
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 777
2-(4-Ethoxyphenyl)-4-(4-ethoxyphenylamino)-2H-1,2,3-
triazole (6j)
3H), 7.18 (d, J = 9.0 Hz, 2H), 7.13 (d, J = 8.4 Hz, 2H), 6.82
(br, 1H), 6.66 (s, 1H), 4.15 (br, 2H), 3.87 (s, 3H). EIMS (70
eV), m/z (%): 368 (M+, 3), 310 (18), 266 (14), 252 (42), 134
(91), 108 (50), 92 (100), 77 (96), 65 (63). Anal. Calcd. for
C17H16N6O4 (368.35) C: 55.43, H: 4.38, N: 22.81. found C:
55.38, H: 4.40, N: 22.81.
Yellow powder; mp 116.5~117 C, IR (KBr), cm-1:
3404 ( N-H), 1596 ( C=N), 1H NMR (DMSO-d6), = 8.82
(s, 1H), 7.80 (d,J = 8.7 Hz, 2H), 7.50 (s, 1H), 7.35 (d,J = 8.5
Hz, 2H), 7.04 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H),
4.05 (q, J = 7.3 Hz, 2H), 3.94 (q, J = 7.2 Hz, 2H), 1.32 (t,J =
7.3 Hz, 3H), 1.29 (t,J = 7.2 Hz, 3H), EIMS (70 eV), m/z (%):
324 (M+, 100), 295 (66), 134 (12), 121 (6), 107 (9), 69 (20).
Anal. Calcd. for C18H20N4O2: C: 66.65, H: 6.21, N: 17.27.
found C: 66.59, H: 6.35, N: 17.33.
3-(4-Methoxyphenyl)-sydnon-4-ylaldehyde 2-(4-methoxy-
phenyl)carbazone (8b)
Yel low pow der; mp 191~192 C, IR (KBr), cm -1 : 3442,
3328, 3226 ( N-H), 1749, 1704 ( C=O), 1611 ( C=N), 1H
NMR (DMSO-d6), = 7.71 (d, J = 9.0 Hz, 2H), 7.20 (d, J =
9.0 Hz, 3H), 7.04 (s, 4H), 6.79 (br, 1H), 6.67 (s, 1H), 4.39 (br,
2H), 3.87 (s, 3H), 3.87 (s, 3H). EIMS (70 eV), m/z (%): 398
(M+, 5), 340 (19), 309 (6), 282 (29), 162 (9), 149 (27), 134
(100), 122 (96), 107 (40), 92 (37), 77 (37). Anal. Calcd. for
C18H18N6O5 (398.37) C: 54.27, H: 4.55, N: 21.09. found C:
54.27, H: 4.63, N: 20.93.
2-(4-Methoxyphenyl)-4-(4-methoxyphenylamino)-2H-
1,2,3-triazole (6k)
Yel low pow der; mp 129.5~130.5 C, IR (KBr), cm-1:
3352 ( N-H), 1598 ( C=N), 1H NMR (DMSO-d6), = 8.85
(s, 1H), 7.83 (d,J = 7.0 Hz, 2H), 7.52 (s, 1H), 7.38 (d,J = 9.0
Hz, 2H), 7.07 (d, J = 7.0 Hz, 2H), 6.89 (d, J = 9.0 Hz, 2H),
3.94 (s, 3H), 3.79 (s, 3H). EIMS (70 eV), m/z (%): 296 (M+,
100), 281 (27), 148 (9), 121 (14), 107 (5), 78 (4). Anal. Calcd.
for C16H16N4O2: C: 64.85, H: 5.44, N: 18.91. found C: 64.64,
H: 5.60, N: 18.80.
2-Methyl-6-[3-(4-methoxyphenyl)sydnon-4-yl]-4-phenyl-
1,2,4,5-tetrazinan-3-one (7c)
Yel low nee dles; mp 176.5~177.5 C, IR (KBr), cm-1:
3256 ( N-H), 1743, 1632 ( C=O),1H NMR (DMSO-d6),
=
7.75 (d, J = 8.9 Hz, 2H), 7.19 (d, J = 8.9 Hz, 2H), 7.15~7.10
(m, 5H), 6.22 (d, J = 9.5 Hz, 1H), 6.09 (d, J = 9.5 Hz, 1H),
4.99 (t, J= 9.5 Hz, 1H), 3.85 (s, 3H), 2.99 (s, 3H). 13C NMR,
= 165.66, 161.97, 154.17, 142.98, 127.76, 126.69, 126.21,
123.22, 121.23, 115.02, 103.31, 63.66, 55.90, 36.72. EIMS
(70 eV),m/z (%): 382 (M+, 22), 324 (6), 308 (5), 280 (4), 252
(20), 191 (13), 175 (25), 159 (16), 146 (41), 134 (88), 119
(34), 107 (67), 92 (50), 77 (100). Anal. Calcd. for C18H18N6O4
(382.37) C: 56.54, H: 4.74, N: 21.98. found C: 56.50, H: 4.71,
N: 22.01.
Prep a ra tion of 6-Sydnonyl-1,2,4,5-tetrazinan-3-one 7
and/or Sydnonecarbaldehyde Carbazone 8
To a stirred so lu tion of 6 mmol of phenylhydrazine,
hydrazine hy drate, methylhydrazine (or 3 mmol of aryl hy-
drazine hy dro chlo ride and 6 mmol triethylamine) in 10 mL of
eth a nol, 3 mmol of -chloroformylarylhydrazone 3a~h was
added.Thereactionsolutionwasstirredatroomtemperature
for 15 min utes. In the cases of ei ther phenylhydrazine or
4-methoxyphenyl-hydrazine, theprecipitatingsolidwascol-
lected by fil tra tion and recrystallization from eth a nol to ob-
tain cy clic com pounds7.Thefiltratewasconcentratedunder
re duced pres sure, then the crude solid was sub jected to chro-
matography(EtOAc:n-hexane=1:2)toobtaincompounds7
and 8. In the case of 4-fluorophenylhydrazine, the pre cip i tat-
ing solid was col lected by fil tra tion and recrystallization
fromethanoltoobtaincycliccompounds7n and 7o. The fil-
tratewasconcentratedunderreducedpressuretoaffordpure
solid prod uct 8n and 8o by recrystallization from eth a nol. In
the other cases, the so lu tion was poured into 100 mL of wa ter.
Tetrazinan-3-one 7 or carbazone 8 precipitated,andwasthen
purifiedbyrecrystallizationfromethanol.
2-(4-Chlorophenyl)-6-[3-(4-methoxyphenyl)sydnon-4-yl]-
4-methyl-1,2,4,5-tetrazinan-3-one (7d)
Yel low pow der; mp 153.5~154.5 C, IR (KBr), cm-1:
3256 ( N-H), 1743, 1632 ( C=O),1H NMR (DMSO-d6),
=
7.76 (d, J = 8.9 Hz, 2H), 7.28~7.11 (m, 6H), 6.28 (d, J = 9.4
Hz, 1H), 6.11 (d, J = 9.4 Hz, 1H), 5.00 (t,J = 9.4 Hz, 1H), 3.86
(s, 3H), 2.99 (s, 3H). 13C NMR, = 165.59, 161.96, 157.55,
154.11, 141.87, 127.57, 126.67, 126.13, 122.21, 115.03,
103.29, 63.53, 55.87, 36.61. EIMS (70 eV), m/z (%): 416
(M++2, 7), 416 (M+, 22), 358 (3), 342 (3), 286 (6), 225 (8),
209 (15), 190 (9), 146 (30), 134 (100), 125 (31), 107 (55), 92
(41), 77 (73). Anal. Calcd. for C18H17N6O4Cl (416.83) C:
51.87, H: 4.11, N: 20.16. found C: 51.99, H: 4.12, N: 20.16.
2-Methyl-6-[3-(4-methoxyphenyl)sydnon-4-yl]-4-(4-
methoxyphenyl)-1,2,4,5-tetrazinan-3-one (7e)
3-(4-Methoxyphenyl)-sydnon-4-ylaldehyde 2-phenyl-
carbazone (8a)
Yellowpowder;mp160~161 C, IR (KBr), cm-1: 3430,
3334, 3232 ( N-H), 1746, 1707 ( C=O), 1605 ( C=N), 1H
NMR (DMSO-d6), = 7.00 (d,J = 9.0 Hz, 2H), 7.55~7.43 (m,
Yel low nee dles; mp 151.5~152.5 C, IR (KBr), cm-1:
3226 ( N-H), 1746, 1641 ( C=O),1H NMR (DMSO-d6),
=

778 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Kuo et al.
7.78 (d, J = 9.0 Hz, 2H), 7.23 (d,J = 9.0 Hz, 2H), 7.18 (d, J =
9.0 Hz, 5H), 6.78 (d, J = 9.0 Hz, 2H), 6.22 (d, J = 9.4 Hz, 1H),
6.08 (d, J = 9.4 Hz, 1H), 5.00 (t, J= 9.4 Hz, 1H), 3.90 (s, 3H),
3.73 (s, 3H), 3.01 (s, 3H). 13C NMR, = 165.65, 161.94,
155.64, 153.71, 136.24, 126.68, 126.19, 123.71, 114.99,
112.93, 103.13, 63.41, 55.89, 55.16, 36.88. EIMS (70 eV),
m/z (%): 412 (M+, 15), 354 (2), 337 (3), 310 (2), 282 (12), 248
(7), 205 (14), 190 (15), 162 (14), 149 (75), 134 (100), 121
(51), 107 (60), 92 (47), 77 (58). Anal. Calcd. for C 19H20N6O5
(412.40) C: 55.34, H: 4.89, N: 20.38. found C: 55.39, H: 4.90,
N: 20.29.
(M+, 16), 400 (2), 310 (4), 266 (12), 252 (10), 162 (12), 146
(14), 134 (64), 121 (32), 107 (75), 91 (100), 77 (88). Anal.
Calcd. for C24H22N6O4 (458.47) C: 62.87, H: 4.84, N: 18.33.
found C: 62.72, H: 4.95, N: 18.30.
3-(4-Methoxyphenyl)sydnon-4-ylaldehyde 5-(4-methyl-
phenyl)-2-phenylcarbazone (8g)
Yel low pow der; mp 144~145 C, IR (KBr), cm -1 : 3412,
1
3323 ( N-H), 1758, 1701 ( C=O), 1605 ( C=N), H NMR
(DMSO-d6), = 7.75 (d, J = 8.9 Hz, 2H), 7.55~7.48 (m, 4H),
7.35 (d, J = 2.3 Hz, 1H), 7.18 (d, J = 2.3 Hz, 1H), 7.14~7.09
(m, 3H), 6.97 (d,J = 8.2 Hz, 2H), 6.74 (s, 1H), 6.55 (d,J = 8.2
Hz, 2H), 3.62 (s, 3H), 2.18 (s, 3H). EIMS (70 eV), m/z (%):
458 (M+, 8), 400 (2), 310 (28), 293 (10), 280 (13), 252 (43),
162 (23), 148 (19), 134 (100), 119 (45), 106 (77), 91 (99), 77
(89). Anal. Calcd. for C24H22N6O4 (458.48) C: 62.87, H: 4.84,
N: 18.33. found C: 62.76, H: 4.94, N: 18.20.
2-(4-Methoxyphenyl)-6-[3-(4-methoxyphenyl)sydnon-4-yl]-
4-phenyl-1,2,4,5-tetrazinan-3-one (7f)
Yel low pow der; mp 143.5~144.5 C, IR (KBr), cm-1:
3256 ( N-H), 1737, 1668 ( C=O),1H NMR (DMSO-d6), =
7.79 (d, J = 8.8 Hz, 2H), 7.34~7.18 (m, 8H), 7.03 (t, J = 6.9
Hz, 1H), 6.83 (d, J = 8.8 Hz, 2H), 6.44 (d, J = 9.7 Hz, 2H),
5.22 (t, J = 9.7 Hz, 1H), 3.86 (s, 3H), 3.72 (s, 3H). 13C NMR,
= 165.67, 161.97, 156.11, 154.42, 142.48, 135.42, 127.85,
126.77, 126.19, 124.31, 123.61, 121.69, 115.04, 113.14,
103.52, 65.06, 55.89, 55.21. EIMS (70 eV), m/z (%): 474
(M+, 4), 457 (5), 416 (2), 399 (12), 309 (35), 279 (23), 252
(18), 149 (71), 108 (86), 91 (61), 77 (100), 65 (40). Anal.
Calcd. for C24H22N6O5 (474.47) C: 60.75, H: 4.67, N: 17.71.
found C: 60.68, H: 4.73, N: 17.66.
2-(4-Methylphenyl)-6-(3-phenylsydnon-4-yl)-4-phenyl-
1,2,4,5-tetrazinan-3-one (7h)
Yel low pow der; mp 129~130 C, IR (KBr), cm -1 : 3208
1
(
N-H), 1734, 1659 ( C=O), H NMR (DMSO-d6),
=
7.89~7.70 (m, 5H), 7.33~7.18 (m, 7H), 7.03 (d, J = 8.1 Hz,
2H), 6.46 (d,J = 9.7 Hz, 1H), 6.44 (d,J = 9.7 Hz, 1H), 5.25 (t,
J = 9.7 Hz, 1H), 2.24 (s, 3H). EIMS (70 eV), m/z (%): 428
(M+, 10), 370 (1), 236 (16), 222 (13), 149 (11), 132 (30), 119
(26), 104 (69), 91 (93), 77 (100). Anal. Calcd. for C23H20N6O3
(458.47) C: 64.48, H: 4.71, N: 19.61. found C: 64.29, H: 4.75,
N: 19.50.
3-(4-Methoxyphenyl)sydnon-4-ylaldehyde 5-(4- methoxy-
phenyl)-2-phenylcarbazone (8f)
Yel low nee dles; mp 181.5~182.5 C, IR (KBr), cm-1:
3346, 3286 ( N-H), 1755, 1695 ( C=O), 1605 ( C=N), 1H
NMR (DMSO-d6), = 7.75 (d,J = 9.0 Hz, 2H), 7.56~7.35 (m,
6H), 7.18 (d,J = 1.7 Hz, 1H), 7.14 (d,J = 9.0 Hz, 2H), 6.78 (d,
J = 9.0 Hz, 2H), 6.72 (s, 1H), 6.59 (d, J = 9.0 Hz, 3H), 3.66 (s,
3H), 3.64 (s, 3H). EIMS (70 eV), m/z (%): 474 (M+, 2), 443
(23), 416 (1), 399 (4), 293 (33), 252 (14), 191 (21), 164 (12),
134 (50), 123 (93), 108 (39), 92 (59), 77 (100). Anal. Calcd.
for C24H22N6O5 (474.48) C: 60.75, H: 4.67, N: 17.71. found
C: 60.81, H: 4.74, N: 17.75.
3-Phenylsydnon-4-ylaldehyde 2-(4-methylphenyl)-5-
phenylcarbazone (8h)
Yel low pow der; mp 175.5~176.5 C, IR (KBr), cm-1:
1
3364 ( N-H), 1752, 1725 ( C=O), 1605 ( C=N), H NMR
(DMSO-d6), = 7.85~7.80 (m, 2H), 7.65~7.59 (m, 4H),
7.33~7.12 (m, 5H), 7.03 (d,J = 8.1 Hz, 2H), 6.75 (s, 1H), 6.72
(t, J = 7.4 Hz, 1H), 6.62 (d, J = 8.1 Hz, 2H), 2.32 (s, 3H).
EIMS (70 eV), m/z (%): 428 (M+, 7), 384 (6), 370 (2), 236
(21), 134 (27), 106 (60), 91 (96), 77 (100), 65 (96). Anal.
Calcd. for C23H20N6O3 (458.48) C: 64.48, H: 4.71, N: 19.62.
found C: 64.31, H: 4.73, N: 19.56.
2-(4-Methylphenyl)-6-[3-(4-methoxyphenyl)sydnon-4-yl]-
4-phenyl-1,2,4,5-tetrazinan-3-one (7g)
2-(4-Methylphenyl)-6-[3-(4-methylphenyl)sydnon-4-yl]-4-
phenyl-1,2,4,5-tetrazinan-3-one (7i)
Yellowpowder;mp155~156 C, IR (KBr), cm-1: 3232,
3172 ( N-H), 1758, 1644 ( C=O),1H NMR (DMSO-d6), =
7.80 (d, J = 8.9 Hz, 2H), 7.39 (d, J = 8.2 Hz, 2H), 7.28~7.18
(m, 6H), 7.06 (d, J = 8.2 Hz, 2H), 6.46 (d, J = 9.7 Hz, 2H),
5.22 (t, J = 9.7 Hz, 1H), 3.87 (s, 3H), 2.25 (s, 3H). 13C NMR,
= 165.65, 161.96, 155.09, 142.33, 139.81, 132.88, 128.37,
127.87, 126.75, 126.17, 123.62, 121.92, 121.58, 115.03,
103.68, 65.33, 55.88, 20.42. EIMS (70 eV), m/z (%): 458
Yel low pow der; mp 181.5~182.5 C, IR (KBr), cm-1:
3236 ( N-H), 1740, 1677 ( C=O),1H NMR (DMSO-d6),
=
7.75 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.36~7.20
(m, 6H), 7.07~7.00 (m, 3H), 6.46 (d, J = 9.4 Hz, 2H), 5.23 (t,
J = 9.4 Hz, 1H), 2.44 (s, 3H), 2.25 (s, 3H). 13C NMR,
=
160.59, 155.09, 142.77, 142.31, 139.78, 132.85, 131.16,
130.37, 128.35, 127.84, 124.94, 123.58, 121.89, 121.54,

1,2,3-Triazoles and 6-Sydnonyl-verdazyls
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 779
103.60, 65.30, 20.90, 20.41. EIMS (70 eV), m/z (%): 442
(M+, 30), 384 (6), 308 (8), 294 (10), 250 (11), 133 (30), 119
(33), 106 (36), 91 (100), 77 (47). Anal. Calcd. for C 24H22N6O3
(442.48) C: 65.15, H: 5.01, N: 18.99. found C: 65.18, H: 5.03,
N: 18.91.
3250, 3214 ( N-H), 1740, 1638 ( C=O), 1H NMR (DMSO-
d6), = 7.80 (d, J = 8.8 Hz, 2H), 7.39~7.18 (m, 10H),
7.09~7.00 (m, 2H), 6.49 (d, J = 9.6 Hz, 2H), 5.24 (t, J = 9.6
Hz, 2H), 3.86 (s, 3H). 13C NMR, = 165.64, 161.97, 155.53,
142.23, 127.90, 126.76, 126.17, 123.67, 121.52, 115.04,
103.78, 65.48, 55.89. EIMS (70 eV), m/z (%): 444 (M+, 54),
386 (8), 310 (11), 279 (12), 252 (22), 134 (39), 119 (40), 107
(39), 91 (44), 77 (100), 65 (18). Anal. Calcd. for C23H20N6O4
(444.45) C: 62.15, H: 4.54, N: 18.91. found C: 61.92, H: 4.61,
N: 18.80.
3-(4-Methylphenyl)sydnon-4-ylaldehyde 2-(4-methyl-
phenyl)-5-phenyl-carbazone (8i)
Yel low nee dles; mp 192~193 C, IR (KBr), cm-1: 3418,
3304 ( N-H), 1761, 1698 ( C=O), 1605 ( C=N), 1H NMR
(DMSO-d6), = 7.70 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 2.0 Hz,
1H), 7.39 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H), 7.16 (t,
J = 7.8 Hz, 2H), 7.02 (d, J = 8.2 Hz, 2H), 6.94 (d,J = 2.0 Hz,
1H), 6.73 (s, 1H), 6.73 (t, J = 7.2 Hz, 1H), 6.58 (d, J = 7.6 Hz,
2H), 2.34 (s, 3H), 2.11 (s, 3H). EIMS (70 eV), m/z (%): 442
(M+, 13), 384 (5), 308 (13), 250 (21), 134 (33), 106 (66), 91
(100), 77 (85), 65 (59). Anal. Calcd. for C24H22N6O3 (442.48)
C: 65.15, H: 5.01, N: 18.99. found C: 65.03, H: 5.02, N:
18.94.
3-(4-Methoxyphenyl)sydnon-4-ylaldehyde 2,5-diphenyl-
carbazone (8k)
Yel low pow der; mp 161~162 C, IR (KBr), cm -1 : 3364,
1
3298 ( N-H), 1746, 1698 ( C=O), 1605 ( C=N), H NMR
(DMSO-d6), = 7.75 (d, J = 9.0 Hz, 2H), 7.71 (d, J = 1.6 Hz,
1H), 7.56~7.45 (m, 3H), 7.37 (d, J = 1.6 Hz, 1H), 7.19~7.08
(m, 6H), 6.74 (s, 1H), 6.72 (t, J = 7.3 Hz, 1H), 6.63 (d, J = 7.7
Hz, 2H), 3.60 (s, 3H). EIMS (70 eV), m/z (%): 444 (M+, 15),
386 (2), 384 (7), 310 (12), 252 (17), 134 (25), 120 (12), 107
(18), 92 (47), 77 (100), 65 (34). Anal. Calcd. for C23H20N6O
(444.45) C: 62.15, H: 4.54, N: 18.91. found C: 62.04, H: 4.61,
N: 18.85.
2-(4-Chlorophenyl)-6-[3-(4-methylphenyl)sydnon-4-yl]-4-
phenyl-1,2,4,5-tetrazinan-3-one (7j)
Yel low pow der; mp 149~150 C, IR (KBr), cm-1: 3256
( N-H), 1731, 1674 ( C=O), 1H NMR (DMSO-d6), = 7.74
(d, J = 8.3 Hz, 2H), 7.49 (d, J = 8.3 Hz, 2H), 7.42~7.22 (m,
8H), 7.09~7.06 (m, 1H), 6.55 (d, J = 9.5 Hz, 1H), 6.50 (d, J =
9.5 Hz, 1H), 5.24 (t, J= 9.5 Hz, 1H), 2.43 (s, 3H).13C NMR,
= 165.55, 155.99, 142.80, 141.98, 141.14, 131.13, 130.39,
127.96, 127.72, 127.17, 124.94, 123.75, 122.58, 121.34,
103.79, 65.49, 20.89. EIMS (70 eV), m/z (%): 464 (M++2,
11), 462 (M+, 40), 404 (8), 328 (12), 294 (12), 270 (15), 236
(21), 153 (32), 118 (53), 91 (100), 77 (80). Anal. Calcd. for
C23H19N6O3Cl (462.90) C: 59.68, H: 4.14, N: 18.16. found C:
59.64, H: 4.01, N: 18.19.
2-(4-Chlorophenyl)-6-[3-(4-methoxyphenyl)sydnon-4-yl]-
4-phenyl-1,2,4,5-tetrazinan-3-one (7l)
Pale yel low pow der; mp 159~160 C, IR (KBr), cm-1:
3256 ( N-H), 1746, 1668 ( C=O),1H NMR (DMSO-d6),
=
7.79 (d, J = 8.9 Hz, 2H), 7.43~7.18 (m, 10H), 7.05 (t, J = 7.2
Hz, 1H), 6.55 (d, J = 9.4 Hz, 1H), 6.50 (d, J = 9.4 Hz, 1H),
5.23 (t, J = 9.4 Hz, 1H), 3.86 (s, 3H). 13C NMR, = 165.57,
161.95, 155.95, 141.99, 141.15, 127.95, 127.70, 127.17,
126.73, 126.12, 123.75, 122.57, 121.34, 115.02, 103.84,
65.50, 55.86. EIMS (70 eV), m/z (%): 480 (M++1, 6), 478
(M+, 17), 420 (3), 344 (6), 310 (10), 286 (12), 252 (9), 153
(28), 134 (45), 108 (35), 91 (46), 77 (100). Anal. Calcd. for
C23H19N6O4Cl (478.90) C: 57.69, H: 4.00, N: 17.55. found C:
57.61, H: 4.02, N: 17.51.
3-(4-Methylphenyl)sydnon-4-ylaldehyde 2-(4-chloro-
phenyl)-5-phenylcarbazone (8j)
Yel low pow der; mp 186.5~187.5 C, IR (KBr), cm-1:
3418, 3304 ( N-H), 1758, 1701 ( C=O), 1605 ( C=N), 1H
NMR (DMSO-d6), = 7.71 (d, J = 8.1 Hz, 2H), 7.59 (d, J =
8.5 Hz, 2H), 7.40 (d,J = 8.1 Hz, 2H), 7.25~7.13 (m, 4H), 7.08
(d, J = 1.6 Hz, 1H), 6.76 (s, 1H), 6.74 (t, J = 7.3 Hz, 1H), 6.61
(d, J = 7.8 Hz, 2H), 2.14 (s, 3H). EIMS (70 eV), m/z (%): 464
(M++2, 3), 462 (M+, 10), 404 (3), 328 (16), 286 (9), 270 (27),
153 (16), 118 (52), 91 (100), 77 (99), 65 (82). Anal. Calcd. for
C23H19N6O3Cl (462.90) C: 59.68, H: 4.14, N: 18.19. found C:
59.55, H: 4.18, N: 18.15.
3-(4-Methoxyphenyl)sydnon-4-ylaldehyde 2-(4-chloro-
phenyl)-5-phenylcarbazone (8l)
Yel low pow der; mp 159.5~160.5 C, IR (KBr), cm-1:
3418, 3310 ( N-H), 1758, 1701 ( C=O), 1605 ( C=N), 1H
NMR (DMSO-d6), = 7.75 (d, J = 8.9 Hz, 2H), 7.71 (d, J =
2.2 Hz, 1H), 7.59 (d,J = 8.6 Hz, 2H), 7.39 (d, J = 2.2 Hz, 1H),
7.25~7.09 (m, 6H), 6.77 (s, 1H), 6.72 (t, J = 7.3 Hz, 1H), 6.63
(d, J = 7.5 Hz, 2H), 3.61 (s, 3H). EIMS (70 eV), m/z (%): 480
(M++2, 1), 478 (M+, 4), 418 (2), 344 (7), 286 (16), 153 (8),
134 (46), 111 (30), 92 (46), 77 (100), 65 (43). Anal. Calcd. for
C23H19N6O4Cl (478.90) C: 57.69, H: 4.00, N: 17.55. found C:
2,4-Diphenyl-6-[3-(4-methylphenyl)sydnon-4-yl]-1,2,4,5-
tetrazinan-3-one (7k)
Yel low pow der; mp 192.5~193.5 C, IR (KBr), cm-1:

780 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Kuo et al.
57.55, H: 4.04, N: 17.51.
2-(4-Fluorophenyl)-4-(4-methylphenyl)-6-[3-(4-methyl-
2-(4-Methoxyphenyl)-6-[3-(4-methoxyphenyl)sydnon-4-yl]-
4-phenyl-1,2,4,5-tetrazinan-3-one (7m)
phenyl)sydnon-4-yl]-1,2,4,5-tetrazinan-3-one (7o)
Pale green nee dles; mp 199~200 C, IR (KBr), cm-1:
3232, 3184 ( N-H), 1756, 1644 ( C=O), 1H NMR (DMSO-
d6), = 7.74 (d, J = 8.3 Hz, 2H), 7.49 (d, J = 8.3 Hz, 2H),
7.38~7.29 (m, 2H), 7.20 (d, J = 8.4 Hz, 2H), 7.14~6.95 (m,
4H), 6.49 (d,J = 9.8 Hz, 1H), 6.43 (d,J = 9.8 Hz, 1H), 5.24 (t,
J = 9.8 Hz, 1H), 2.44 (s, 3H), 2.36 (s, 3H). EIMS (70 eV), m/z
(%): 460 (M+, 7), 402 (1), 385 (3), 308 (4), 250 (11), 133 (23),
118 (47), 106 (40), 95 (34), 91 (100), 77 (42). Anal. Calcd. for
C24H21N6O3F (460.47) C: 62.60, H: 4.60, N: 18.25. found C:
62.62, H: 4.67, N: 18.33.
Yel low pow der; mp 143.5~144.5 C, IR (KBr), cm-1:
3256 ( N-H), 1737, 1668 ( C=O),1H NMR (DMSO-d6), =
7.79 (d, J = 8.8 Hz, 2H), 7.34~7.18 (m, 8H), 7.03 (t, J = 6.9
Hz, 1H), 6.83 (d, J = 8.8 Hz, 2H), 6.44 (d, J = 9.7 Hz, 2H),
5.22 (t, J = 9.7 Hz, 1H), 3.86 (s, 3H), 3.72 (s, 3H). EIMS (70
eV), m/z (%): 474 (M+, 4), 457 (5), 416 (2), 399 (12), 309
(35), 279 (23), 252 (18), 149 (71), 108 (86), 91 (61), 77 (100),
65 (40). Anal. Calcd. for C24H22N6O5 (474.47) C: 60.75, H:
4.67, N: 17.71. found C: 60.68, H: 4.73, N: 17.66.
3-(4-Methoxyphenyl)sydnon-4-ylaldehyde 2-(4-methoxy-
phenyl)-5-phenylcarbazone (8m)
3-(4-Methylphenyl)sydnon-4-ylaldehyde 5-(4-fluoro-
phenyl)- 2-(4-methylphenyl)-carbazone (8o)
Yel low pow der; mp 160.5~161.5 C, IR (KBr), cm-1:
3430, 3310 ( N-H), 1752, 1713 ( C=O), 1605 ( C=N), 1H
NMR (DMSO-d6), = 7.75 (d, J = 8.9 Hz, 2H), 7.68 (d, J =
2.3 Hz, 1H), 7.27 (d,J = 2.3 Hz, 1H), 7.19~7.06 (m, 8H), 6.75
(s, 1H), 6.68 (t, J = 7.3 Hz, 1H), 6.62 (d, J = 7.7 Hz, 2H), 3.78
(s, 3H), 3.59 (s, 3H). EIMS (70 eV), m/z (%): 474 (M+, 3), 414
(1), 340 (5), 309 (26), 282 (8), 257 (16), 149 (39), 122 (72),
108 (100), 93 (47), 77 (92). Anal. Calcd. for C24H22N6O5
(474.47) C: 60.75, H: 4.67, N: 17.71. found C: 60.58, H: 4.74,
N: 17.60.
Yel low pow der; mp 126.5~127.5 C, IR (KBr), cm-1:
3532, 3340 ( N-H), 1749, 1692 ( C=O), 1599 ( C=N), 1H
NMR (DMSO-d6), = 7.71 (d, J = 8.3 Hz, 2H), 7.65 (d, J =
2.3 Hz, 1H), 7.41 (d,J = 8.3 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H),
7.05~6.95 (m, 5H), 6.73 (s, 1H), 6.62~6.55 (m, 2H), 2.34 (s,
3H), 2.14 (s, 3H), EIMS (70 eV), m/z (%): 460 (M+, 9), 308
(20), 294 (12), 250 (36), 236 (19), 150 (16), 106 (61), 91
(100), 77 (49), 65 (50). Anal. Calcd. for C H21N6O3F
24
(460.46) C: 62.60, H: 4.60, N: 18.46. found C: 62.61, H: 4.62,
N: 18.36.
2-(4-Fluorophenyl)-6-[3-(4-methylphenyl)sydnon-4-yl]-4-
phenyl-1,2,4,5-tetrazinan-3-one (7n)
3-(4-Methylphenyl)sydnon-4-ylaldehyde 5-(4-ethoxy-
carbonylphenyl)-2-(4-methylphenyl)carbazone (8p)
Yellow pow der; mp 233~233.5 C, IR (KBr), cm-1:
3370, 3316 ( N-H), 1764, 1710, 1680 ( C=O), 1608 (
C=N), 1H NMR (DMSO-d6), = 8.38 (d,J = 1.2 Hz, 1H), 7.79
(d, J = 8.8 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.4
Hz, 2H), 7.34 (d, J = 8.2 Hz, 2H), 7.05 (d, J = 8.2 Hz, 2H),
6.97 (d, J = 1.2 Hz, 1H), 6.74 (s, 1H), 6.63 (d,J = 8.8 Hz, 2H),
4.24 (q, J = 7.1 Hz, 2H), 2.34 (s, 3H), 2.10 (s, 3H), 1.28 (t,J =
7.1 Hz, 3H), FABMS,m/z (%): 515 (M+ +1, 86), Anal. Calcd.
for C27H26N6O5 (514.55) C: 63.03, H: 5.09, N: 16.33. found
C: 63.07, H: 5.13, N: 16.20.
Pale green nee dles; mp 181.5~182.5 C, IR (KBr),
1
cm-1: 3256 ( N-H), 1734, 1674 ( C=O), H NMR (DMSO-
d6), = 7.74 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H),
7.40~7.20 (m, 6H), 7.15~7.01 (m, 3H), 6.53 (d, J = 9.6 Hz,
1H), 6.47 (d,J = 9.6 Hz, 1H), 5.25 (t, J = 9.6 Hz, 1H), 2.44 (s,
3H). EIMS (70 eV), m/z (%): 446 (M+, 14), 388 (2), 254 (11),
236 (20), 137 (27), 118 (80), 109 (53), 95 (56), 91 (100), 77
(99), 65 (49). Anal. Calcd. for C H19N6O3F (446.45) C:
23
61.88, H: 4.29, N: 18.82. found C: 61.87, H: 4.38, N: 18.85.
3-(4-Methylphenyl)sydnon-4-ylaldehyde 5-(4-fluoro-
phenyl)-2-phenylcarbazone (8n)
3-(4-Methylphenyl)sydnon-4-ylaldehyde-5-(4-ethoxy-
carbonylphenyl)-2-(4-chlorophenyl)carbazone (8q)
Yel low pow der; mp 192-193 C, IR (KBr), cm-1: 3370,
3316 ( N-H), 1767, 1716, 1695 ( C=O), 1608 ( C=N), 1H
NMR (DMSO-d6), = 8.40 (d, J = 1.2 Hz, 1H), 7.80 (d, J =
8.7 Hz, 2H), 7.71 (d,J = 8.2 Hz, 2H), 7.60 (d, J = 8.7 Hz, 2H),
7.41 (d,J = 8.2 Hz, 2H), 7.25 (d, J = 8.7 Hz, 2H), 7.12 (d, J =
1.2 Hz, 1H), 6.77 (s, 1H), 6.64 (d, J = 8.7 Hz, 2H), 4.24 (q,J =
7.1 Hz, 2H), 2.13 (s, 3H), 1.28 (t, J = 7.1 Hz, 3H), FABMS
m/z (%): 535 (M++1, 83), Anal. Calcd. for C26H23N6O5Cl
Yel low pow der; mp 178.5~179.5 C, IR (KBr), cm-1:
3352, 3310 ( N-H), 1752, 1701 ( C=O), 1614 ( C=N), 1H
NMR (DMSO-d6), = 7.71 (d, J = 8.3 Hz, 2H), 7.67 (d, J =
2.0 Hz, 1H), 7.58~7.40 (m, 5H), 7.19~7.02 (m, 4H), 6.97 (d,J
= 2.0 Hz, 1H), 6.74 (s, 1H), 6.64~6.58 (m, 2H), 2.15 (s, 3H),
EIMS (70 eV),m/z (%): 446 (M+, 33), 294 (25), 236 (36), 146
(16), 126 (41), 106 (49), 91 (100), 77 (88), 65 (53). Anal.
Calcd. for C23H19N6O2F (446.44) C: 61.88, H: 4.29, N: 18.83.
found C: 61.83, H: 4.38, N: 18.79.

1,2,3-Triazoles and 6-Sydnonyl-verdazyls
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 781
(534.96) C: 58.38, H: 4.33, N: 15.71. found C: 58.51, H: 4.37,
N: 15.68.
2-(4-Chlorophenyl)-6-[3-(4-methoxyphenyl)sydnon-4-yl]-
4-phenyl-3,4-dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl
radical (9e)
Preparationof6-Sydnonyl-3,4-dihydro-3-oxo-1,2,4,5-
tetrazin-1(2H)-yl Radical 9a~9f
Dark green pow der; mp 198.5~198.5 C, IR (KBr),
cm-1: 1767, 1701 ( C=O), UV max (EtOAc) 259, 323, 337,
450, 584 nm. EIMS (70 eV), m/z (%): 478 (M++3, 3), 477
(M++2, 3), 476 (M++1, 8), 475 (M+, 2), 446 (11), 417 (10),
294 (8), 272 (15), 153 (95), 134 (57), 119 (100), 91 (92), 77
(75). Anal. Calcd. for C23H16N6O4Cl (475.87) C: 58.05, H:
3.39, N: 17.66. found C: 58.03, H: 3.46, N: 17.63.
2-(4-Methoxyphenyl)-6-[3-(4-methoxyphenyl)sydnon-4-yl]-
4-phenyl-3,4-dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl
radical (9f)
To a so lu tion of 0.414 g (1 mmol) of 7i in 10 mL di-
chloro methane and 1 mL of ace tic acid was added 0.29 g (1.2
mmol) of lead di ox ide. The so lu tion was stirred at room tem-
per a ture for 8 hours. Af ter fil tra tion, the fil trate was washed
with wa ter un til it was neu tral. The or ganic layer was dried
withmagnesiumsulfate,thenevaporated.Thecrudeproduct
was recrystallized with acetonitrile to ob tain 9a (0.27g,
65%).
2-(4-Methylphenyl)-4-phenyl-6-(3-phenylsydnon-4-yl)-3,4-
dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl rad i cal (9a)
Dark green pow der; mp 172~173 C, IR (KBr), cm-1:
Dark green pow der; mp 174.5~175.5 C, IR (KBr),
cm-1: 1764, 1695 ( C=O), UV max (EtOAc) 265, 303, 357,
459, 588 nm. EIMS (70 eV), m/z (%): 472 (M++1, 20), 471
(M+, 7), 414 (8), 413 (12), 309 (7), 268 (7), 206 (6), 149
(100), 134 (88), 119 (57), 91 (55), 77 (62). Anal. Calcd. for
C24H19N6O5 (417.45) C: 61.14, H: 4.06, N: 17.83. found C:
61.01, H: 4.06, N: 17.86.
1761, 1713 ( C=O), UV
(EtOAc) 265, 306, 350, 439,
max
578 nm. EIMS (70 eV),m/z (%): 426 (M++1, 18), 425 (M+, 6),
368 (13), 367 (18), 133 (29), 119 (31), 104 (45), 91 (70), 77
(100), 65 (25). Anal. Calcd. for C23H17N6O3 (425.43) C:
64.94, H: 4.03, N: 19.75. found C: 64.81, H: 4.16, N: 19.79.
2-(4-Methylphenyl)-6-[3-(4-methylphenyl)sydnon-4-yl]-4-
phenyl-3,4-dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl radical
(9b)
ACKNOWLEDGMENT
Dark green pow der; mp 164~164.5 C, IR (KBr), cm-1:
WethanktheNationalScienceCounciloftheRepublic
of China for fi nan cial sup port of the work.
1761, 1713 ( C=O), UV
(EtOAc) 259, 320, 343, 455,
max
580 nm. EIMS (70 eV),m/z (%): 440 (M++1, 21), 439 (M+, 9),
382 (11), 381 (16), 226 (8), 133 (46), 119 (61), 105 (22), 91
(100), 77 (57). Anal. Calcd. for C24H19N6O3 (439.46) C:
65.60, H: 4.36, N: 19.12. found C: 65.61, H: 4.36, N: 19.17.
2-(4-Chlorophenyl)-6-[3-(4-methylphenyl)sydnon-4-yl]-4-
phenyl-3,4-dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl radical
(9c)
Received September 13, 2000.
Key Words
2-Arylamino-2H-1,2,3-triazole;
3,4-Dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl radical.
Dark green pow der; mp 188.5~189.5 C, IR (KBr),
cm-1: 1767, 1701 ( C=O), UV max (EtOAc) 264, 315, 350,
442, 586 nm. EIMS (70 eV), m/z (%): 462 (M++3, 10), 461
(M++2, 5), 460 (M++1, 33), 459 (M+, 15), 402 (18), 401 (35),
153 (44), 118 (72), 91 (100), 77 (54), 65 (29). Anal. Calcd. for
C23H16N6O3Cl (459.87) C: 60.07, H: 3.51, N: 18.27. found C:
59.97, H: 3.61, N: 18.18.
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6-[3-(4-Methoxyphenyl)sydnon-4-yl]-2,4-diphenyl-3,4-
dihydro-3-oxo-1,2,4,5-tetrazin-1(2H)-yl rad i cal (9d)
Dark green pow der; mp 219~220 C, IR (KBr), cm-1:
3. Ruccia, M.; Vivona, N.; Spinelli, D. Adv. Hetercycl.
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4. Vivona, N.; Macaluso, G.; Cusmano, C.; Frenna, V. J.
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1776, 1707 ( C=O), UV
(EtOAc) 265, 309, 347, 448,
max
576 nm. EIMS (70 eV),m/z (%): 442 (M++1, 35), 441 (M+, 7),
384 (16), 383 (15), 134 (60), 119 (100), 105 (13), 91 (68), 77
(87). Anal. Calcd. for C 23H17N6O4 (441.43) C: 62.58, H: 3.88,
N: 19.04. found C: 62.52, H: 3.88, N: 19.07.
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