The syntheses and reactions of 3-arylsydnone-4-carboxamide phenylhydrazones

Article abstract of DOI:10.1002/jccs.200100129

Reactions of aniline with 3-arylsydnone-4-carbohydroximic acid chlorides (1) gave the desired substitution products 5. 3-Arylsydnone-4-carboxamide phenylhydrazones (7) were obtained unexpectedly by the reaction of carbohydroximic acid chlorides 1 with phe

Full text of DOI:10.1002/jccs.200100129

JournaloftheChineseChemicalSociety, 2001, 48, 883-892
883
The SynthesesandReactionsof3-Arylsydnone-4-carboxamide
Phenylhydrazones
Mei-Hsiu Shiha,b
(
), Li-Hui Lua (
) and Mou-Yung Yeha* (
)
aDepartmentofChemistry,NationalChengKungUniversity,Tainan,Taiwan701,R.O.C.
bDepartmentofChemicalEngineering,SouthernTaiwanUniversityofTechnology,
Tainan, Tai wan 710, R.O.C.
Reactionsofanilinewith3-arylsydnone-4-carbohydroximicacidchlorides( 1)gavethedesiredsubstitu-
tion prod ucts5. 3-Arylsydnone-4-carboxamide phenylhydrazones (7) were ob tained un ex pect edly by the re-
ac tion of carbohydroximic acid chlo rides 1 withphenylhydrazineinsuitableconditions.Compounds7 could
re act with both ar o matic and aliphatic al de hydes in the pres ence of acid cat a lyst to give 3-aryl-4-(1 -phenyl-
5 -substituted-1 ,2 ,4 -triazol-3 -yl)sydnones (11 ).
INTRODUCTION
Many sydnone com pounds have been found to have
H2N
OH
Cl
OH
Ar
Ar
N
N
N
N
N
N
pharmacological and biologicalactivities.1-9 In addition,
1,2,4- triazolyl de riv a tives are also well known to show spe-
cialpharmacologicalactivities.10-16 It there fore should be sig-
nif i cant to syn the size sydnone com pounds hav ing a 1,2,4-
triazolylgroupsubstitutedatasuitableposition. However, a
sydnoneringissosensitivetoacids,alkaliesandheatthatre-
actionconditionsforthepreparationofsydnonederivatives
seem to be lim ited. In our pre vi ous work, 3-arylsydnone-4-
carbohydroximic acid chlo rides (1) are sta ble at room tem-
per a ture and are eas ily con verted into 3-arylsydnone-4- car-
bonitrileoxidesinpolarsolventorbasicaqueoussolution.17
The ac tive nitrile ox ides gen er ated by this route could un-
dergo cycloaddition with dipolarophiles to give 4-hetero-
cyclic sydnones.18-22 3-Arylsydnone-4- carbohydroximic acid
chlo rides could be used to re act with some nucleophiles to
give the pre cur sors which were ex pected to be cyclized with
other re agents to give the de sired 4-heterocyclic sydnones.
Wenowreportthestudiesontheformationof1,2,4,-triazolyl
groupsubstitutedsydnones.
O
O
O
O
1
2
H2NHN
N
OH
HOHN
N
OH
Ar
N
Ar
N
N
O
N
O
O
O
4
3
(5) sucessfully as com mon nucleophilic re agents men tioned
above. In or der to get the de sired prod ucts, 1,2,4-triazol-3-
yl-sydnones,phenylhydrazineshoulddefinitelybesuggested
toreactwithcarbohydroximicacidchlorides1 to give the de-
siredprecursors.Howeverthesubstitutionproductswerenot
only the ex pected N-phenylamino-3-arylsydnone-4- carbox-
am ide ox imes (6), but also 3-arylsydnone-4-carboxamide
phenylhydrazones (7) and other com pounds (Scheme I).
It is hard to ex plain which re ac tion con di tions were
changedincludingthereactiontemperature,reactiontime
and the quan tity of pyridine us age. Through sev eral ex per i-
mentaltests, theproblemwasfinallysolved. Ifthequantityof
phenylhydrazineusagewasincreasedto2.5equivalentofthe
starting material 3-arylsydnone-4-carbohydroximic acid
chloride(1), only prod uct7 would be ob tained in long re ac-
tion time as shown in Scheme I.
RESULTSANDDISCUSSION
In pre vi ous work, 3-arylsydnone-4-carbohydroximic
acidchlorides( 1) could eas ily re act with nucleophiles such as
ammonia,hydroxylamineandhydraziniumhydroxidetogive
thecorrespondingproducts2-4which are good precusors23-24
for the syn the ses of 4-heterocyclic sydnones.
Althoughthereactionmechanismbetweencompound1
and phenylhydrazine needs fur ther in ves ti ga tion, one might
speculatethatthemechanismwouldprobablybesimilarto
that of phenylosazones syn the ses25-27 and nitrosative cleav-
age of ter tiary amine.28-29 Amoleculeofanilinewasreleased
and elim i na tion of nitroxyl was pro posed in the mech a nism.
Re ac tion of an i line with carbohydroximic acid chlo-
rides 1give N-phenyl-3-arylsydnone-4-carboxamide ox imes

884 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
Shih et al.
Scheme I
could cyclize with al de hydes to form 1,2,4-oxadiazol-3-yl
sydnones.23-24 The for mer could only re act with ar o matic al-
de hydes to give com pounds8, but the lat ter re acted with both
aliphatic and ar o matic al de hydes sucessfully to af ford com-
pounds 8 and 9. There fore, 3-arylsydnone-4-carboxamide
phenylhydrazones (7) were next sug gested to re act with al de-
hydes 10. In deed, the cyclizations were com pletely suc cess-
fuleitherwitharomaticoraliphaticaldehydesunderacidcat-
a lyst. The re ac tion prod ucts 3-aryl-4-(1 -phenyl-5 -sub sti-
tuted-1 ,2 ,4 -triazol-3 -yl)sydnones (11) were ob tained in
highyield(SchemeIII).Thepossiblecyclizationmechanism
is sug gested in Scheme IV.
Cl
OH
PhHN
OH
Ar
Ar
N
N
EtOH
pyridine, 0O
N
N
+
PhNH2
C
N
N
O
O
O
O
1
5
PhHNHN
Ar
OH
N
1.5 equiv PhNHNH2
pyridine
+ 7 + others
N
Cl
OH
N
O
O
Ar
N
6
N
EtOH
0 O
N
C
O
O
H2N
NHPh
1
Ar
O
O
N
N
C
Ar'
N
C
R
2.5 equiv PhNHNH2
pyridine
N
Ar
C
N
Ar
C
N
N
O
O
N
N
7
N
N
O
O
O
O
8
9
Pyridine used in the re ac tion was not only to re move hy dro-
gen chlo ride, but also used as a nucleophilic as sis tant. There-
fore, the mech a nism might be sug gested as shown in Scheme
II.
Scheme III
Ph
N
Scheme II
Ar'CHO
N
C Ar'
10a~10e
HO
Cl
Ar
C N
N
N
Cl
OH
H+
Ar
Ar
N
C
N
N
pyridine
EtOH , 0 oC
O
O
N
N
H2N
NHPh
11aa~11ce
N
N
Ar
N
O
O
O
O
EtOH
N
1
Ph
N
O
PhNHNH2
O
7
N
N
C
R
RCHO
10f~10h
Ar
C N
N
Ph
H
H+
N
H
N
O
O
H
N
O
HN
O
_
PhNH2
11af~11ch
Ar
Ar
N
O
N
N
N
N
N
O
O
O
6
PhNHNH2
Amongthesenewproducts, theyellowcrystal11ca ob-
tained was an a lyt i cally pure and suit able for X-ray struc ture
determination.Themolecularstructureof3-(4 -methoxy-
phenyl)-4-[1 -phenyl-5 -(4 -dimethylaminophenyl)-1 ,2 ,4 -
triazol-3 -yl] sydnone (11ca) is shown in Fig. 1. De tails of
crystaldataaresummarizedinTables1-4.
H2N
NHPh
H2N
O
N
O
Ar
Ar
N
Ph
_
N
N
HNO
N
N
H
H
N
N
O
O
O
7
In summary, the experimental results showed that
3-arylsydnone-4-carbohydroximic acid chlo rides eas ily re-
acted with nucleophiles to give good pre cur sors for syn the-
It is known that 3-arylsydnone-4-carboxamide ox imes
(2) andN-hydroxy-3-arylsydnone-4-carboxamideoximes( 3)

3-Arylsydnone-4-carboxamide Phenylhydrazones
J. Chin. Chem. Soc., Vol. 48, No. 5, 2001 885
Table 1. Crystal Data of Compound 11ca
Scheme IV
Diffractometer
Rigaku AFC7S
.
.
Formula
C25H22N6O3
454.49
Monoclinic
P21/n(#14)
12.692(2)
8.517(1)
21.254(3)
96.75(1)
2281.4(6)
4
1.323
952.00
0.90
0.40 0.76 0.96
298
H2N
Formula weight
Cryst system
Space group
a/Å
b/Å
c/Å
Ar
C NNHPh
N
N
O
O
7
H+
R
CHO
R
CH
R
O
H
Ph
N
(deg)
V/Å3
H
R
N
C
NH CH
Z
Ar
C N
Dcalc(g cm-3)
F000
Ar
C N NHPh
+
_
H
N
H
N
N
N
O
O
(Mo,K ), cm-1
Crystal size (mm)
Temperature (K)
Scan type
O
O
Ph
N
-2
N
C R
2
max, deg
50.0
4512
4307
3087
Ar
C N
oxidation
Reflections measured
Unique reflections
No. observations [I>3.00 (I)]
No. variables
N
N
O
O
11
307
Residuals: R; Rw
GoF
0.044; 0.049
3.67
siz ing 4-heterocyclic sydnones. 3-Arylsydnone-4-car box-
amide phenylhydrazones (7) could be iso lated in a pure state
throughlongtimereactionofcarbohydroximicacidchlorides
1 andanexcessamountofphenylhydrazine. Theprecursors7
could cyclize with both ar o matic and aliphatic al de hydes in
the presence of acid cat a lyst to af ford the de sired 1,2,4-
triazolyl sub sti tuted sydnones. The quan tity of sul fu ric acid
us age should be con trolled ad e quately to im prove the re ac-
tionrate.Fromseveralexperimentaltests,itcanbefoundthat
a small amount of sul fu ric acid cat a lyzes the re ac tion. How-
ever, a large amount of sul fu ric acid re tards the re ac tion and
Table 2. Selected Bond Distances Å for Compound 11ca
O(1)-N(2)
O(2)-C(1)
O(3)-C(9)
N(1)-C(2)
N(3)-N(4)
N(4)-C(11)
N(5)-C(10)
N(6)-C(15)
N(6)-C(19)
C(2)-C(10)
C(3)-C(8)
1.377(2)
1.204(2)
1.419(3)
1.352(2)
1.372(2)
1.358(2)
1.353(2)
1.375(3)
1.441(3)
1.447(3)
1.370(3)
1.379(3)
1.379(3)
1.390(3)
1.375(3)
1.403(3)
1.359(3)
1.393(4)
1.361(5)
O(1)-C(1)
O(3)-C(6)
N(1)-N(2)
N(1)-C(3)
N(3)-C(10)
N(4)-C(20)
N(5)-C(11)
N(6)-C(18)
C(1)-C(2)
C(3)-C(4)
C(4)-C(5)
C(6)-C(7)
C(11)-C(12)
C(12)-C(17)
C(14)-C(15)
C(16)-C(17)
C(20)-C(25)
C(22)-C(23)
C(24)-C(25)
1.419(2)
1.368(2)
1.313(2)
1.452(2)
1.328(2)
1.444(2)
1.333(2)
1.447(3)
1.414(3)
1.366(3)
1.385(3)
1.382(3)
1.459(3)
1.389(3)
1.400(3)
1.373(3)
1.364(3)
1.357(5)
1.390(4)
C(5)-C(6)
C(7)-C(8)
C(12)-C(13)
C(13)-C(14)
C(15)-C(16)
C(20)-C(21)
C(21)-C(22)
C(23)-C(24)
Fig. 1. Molecularstructureof3-(4 -methoxyphenyl)-
4-[1 -phenyl-5 -(4 -dimethylaminophenyl)-
1 ,2 ,4 -triazol-3 -yl]sydnone (11ca).

886 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
Shih et al.
Table 3. Selected Bond Angles/deg for Compound 11ca
N(2)-O(1)-C(1)
N(2)-N(1)-C(2)
C(2)-N(1)-C(3)
N(4)-N(3)-C(10)
N(3)-N(4)-C(20)
C(10)-N(5)-C(11)
C(15)-N(6)-C(19)
O(1)-C(1)-O(2)
O(2)-C(1)-C(2)
N(1)-C(2)-C(10)
N(1)-C(3)-C(4)
C(4)-C(3)-C(8)
C(4)-C(5)-C(6)
111.4(2)
115.2(2)
128.3(2)
101.5(2)
117.1(2)
103.9(2)
120.9(2)
119.9(2)
136.7(2)
125.0(2)
119.5(2)
122.1(2)
119.3(2)
115.3(2)
120.4(2)
115.4(2)
124.2(2)
128.4(2)
125.2(2)
117.2(2)
121.7(2)
121.1(2)
121.3(2)
119.0(2)
121.7(2)
119.9(3)
120.0(3)
C(6)-O(3)-C(9)
117.8(2)
116.6(2)
104.0(2)
110.6(2)
132.1(2)
121.2(2)
116.1(2)
103.4(2)
106.1(2)
128.9(2)
118.3(2)
119.4(2)
124.5(2)
120.3(2)
118.5(2)
120.4(2)
108.6(2)
123.0(2)
117.5(2)
121.4(2)
122.4(2)
116.5(2)
121.9(2)
119.2(2)
118.9(3)
120.8(3)
118.7(3)
N(2)-N(1)-C(3)
O(1)-N(2)-N(1)
N(3)-N(4)-C(11)
C(11)-N(4)-C(20)
C(15)-N(6)-C(18)
C(18)-N(6)-C(19)
O(1)-C(1)-C(2)
N(1)-C(2)-C(1)
C(1)-C(2)-C(10)
N(1)-C(3)-C(8)
C(3)-C(4)-C(5)
O(3)-C(6)-C(5)
C(5)-C(6)-C(7)
C(3)-C(8)-C(7)
O(3)-C(6)-C(7)
C(6)-C(7)-C(8)
N(3)-C(10)-N(5)
N(5)-C(10)-C(2)
N(4)-C(11)-C(12)
C(11)-C(12)-C(13)
C(13)-C(12)-C(17)
C(13)-C(14)-C(15)
N(6)-C(15)-C(16)
C(15)-C(16)-C(17)
N(4)-C(20)-C(21)
C(21)-C(20)-C(25)
C(21)-C(22)-C(23)
C(23)-C(24)-C(25)
N(3)-C(10)-C(2)
N(4)-C(11)-N(5)
N(5)-C(11)-C(12)
C(11)-C(12)-C(17)
C(12)-C(13)-C(14)
N(6)-C(15)-C(14)
C(14)-C(15)-C(16)
C(12)-C(17)-C(16)
N(4)-C(20)-C(25)
C(20)-C(21)-C(22)
C(22)-C(23)-C(24)
C(20)-C(25)-C(24)
re duces yields be cause ex cess acid may protonate the amino
accordingtomethodsintheliterature.17
group of com pound7and re duce its nuclophilicity.
Syntheses of N-Phenyl-3-arylsydnone-4-carboxamide
Oximes (5a-5d)
EXPERIMENTALSECTION
To the ice-cooled so lu tion of an i line (121.1 mg, 1.3
mmol) in 0.5 mL 95% eth a nol, pyridine (118.7 mg, 1.5 mmol)
was added. The mixed base so lu tion was stirred at 0 C. Then,
the ice-cooled solution of 3-phenylsydnone-4-car bohy-
droximic acid chlo ride (239.5 mg, 1.0 mmol) in 4 mL 95%
eth a nol was slowly added to the above ba sic so lu tion over 1
h. The re ac tion mix ture was stirred at 0 C for 3-4 h. The yel-
low pre cip i tate was col lected by fil tra tion and washed with
95% eth a nol. The fil trate was poured into crushed ice, and the
crude prod uct was col lected by fil tra tion. All the solid prod-
ucts were com bined and recrystallized from eth a nol to af ford
220.2 mg (74%) of N-phenyl-3-phenylsydnone-4-carbox-
amideoxime (5a) as yel low crys tal line. The prop er ties and
analyticaldataofnewcompounds5a-5d arelistedasfollows.
AllmeltingpointsweredeterminedonaYanacoMP-J3
micromeltingpointapparatusandareuncorrected.IRspectra
were re corded on a Hitachi 270-30 In fra red Spectro photo-
meter. Mass spec tra were mea sured on a VG 70-250S GC/
MS/MSspectrometer. 1H NMR spec tra were run on a Bruker
AMX-200 NMR spec trom e ter, us ing TMS as in ter nal stan-
dard. El e men tal anal y ses were taken with a Heraeus CHN-
O-Rapid Analyzer. X-ray spectra were performed on a
Rigaku AFC7S diffractometer.
StartingMaterials
3-Phenylsydnone-4-carbohydroximic acid chloride
(1a), 3-(4 -methylphenyl)sydnone-4-carbohydroximic acid
chloride (1b), 3-(4 -methoxyphenyl)sydnone-4-carbohy-
droximic acid chlo ride (1c) and 3-(4 -ethoxyphenyl)syd-
none-4-carbohydroximic acid chlo ride (1d) were pre pared
N-Phenyl-3-phenylsydnone-4-carboxamide Oxime (5a)
Yel low nee dles; yield 74%; mp 143-144 C; IR (KBr)
3336, 3295, 1754 cm-1; 1H NMR (DMSO-d6), 10.89 (s, 1H),

3-Arylsydnone-4-carboxamide Phenylhydrazones
J. Chin. Chem. Soc., Vol. 48, No. 5, 2001 887
Table 4. Atomic Coordinates for Compound 11ca
N-Phenyl-3-(4 -methoxylphenyl)sydnone-4-carboxamide
Oxime (5c)
Atom
X
Y
Z
White plates; yield 90%; mp 170-171 C; IR (KBr)
3382, 3238, 1776 cm-1; 1H NMR (DMSO-d6), 10.86(s, 1H),
8.50 (s, 1H), 7.29 (d,J = 9.2 Hz, 2H), 7.13-6.90 (m, 3H), 7.07
(d, J = 9.2 Hz, 2H), 6.59 (d, J = 7.1 Hz, 2H), 3.83 (s, 3H);
EIMS (20 eV) m/z (%): 326 (M+, 2), 296 (14), 268 (34), 250
(64), 134 (100). Anal. Calcd for C16H14N4O4: C, 58.89; H,
4.32; N, 17.17. Found: C, 58.98; H, 4.33; N, 17.14.
O(1)
O(2)
O(3)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
0.3941(1)
0.4478(1)
0.7105(1)
0.5112(1)
0.4253(1)
0.6663(1)
0.7517(1)
0.6885(1)
1.0735(2)
0.4642(2)
0.5405(2)
0.5632(2)
0.6451(2)
0.6971(2)
0.6647(2)
0.5806(2)
0.5295(2)
0.7995(2)
0.6319(2)
0.7645(2)
0.8460(2)
0.9441(2)
1.0185(2)
0.9991(2)
0.8999(2)
0.8265(2)
1.1733(2)
1.0453(2)
0.8051(2)
0.8799(2)
0.9261(3)
0.8958(3)
0.8218(3)
0.7750(2)
0.1327(2)
0.2210(2)
0.3716(2)
0.2298(2)
0.1428(2)
0.3917(2)
0.4894(2)
0.4531(2)
0.8857(3)
0.2165(3)
0.2783(3)
0.2607(3)
0.1669(3)
0.2001(3)
0.3269(3)
0.4187(3)
0.3865(3)
0.2847(4)
0.3754(3)
0.5248(3)
0.6223(3)
0.6572(3)
0.7441(3)
0.8017(3)
0.7660(3)
0.6783(3)
0.9310(3)
0.9662(4)
0.5441(3)
0.4511(4)
0.4993(5)
0.6366(5)
0.7298(4)
0.6833(3)
0.50327(7)
0.60285(7)
0.23978(8)
0.45142(8)
0.44348(8)
0.59255(8)
0.59028(8)
0.49120(8)
0.4225(1)
0.5482(1)
0.51149(9)
0.39535(9)
0.3822(1)
0.3299(1)
0.2921(1)
0.3058(1)
0.3581(1)
0.2246(1)
0.53143(9)
0.5294(1)
0.5059(1)
0.5392(1)
0.5124(1)
0.4504(1)
0.4172(1)
0.4443(1)
0.4579(1)
0.3632(1)
0.6500(1)
0.6824(1)
0.7420(2)
0.7667(1)
0.7336(1)
0.6741(1)
N-Phenyl-3-(4 -ethoxyphenyl)sydnone-4-carboxamide
Oxime (5d)
White plates; yield 92%; mp 155-156 C; IR (KBr)
3384, 3208, 1760 cm-1; 1H NMR (DMSO-d6), 10.86 (s, 1H),
8.50 (s, 1H), 7.26 (d,J = 9.2 Hz, 2H), 7.13-6.83 (m, 3H), 7.04
(d, J = 9.2 Hz, 2H), 6.58 (d, J = 7.3 Hz, 2H), 4.11 (q, J = 6.9
Hz, 2H), 1.35 (t,J = 6.9 Hz, 3H); EIMS (20 eV) m/z (%): 340
(M+, 10), 310 (11), 282 (23), 264 (45), 148 (100). Anal. Calcd
for C 17H16N4O4: C, 60.00; H, 4.74; N, 16.46. Found: C, 60.00;
H, 4.75; N, 16.52.
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
Syntheses of 3-Arylsydnone-4-carboxamide
Phenylhydrazones (7a-7d)
To an ice cooled so lu tion of phenylhydrazine (248.7
mg, 2.3 mmol) in 95% eth a nol (0.5 mL), pyridine (197.8 mg,
2.5 mmol) was added. The mixed ba sic so lu tion was stirred at
0 C. An ice-cooled so lu tion of 3-phenylsydnone-4-car bo-
hydroximic acid chlo ride (239.5 mg, 1.0 mmol) in 95% eth a-
nol (4 mL) was slowly added to the above ba sic so lu tion over
1 h. The re ac tion mix ture was stirred for fur ther 2-3 h at 0 C,
thenkeptstirringatroomtemperatureuntilthereactionwas
completed.Theresultingdarkredsolutionwasconcentrated
and fil tered. The ob tained red solid was recrystallized from
95% ethanol to afford 3-phenylsydnone-4-carboxamide
phenylhydrazone (7a, 104.1 mg, 35%).
8.52 (s, 1H), 7.69-7.31 (m, 5H), 7.19-6.90 (m, 3H), 6.57 (d, J
= 7.3 Hz, 2H); EIMS (20 eV) m/z (%): 296 (M+, 17), 266 (75),
238 (26), 220 (100), 104 (52). Anal. Calcd for C 15H12N4O3: C,
60.81; H, 4.08; N, 18.91. Found: C, 60.80; H, 4.12; N, 18.89.
3-Phenylsydnone-4-carboxamide Phenylhydrazone (7a)
Red needles; yield 35%; mp 171-172 C; IR (KBr)
3460, 3364, 3320, 1722 cm-1; 1H NMR (DMSO-d6), 8.38 (s,
1H), 7.73-7.67 (m, 5H), 6.90 (t, J = 8.1 Hz, 2H), 6.53 (tt, J =
8.1, 1.4 Hz, 1H), 6.21 (dd, J = 8.1, 1.4 Hz, 2H), 5.95 (s, 2H);
EIMS (70 eV) m/z (%): 295 (M+, 25), 265 (33), 237 (48), 104
(47), 92(100). Anal. Calcd for C 15H13N5O2: C, 61.01; H, 4.44;
N, 23.72. Found: C, 60.99; H, 4.48; N, 23.72.
N-Phenyl-3-(4 -methylphenyl)sydnone-4-carboxamide
Oxime (5b)
Yel low nee dles; yield 72%; mp 146-147 C; IR (KBr)
3308, 3250, 1758, 1738 cm-1; 1H NMR (DMSO-d6), 10.85
(s, 1H), 8.50 (s, 1H), 7.37 (d, J = 8.0 Hz, 2H), 7.24 (d,J = 8.0
Hz, 2H), 7.20-6.69 (m, 3H), 6.60 (d, J = 7.3 Hz, 2H), 2.39 (s,
3H); EIMS (20 eV) m/z (%): 310 (M+, 6), 280 (43), 252 (20),
234 (82), 118 (100). Anal. Calcd for C16H14N4O3: C, 61.93;
H, 4.55; N, 18.05. Found: C, 61.92; H, 4.60; N, 18.06.
3-(4 -Methylphenyl)sydnone-4-carboxamide
Phenylhydrazone (7b)
Red needles; yield 40%; mp 167-168 C; IR (KBr)
3432, 3332, 3304, 1724 cm-1; 1H NMR (DMSO-d6), 8.36 (s,

888 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
Shih et al.
+
1H), 7.60 (d, J = 8.6 Hz, 2H), 7.46 (d, J = 8.6 Hz, 2H), 6.95 (t,
J = 7.3 Hz, 2H), 6.58 (t, J = 7.3 Hz, 1H), 6.24 (d, J = 7.3 Hz,
2H), 5.93 (s, 2H), 2.47 (s, 3H); EIMS (20 eV) m/z (%): 309
(M+, 100), 279 (92), 251 (79), 118 (47), 92 (51). Anal. Calcd
for C 16H15N5O2: C, 62.13; H, 4.89; N, 22.64. Found: C, 62.04;
H, 4.93; N, 22.60.
m/z (%): 424 (M+, 23), 366 (M+-NO-CO, 100), 77 (C6H5 ,
19). Anal. Calcd for C 24H20N6O2: C, 67.91; H, 4.75; N, 19.80.
Found: C, 67.77; H, 4.80; N, 19.64.
3-(4 -Methylphenyl)-4-[1 -phenyl-5 -(4 -dimethylamino-
phenyl)-1 ,2 ,4 -triazol-3 -yl]sydnone (11ba)
Yellow crystals from CH2Cl2/EtOH; yield 80%; mp
191-192 C; IR (KBr) 1768 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.71 (d, J= 8.4 Hz, 2H), 7.56-7.30 (m, 7H), 7.07 (d, J =
9.0 Hz, 2H), 6.59 (d, J = 9.0 Hz, 2H), 2.90 (s, 6H), 2.44 (s,
3H); EIMS (30 eV)m/z (%): 438 (M+, 13), 380 (M+-NO-CO,
3-(4 -Methoxyphenyl)sydnone-4-carboxamide
Phenylhydrazone (7c)
Red needles; yield 50%; mp 189-190 C; IR (KBr)
1
3436, 3332, 3308, 1726, 1716 cm-1; H NMR (DMSO-d6),
+
8.37 (s, 1H), 7.65 (d, J = 9.1 Hz, 2H), 7.18 (d,J = 9.1 Hz, 2H),
6.95 (t, J = 7.2 Hz, 2H), 6.55 (t, J = 7.2 Hz, 1H), 6.31 (d, J =
7.2 Hz, 2H), 5.94 (s, 2H), 3.87 (s, 3H); EIMS (70 eV) m/z
(%): 325 (M+, 59), 295 (43), 267 (45), 134 (100), 92 (94).
Anal. Calcd for C16H15N5O3: C, 59.07; H, 4.65; N, 21.53.
Found: C, 58.93; H, 4.66; N, 21.48.
100), 91 (CH3C6H4 , 7). Anal. Calcd for C25H22N6O2: C,
68.48; H, 5.06; N, 19.17. Found: C, 68.21; H, 5.16; N, 19.08.
3-(4 -Methoxyphenyl)-4-[1 -phenyl-5 -(4 -dimethylamino-
phenyl)-1 ,2 ,4 -triazol-3 -yl]sydnone (11ca)
Yellow crystals from CH2Cl2/EtOH; yield 87%; mp
235-236 C; IR (KBr) 1770 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.77 (d, J = 9.0 Hz, 2H), 7.56-7.35 (m, 5H), 7.18 (d, J =
9.0 Hz, 2H), 7.10 (d,J = 8.9 Hz, 2H), 6.60 (d, J = 8.9 Hz, 2H),
3.86 (s, 3H), 2.90 (s, 6H); EIMS (30 eV) m/z (%): 454 (M+,
12), 396 (M+-NO-CO, 100). Anal. Calcd for C25H22N6O3: C,
66.07; H, 4.88; N, 18.49. Found: C, 65.98; H, 4.93; N, 18.43.
3-(4 -Ethoxyphenyl)sydnone-4-carboxamide
Phenylhydrazone (7d)
Red needles; yield 52%; mp 180-182 C; IR (KBr)
3448, 3348, 3324, 1722 cm-1; 1H NMR (DMSO-d6), 8.37 (s,
1H), 7.63 (d, J = 9.0 Hz, 2H), 7.16 (d, J = 9.0 Hz, 2H), 6.95 (t,
J = 7.2 Hz, 2H), 6.55 (t, J = 7.2 Hz, 1H), 6.33 (d, J = 7.2 Hz,
2H), 5.95 (s, 2H), 4.14 (q, J = 6.9 Hz, 2H), 1.38 (t, J = 6.9 Hz,
3H); EIMS (20 eV)m/z (%): 339 (M+, 53), 309 (34), 281 (31),
148 (82), 92 (100). Anal. Calcd for C17H17N5O3: C, 60.17; H,
5.05; N, 20.64. Found: C, 59.94; H, 5.05; N, 20.43.
3-(4 -Ethoxyphenyl)-4-[1 -phenyl-5 -(4 -dimethylamino-
phenyl)-1 ,2 ,4 -triazol-3 -yl]sydnone (11da)
Yellow crystals from CH2Cl2/EtOH; yield 85%; mp
195-196 C; IR (KBr) 1770 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.75 (d, J = 8.9 Hz, 2H), 7.56-7.32 (m, 5H), 7.15 (d, J =
8.9 Hz, 2H), 7.09 (d,J = 9.0 Hz, 2H), 6.60 (d, J = 9.0 Hz, 2H),
4.14 (q, J = 6.9 Hz, 2H), 2.91 (s, 6H), 1.36 (t,J = 6.9 Hz, 3H);
EIMS (70 eV)m/z (%): 468 (M+, 17), 410 (M+-NO-CO, 100).
Anal. Calcd for C26H24N6O3: C, 66.65; H, 5.16; N, 17.94.
Found: C, 66.48; H, 5.24; N, 17.86.
Syntheses of 3-Aryl-4-(1 -phenyl -5 -aryl-1 ,2 ,4 -triazol-
3 -yl)sydnones (11aa-11ce)
Typicalproceduresforthesynthesesofsydnonederiva-
tives 11aa-11ce were as fol lows:
To a so lu tion of 3-phenylsydnone-4-carboxamide phen-
ylhydrazone (7a, 118.1 mg, 0.4 mmol) and 4-(dimethyl-
amino)benzaldehyde ( 10a, 71.6 mg, 0.48 mmol) in 95% eth a-
nol (3 mL), a drop of sul fu ric acid (98%) was added as cat a-
lytic agent. The re ac tion mix ture was stirred at room tem per-
a ture for 4 days. The pre cip i ta tion solid was col lected by fil-
trationandthenrecrystallizedfromdichloromethane-ethanol
to af ford 3-phenyl-4-[1 -phenyl-5 -(4 -dimethylaminophen-
yl)-1 ,2 ,4 -triazol-3 -yl]sydnone (11aa, 128.0 mg, 75%).
3-Phenyl-4-[1 -phenyl-5 -(3 -methoxyphenyl)-1 ,2 ,4 -
triazol-3 -yl]sydnone (11ab)
White crystals from CH2Cl2/EtOH; yield 75%; mp
199-200 C; IR (KBr) 1770 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.92-7.65 (m, 5H), 7.56-7.18 (m, 6H), 7.05-6.74 (m, 3H),
3.61 (s, 3H); EIMS (30 eV) m/z (%): 411 (M+, 15), 353 (M+-
NO-CO, 100), 77 (C6H5+, 18). Anal. Calcd for C23H17N5O3:
C, 67.15; H, 4.16; N, 17.02. Found: C, 67.12; H, 4.22; N,
17.02.
3-Phenyl-4-[1 -phenyl-5 -(4 -dimethylaminophenyl)-
1 ,2 ,4 -triazol-3 -yl]sydnone (11aa)
Yellow crystals from CH2Cl2/EtOH; yield 75%; mp
212-213 C; IR (KBr) 1766 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.91-7.64 (m, 5H), 7.56-7.28 (m, 5H), 7.04 (d, J = 9.0
Hz, 2H), 6.58 (d, J = 9.0 Hz, 2H), 2.89 (s, 6H); EIMS (70 eV)
3-(4 -Methylphenyl)-4-[1 -phenyl-5 -(3 -methoxyphenyl)-
1 ,2 ,4 -triazol-3 -yl]sydnone (11bb)
Yellow crystals from CH2Cl2/EtOH; yield 78%; mp
194-195 C; IR (KBr) 1768 ( C=O) cm-1; 1H NMR (DMSO-

3-Arylsydnone-4-carboxamide Phenylhydrazones
J. Chin. Chem. Soc., Vol. 48, No. 5, 2001 889
d6), 7.73 (d, J = 8.4 Hz, 2H), 7.57-7.18 (m, 8H), 6.97-6.79
(m, 3H), 3.62 (s, 3H), 2.43 (s, 3H); EIMS (30 eV) m/z (%):
213-214 C; IR (KBr) 1774 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.78 (d, J = 9.0 Hz, 2H), 7.55-7.42 (m, 5H), 7.39-7.26
(m, 5H), 7.18 (d,J = 9.0 Hz, 2H), 3.86 (s, 3H); EIMS (70 eV)
+
425 (M+, 14), 367 (M+-NO-CO, 100), 91 (CH3C6H4 , 20).
+
Anal. Calcd for C24H19N5O3: C, 67.76; H, 4.50; N, 16.46.
Found: C, 67.53; H, 4.55; N, 16.35.
m/z (%): 411 (M+, 4), 353 (M+-NO-CO, 100), 107 (CH3OC6H4 ,
6). Anal. Calcd for C23H17N5O3: C, 67.15; H, 4.16; N, 17.02.
Found: C, 66.91; H, 4.25; N, 16.95.
3-(4 -Methoxyphenyl)-4-[1 -phenyl-5 -(3 -methoxyphenyl)-
1 ,2 ,4 -triazol-3 -yl]sydnone (11cb)
3-(4 -Ethoxyphenyl)-4-(1 ,5 -diphenyl-1 ,2 ,4 -triazol-3 -yl)-
sydnone (11dc)
Yellow crystals from CH2Cl2/EtOH; yield 81%; mp
208-209 C; IR (KBr) 1766 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.79 (d, J = 9.0 Hz, 2H), 7.57-7.35 (m, 5H), 7.27-7.14
(m, 3H), 7.03-6.76 (m, 3H), 3.86 (s, 3H), 3.62 (s, 3H); EIMS
(30 eV) m/z (%): 441 (M+, 6), 383 (M+-NO-CO, 100), 107
White nee dles from CH3COCH3/EtOH; yield 88%; mp
197-198 C; IR (KBr) 1766 ( C=O) cm-1; 1H NMR (DMSO-
d6), 7.76 (d, J = 9.0 Hz, 2H), 7.55-7.42 (m, 5H), 7.39-7.23
(m, 5H), 7.15 (d, J = 9.0 Hz, 2H), 4.14 (q, J = 6.9 Hz, 2H),
1.36 (t, J = 6.9 Hz, 3H); EIMS (70 eV) m/z (%): 425 (M+, 3),
+
(CH3OC6H4 , 4). Anal. Calcd for C24H19N5O4: C, 65.30; H,
+
4.34; N, 15.87. Found: C, 65.11; H, 4.40; N, 15.89.
367 (M+-NO-CO, 100), 121 (C2H5OC6H4 , 3). Anal. Calcd
for C 24H19N5O3: C, 67.76; H, 4.50; N, 16.46. Found: C, 67.71;
H, 4.53; N, 16.41.
3-(4 -Ethoxyphenyl)-4-[1 -phenyl-5 -(3 -methoxyphenyl)-
1 ,2 ,4 -triazol-3 -yl]sydnone (11db)
Yellow crystals from CH2Cl2/EtOH; yield 80%; mp
3-Phenyl-4-[1 -phenyl-5 -(4 -nitrophenyl)-1 ,2 ,4 -triazol-
3 -yl]sydnone (11ad)
1
214-215 C; IR (KBr) 1766 ( C=O) cm-1; H NMR (Ac e-
tone-d6 + DMSO-d6), 7.78 (d,J = 9.0 Hz, 2H), 7.58-7.42 (m,
5H), 7.27-7.14 (m, 3H), 7.04-6.93 (m, 3H), 4.19 (q, J = 6.9
Hz, 2H), 3.68 (s, 3H), 1.41 (t, J = 6.9 Hz, 3H); EIMS (30 eV)
m/z(%): 455 (M+, 5), 397 (M+-NO-CO, 100), 121 (C2H5OC6H4+,
5). Anal. Calcd for C25H21N5O4: C, 65.93; H, 4.65; N, 15.38.
Found: C, 65.85; H, 4.74; N, 15.17.
YellowneedlesfromCH3COCH3/EtOH; yield 72%; mp
195-196 C; IR (KBr) 1770 ( C=O), 1524, 1340 ( NO2)
1
cm-1; H NMR (Acetone-d6), 8.23 (d, J = 9.1 Hz, 2H),
7.93-7.67 (m, 7H), 7.62-7.35 (m, 5H); EIMS (30 eV)m/z (%):
+
426 (M+, 8), 368 (M+-NO-CO, 100), 77 (C6H5 , 3). Anal.
Calcd for C22H14N6O4: C, 61.97; H, 3.31; N, 19.71. Found: C,
61.76; H, 3.47; N, 19.58.
3-Phenyl-4-(1 ,5 -diphenyl-1 ,2 ,4 -triazol-3 -yl)sydnone
(11ac)
3-(4 -Methylphenyl)-4-[1 -phenyl-5 -(4 -nitrophenyl)-
1 ,2 ,4 -triazol-3 -yl]sydnone (11bd)
White nee dles from CH3COCH3/EtOH; yield 74%; mp
1
209-210 C; IR (KBr) 1761 ( C=O) cm-1; H NMR (Ac e-
YellowneedlesfromCH3COCH3/EtOH; yield 76%; mp
163-164 C; IR (KBr) 1770 ( C=O), 1524, 1344 ( NO2)
cm-1; 1HNMR(Acetone-d6), 8.23 (d, J = 8.8 Hz, 2H), 7.75
(d, J = 8.8 Hz, 2H), 7.68-7.49 (m, 7H), 7.42 (d, J = 8.8 Hz,
2H), 2.49 (s, 3H); EIMS (30 eV) m/z (%): 440 (M+, 5), 382
tone-d6), 7.92-7.63 (m, 5H), 7.58-7.38 (m, 5H), 7.37-7.31
(m, 5H); EIMS (30 eV) m/z (%): 381(M+, 9), 323 (M+-NO-
+
CO, 100), 77 (C6H5 , 4). Anal. Calcd for C22H15N5O2: C,
69.28; H, 3.96; N, 18.36. Found: C, 69.21; H, 4.14; N, 18.18.
+
(M+-NO-CO, 100), 91 (CH3C6H4 , 6). Anal. Calcd for
3-(4 -Methylphenyl)-4-(1 ,5 -diphenyl-1 ,2 ,4 -triazol-3 -yl)-
sydnone (11bc)
C23H16N6O4: C, 62.73; H, 3.66; N, 19.08. Found: C, 62.54; H,
3.75; N, 19.04.
White nee dles from CH3COCH3/EtOH; yield 70%; mp
1
210-210.5 C; IR (KBr) 1770 ( C=O) cm-1; H NMR
3-(4 -Methoxyphenyl)-4-[1 -phenyl-5 -(4 -nitrophenyl)-
1 ,2 ,4 -triazol-3 -yl]sydnone (11cd)
(DMSO-d6), 7.73 (d, J = 8.5 Hz, 2H), 7.54-7.44 (m, 5H),
7.41-7.24 (m, 7H), 2.43 (s, 3H); EIMS (30 eV) m/z (%): 395
YellowneedlesfromCH3COCH3/EtOH; yield 83%; mp
239-240 C; IR (KBr) 1772 ( C=O), 1528, 1346 ( NO2)
cm-1; 1H NMR (DMSO-d6), 8.23 (d,J = 9.0 Hz, 2H), 7.79 (d,
J = 9.0 Hz, 2H), 7.61-7.48 (m, 5H), 7.47 (d, J = 9.0 Hz, 2H),
7.17 (d,J = 9.0 Hz, 2H), 3.86 (s, 3H); EIMS (70 eV)m/z (%):
(M+, 11), 337 (M+-NO-CO, 100), 91 (CH3C6H4 , 19). Anal.
+
Calcd for C 23H17N5O2: C, 69.86; H, 4.33; N, 17.71. Found: C,
69.84; H, 4.36; N, 17.66.
+
3-(4 -Methoxyphenyl)-4-(1 ,5 -diphenyl-1 ,2 ,4 -triazol-3 -
yl)sydnone (11cc)
456 (M+, 4), 398 (M+-NO-CO, 100), 107 (CH3OC6H4 , 9).
Anal. Calcd for C23H16N6O5: C, 60.53; H, 3.53; N, 18.41.
Found: C, 60.37; H, 3.62; N, 18.39.
White nee dles from CH3COCH3/EtOH; yield 85%; mp

890 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
Shih et al.
3-Phenyl-4-[1 -phenyl-5 -(furan-2 -yl)-1 ,2 ,4 -triazol-3 -yl]
sydnone (11ae)
C18H15N5O2: C, 64.86; H, 4.54; N, 21.01. Found: C, 64.73; H,
4.57; N, 20.99.
YellowneedlesfromCH3COCH3/EtOH; yield 90%; mp
257-258 C; IR (KBr) 1786, 1768 ( C=O) cm-1; 1H NMR
(Acetone-d6), 7.86-7.64 (m, 5H), 7.60-7.42 (m, 6H), 6.58-
6.49 (m, 2H); EIMS (30 eV) m/z (%): 371 (M+, 15), 313 (M+-
3-(4 -Methylphenyl)-4-(1 -phenyl-5 -ethyl-1 ,2 ,4 -triazol-
3 -yl)sydnone (11bf)
White nee dles from EtOH; yield 78%; mp 202-203 C;
IR (KBr) 1762 ( C=O) cm-1; 1H NMR (DMSO-d6), 7.66 (d,
J = 8.3 Hz, 2H), 7.52-7.47 (m, 5H), 7.43 (d, J = 8.3 Hz, 2H),
2.71 (q, J = 7.4 Hz, 2H), 2.42 (s, 3H), 1.05 (t,J = 7.4 Hz, 3H);
EIMS (30 eV)m/z (%): 347 (M+, 10), 289 (M+-NO-CO, 100),
91 (CH3C6H4+, 23). Anal. Calcd for C 19H17N5O2: C, 65.70; H,
4.93; N, 20.16. Found: C, 65.42; H, 4.97; N, 20.09.
+
NO-CO, 100), 77 (C6H5 , 35). Anal. Calcd for C20H13N5O3:
C, 64.68; H, 3.53; N, 18.86. Found: C, 64.49; H, 3.59; N,
18.79.
3-(4 -Methylphenyl)-4-[1 -phenyl-5 -(furan-2 -yl)-1 ,2 ,4 -
triazol-3 -yl]sydnone (11be)
White nee dles from CH3COCH3/EtOH; yield 91%; mp
208-209 C; IR (KBr) 1768, 1748 ( C=O) cm-1; 1H NMR
(Acetone-d6), 7.71 (d, J = 8.8 Hz, 2H), 7.61-7.42 (m, 8H),
6.58-6.48 (m, 2H), 2.47 (s, 3H); EIMS (30 eV) m/z (%): 385
3-(4 -Methoxyphenyl)-4-(1 -phenyl-5 -ethyl-1 ,2 ,4 -triazol-
3 -yl)sydnone (11cf)
White nee dles from EtOH; yield 72%; mp 193-194 C;
IR (KBr) 1776, 1766 ( C=O) cm-1; 1H NMR (DMSO-d6),
7.71 (d, J = 9.0 Hz, 2H), 7.61-7.42 (m, 5H), 7.15 (d, J = 9.0
Hz, 2H), 3.85 (s, 3H), 2.72 (q,J = 7.5 Hz, 2H), 1.07 (t, J = 7.5
Hz, 3H); EIMS (30 eV) m/z (%): 363 (M+, 5), 305 (M+-NO-
CO, 100), 107 (CH3OC6H4+, 2). Anal. Calcd for C19H17N5O3:
C, 62.80; H, 4.72; N, 19.27. Found: C, 62.64; H, 4.75; N,
19.19.
+
(M+, 15), 327 (M+-NO-CO, 100), 91 (CH3C6H4 , 31). Anal.
Calcd for C 21H15N5O3: C, 65.45; H, 3.92; N, 18.17. Found: C,
65.39; H, 4.05; N, 17.98.
3-(4 -Methoxyphenyl)-4-[1 -phenyl-5 -(furan-2 -yl)-1 ,2 ,4 -
triazol-3 -yl]sydnone (11ce)
White nee dles from CH3COCH3/EtOH; yield 85%; mp
212-213 C; IR (KBr) 1790, 1774 ( C=O) cm-1; 1H NMR
(Acetone-d6), 7.74 (d, J = 9.1 Hz, 2H), 7.60-7.34 (m, 6H),
7.16 (d, J = 9.1 Hz, 2H), 6.59-6.49 (m, 2H), 3.90 (s, 3H);
EIMS (70 eV) m/z (%): 401 (M+, 6), 343 (M+-NO-CO, 100),
3-Phenyl-4-(1 -phenyl-5 -isopropyl-1 ,2 ,4 -triazol-3 -yl)-
sydnone (11ag)
White nee dles from CH3COCH3/EtOH; yield 90%; mp
158-159 C; IR (KBr) 1794, 1774 ( C=O) cm-1; 1H NMR
(Acetone-d6), 7.82-7.64 (m, 5H), 7.61-7.39 (m, 5H), 3.25-
2.96 (m, 1H), 1.10 (d,J = 6.8 Hz, 6H); EIMS (30 eV) m/z (%):
+
107 (CH3OC6H4 , 3). Anal. Calcd for C21H15N5O4: C, 62.84;
H, 3.77; N, 17.45. Found: C, 62.73; H, 3.82; N, 17.37.
+
Syntheses of 3-Aryl-4-(1 -phenyl-5 -alkyl-1 ,2 ,4 -triazol-
3 -yl)sydnones (11af-11ch)
Typicalproceduresforthesynthesesofsydnonederiva-
tives 11af-11ch were as fol lows:
347 (M+, 15), 289 (M+-NO-CO, 100), 77 (C6H5 , 4). Anal.
Calcd for C19H17N5O2: C, 65.70; H, 4.93; N, 20.16. Found: C,
65.64; H, 4.96; N, 20.14.
3-Phenyl-4-(1 -phenyl-5 -ethyl-1 ,2 ,4 -triazol-3 -yl)-
sydnone (11af) was pre pared in 73% yield (97.2 mg, 2.9
mmol) from a eth a nol so lu tion of 3-phenylsydnone-4-car-
boxamide phenylhydrazone (7a, 118.1 mg, 0.4 mmol) and
propionaldehyde (10f, 185.9 mg, 3.2 mmol) in the pres ence
of sul fu ric acid cat a lyst by a pro ce dure sim i lar to that for
compound11aa.
3-(4 -Methylphenyl)-4-(1 -phenyl-5 -isopropyl-1 ,2 ,4 -
triazol-3 -yl)sydnone (11bg)
White plates from CH3COCH3/EtOH; yield 94%; mp
1
147-148 C; IR (KBr) 1778 ( C=O) cm-1; H NMR (Ac e-
tone-d6), 7.65 (d, J = 8.5 Hz, 2H), 7.56-7.40 (m, 7H), 3.26-
2.97 (m, 1H), 2.46 (s, 3H), 1.12 (d,J = 6.8 Hz, 6H); EIMS (30
eV) m/z (%): 361 (M+, 12), 303 (M+-NO-CO, 100), 91
+
(CH3C6H4 , 12). Anal. Calcd for C20H19N5O2: C, 66.47; H,
3-Phenyl-4-(1 -phenyl-5 -ethyl-1 ,2 ,4 -triazol-3 -yl)sydnone
(11af)
5.30; N, 19.38. Found: C, 66.42; H, 5.34; N, 19.36.
White nee dles from EtOH; yield 73%; mp 212-213 C;
3-(4 -Methoxyphenyl)-4-(1 -phenyl-5 -isopropyl-1 ,2 ,4 -
triazol-3 -yl)sydnone (11cg)
1
IR (KBr) 1766 ( C=O) cm-1; H NMR (DMSO-d6), 7.85-
7.68 (m, 5H), 7.63-7.39 (m, 5H), 2.70 (q, J = 7.5 Hz, 2H),
1.04 (t, J = 7.5 Hz, 3H); EIMS (30 eV)m/z (%): 333 (M+, 13),
White nee dles from CH3COCH3/EtOH; yield 92%; mp
149-150 C; IR (KBr) 1792, 1776 ( C=O) cm-1; 1H NMR
(Acetone-d6), 7.70 (d, J = 9.1 Hz, 2H), 7.62-7.43 (m, 5H),
+
275 (M+-NO-CO, 100), 77 (C6H5 , 25). Anal. Calcd for

3-Arylsydnone-4-carboxamide Phenylhydrazones
J. Chin. Chem. Soc., Vol. 48, No. 5, 2001 891
7.15 (d, J = 9.1 Hz, 2H), 3.91 (s, 3H), 3.27-2.98 (m, 1H), 1.14
(d, J = 6.8 Hz, 6H); EIMS (30 eV) m/z (%): 377 (M+, 7), 319
versityofTechnologyishighlyappreciated.
+
(M+-NO-CO, 100), 107 (CH3OC6H4 , 3). Anal. Calcd for
C20H19N5O3: C, 63.65; H, 5.07; N, 18.56. Found: C, 63.44; H,
5.06; N, 18.49.
Received May 3, 2001.
Key Words
3-Phenyl-4-(1 -phenyl-5 -propyl-1 ,2 ,4 -triazol-3 -yl)-
sydnone (11ah)
Sydnones; Nitrile oxides; Carbohydroximic acid
chlorides; 1,2,4-Triazoles; Carboxamide ox imes;
3-Arylsydnone-4-carboxamide phenylhydrazones;
3-Aryl-4-(1-phenyl-5-substituted-1,2,4-triazol-3-yl)-
sydnones.
YellowneedlesfromCH3COCH3/EtOH; yield 74%; mp
167-168 C; IR (KBr) 1788, 1776 ( C=O) cm-1; 1H NMR
(Acetone-d6), 7.86-7.63 (m, 5H), 7.62-7.42 (m, 5H), 2.71 (t,
J = 7.4 Hz, 2H), 1.78-1.41 (m, 2H), 0.80 (t, J = 7.2 Hz, 3H);
EIMS (30 eV)m/z (%): 347 (M+, 10), 289 (M+-NO-CO, 100),
+
77 (C6H5 , 2). Anal. Calcd for C19H17N5O2: C, 65.70; H, 4.93;
REFERENCES
N, 20.16. Found: C, 65.63; H, 4.96; N, 20.16.
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demic Press: New York, 1969; pp 117-171.
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1967, 4, 160.
3-(4 -Methylphenyl)-4-(1 -phenyl-5 -propyl-1 ,2 ,4 -triazol-
3 -yl)sydnone (11bh)
White plates from CH3COCH3/EtOH; yield 70%; mp
1
145-146 C; IR (KBr) 1762 ( C=O) cm-1; H NMR (Ac e-
tone-d6), 7.66 (d, J = 8.5 Hz, 2H), 7.56-7.41 (m, 7H), 2.72
(t, J = 7.4 Hz, 2H), 2.46 (s, 3H), 1.78-1.44 (m, 2H ), 0.81 (t, J
= 7.0 Hz, 3H); EIMS (30 eV) m/z (%): 361 (M+, 7), 303
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C20H19N5O2: C, 66.47; H, 5.30; N, 19.38. Found: C, 66.46; H,
5.27; N, 19.39.
7. Saito, Y.; Kamitani, T. Ja pan Pat ent 1970, 7021710;
Chem. Abstr . 1970, 73, 87926k.
3-(4 -Methoxyphenyl)-4-(1 -phenyl-5 -propyl-1 ,2 ,4 -
triazol-3 -yl)sydnone (11ch)
8. Masuda, K.; Okutani, T. Ja pan Pat ent1970, 7020903;
Chem. Abstr . 1970, 74, 87928n.
White plates from CH3COCH3/EtOH; yield 86%; mp
169-170 C; IR (KBr) 1790, 1780 ( C=O) cm-1; 1H NMR
(Acetone-d6), 7.71 (d, J = 9.1 Hz, 2H), 7.62-7.45 (m, 5H),
7.16 (d, J = 9.1 Hz, 2H), 3.92 (s, 3H), 2.73 (t,J = 7.4 Hz, 2H),
1.76-1.39 (m, 2H), 0.82 (t,J = 7.2 Hz, 3H); EIMS (30 eV)m/z
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+
(%): 377 (M+, 5), 319 (M+-NO-CO, 100), 107 (CH3OC6H4 ,
1). Anal. Calcd for C20H19N5O3: C, 63.65; H, 5.07; N, 18.56.
Found: C, 63.44; H, 5.06; N, 18.49.
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Crystallography
Crys tal data for com pound 11ca are sum ma rized in Ta-
ble 1. Se lected bond dis tances and bond an gles are listed in
Ta ble 2 and Ta ble 3, re spec tively. Atomic co or di nates are
giveninTable4.
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Marsico, J. W.; Press, J. B.; Tauber, J.; Tomcufcik, A. S.
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ACKNOWLEDGMENT
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Nakai, A.; Ogawa, K.; Spevak, P.; Tanaka, M.; Yamabe,
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Fi nan cial sup port of this work by the Na tional Sci ence
Coun cil of the Re pub lic of China and South ern Tai wan Uni-

892 J. Chin. Chem. Soc., Vol. 48, No. 5, 2001
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