The reaction studies of α-chloroformylarylhydrazines with thiols, thioureas and α-cyclodiketones

Article abstract of DOI:10.1002/jccs.200100036

The reactions of α-chloroformylarylhydrazines 1 with various types of mercaptan, thiourea and α-cyclodiketone have been studied intensively. 1-Arylhydrazinecarbothioates 2 were obtained via thioesterization when α-chloroformylarylhydrazines reacted with thiols. On the other hand, compounds 3 were obtained when α-chloroformylarylhydrazines reacted with thio-containing heterocyclic compounds, which suggested a totally different mechanism in these types of reactions. Further studies on the reaction of α-chloroformylarylhydrazines 1 with thiourea compounds confirmed a novel cyclization and de-cyclization mechanism, which led to give 2-arylhydrazinecarboximidamides 5 and 1,3,4-thiadiazolin-5-ones 6. In addition, various 1,3,4-oxadiazines 9 were obtained by reacting α-chloroformylarylhydrazines with α-cyclodiketones, showing ring cyclization was involved in this type of reaction.

Full text of DOI:10.1002/jccs.200100036

JournaloftheChineseChemicalSociety, 2001, 48, 215-228
215
The Re ac tion Studies of -Chloroformylarylhydrazines with Thiols,
Thioureas and -Cyclodiketones
Wen-Fa Kuoa (
), Ming-Shyue Wua (
),
Chun-Yen Chiub (
) and Mou-Yung Yeh*a (
)
aDepartmentofChemistry,NationalChengKungUniversity,Tainan,Taiwan70101,R.O.C.
bDepartmentofEnvironmentalEngineeringandHealth,TajenInstituteofTechnology,PingTung 907, R.O.C.
The re ac tions of -chloroformylarylhydrazines 1 with var i ous types of mercaptan, thiourea and
-
cyclodiketone have been stud ied in ten sively. 1-Arylhydrazinecarbothioates 2 were obtained via thio-
esterization when -chloroformylarylhydrazines re acted with thiols. On the other hand, com pounds 3 were
ob tained when -chloroformylarylhydrazines re acted with thio-containing heterocyclic com pounds, which
sug gested a to tally dif fer ent mech a nism in these types of re ac tions. Fur ther stud ies on the re ac tion of
-
chloroformylarylhydrazines1 with thiourea com pounds con firmed a novel cyclization and de-cyclization
mech a nism, which led to give 2-arylhydrazinecarboximidamides 5 and 1,3,4-thiadiazolin-5-ones 6. In ad di-
tion, var i ous 1,3,4-oxadiazines 9 were ob tained by re act ing -chloroformylarylhydrazines with -cyclo-
diketones, show ing ring cyclization was in volved in this type of re ac tion.
INTRODUCTION
-Chloroformylarylhydrazines 1 andtheirderivatives
The syn thetic meth ods for pre par ing 2-arylhydrazine-
carboximidamide type com pounds, such as com pounds5,4,5
and 1,3,4-thiadiazolin-5-one type com pounds, such as com-
pounds 6,6,7 havebeenreportedearlier.Andthederivativesof
compounds5havebeenknowntopossessseveralbiological
andpharmacologicalactivities.8-10 Fur ther study of com-
pounds 1 in this re port has led to a better and new syn thetic
route to these two types com pounds by re act ing with thio-
ureas.
The syn the sis of 1,3,4-oxadiazine type com pounds,
compounds 9, have been re ported11,12 and found to pos sess
potentialmonoamineoxidaseinhibitoractivity.13 Our study
inthisreportbyreactingcompounds1 with -cyclodiketones
8 has led to a better method to pre pare this type of com pound
anditsderivatives.Thedetaileddiscussionsofvariousreac-
tions based on com pounds 1 arepresentedherein.
are potent precursors for preparing heterocyclic com-
pounds.1-2 The nucleophilic sub sti tu tion re ac tion of com-
pounds 1withalcohols1 and amines3 has been re ported in our
pre vi ous stud ies. Since com pounds1 can un dergo nucleo-
philic substitutionreactions with potent nucleophilic re-
agents, it is worth us ing com pounds 1 as synthons to ex plore
fur ther. In this study by us ing thiols as nucleophiles, it is
found that when compounds 1 react with butylthiol and
thiophenol, prod ucts 2 (a substitutional prod uct) were ob-
tained (Scheme I); however, when reacting with thio-
containing heterocyclic com pounds, such as com pounds 11,
theexpectedproducts(compounds2 ) were not ob served. In-
stead, com pounds 3 (Scheme II) were ob tained, which re-
veals that re ac tion stud ies on the com pounds 1with var i ous
mercaptansareofimportanceandofinterest.
RESULTS AND DISCUSSION
Scheme I
The prep a ra tion of 1-arylhydrazinecarboxylate hy dro-
chlorides 10 were easily accomplished by re act ing com-
pounds 1with alkyl al co hols.1 Ex tended syn thetic work by
us ing thiols and thiophenols, in stead of al co hol, were stud-
ied. As shown in Scheme I, 1-arylhydrazinecarbothioates2, a
di rect substitutional prod uct, were ob tained with high yields.
Basedonspectralanalysis,compounds 2 were not found in
the state of a hy dro chlo ride salt, which is dif fer ent from the
O
HS
R
Ar
Ar
N
C
SR
2
O
C
R = Alkyl, Aryl
NH2
Ar
N
Cl
NH2
HCl
O
C
R
HO
N
OR
1
10
R = Alkyl
NH2 HCl

216 J. Chin. Chem. Soc., Vol. 48, No. 2, 2001
Kuo et al.
Scheme II
N
S
11c
HS
HS
N
S
Ar NH NH
HCl
O
3f - 3h
Ar
N
C
Cl
HCl
NH2
N
O
C
N
Ar
N
S
1
X
X
NH2
11a
X = S
2'
11b X = NH
H
N
O
S
arylhydrazine
N
11a, 11b
Ar NH NH
N
X
N
X
Ar
H
3a, 3b X = S
7
3c ,
,
3d 3e X = NH HCl
prod uct ob tained when the nucleophile is alkyl al co hol, in
which hy dro chlo ride salt of the com pounds were ob tained.1
One pos si ble ex pla na tion is that alkoxy groups would better
con ju gate with a car bonyl group than alkylthiol groups and
thus re sult in a high elec tronic den sity borne by amino ni tro-
gen to form a salt with hy dro chlo ride. Ta ble 1 shows com-
pounds, 2a~2f, ob tained from var i ous thiols re act ing with
compounds 1. However, some reactions did not proceed
when nucleophilic re agents were phe nols (Scheme I). These
resultsshowthatmercaptanspossessabetternucleophilicef-
fect than alkoxy groups.
by substitution reaction through the exchange between
arylhydrazine and the sulhydryl moi ety of com pound 11a, re-
actionsofcompounds1 with arylhydrazines were car ried out
un der the same con di tion; nev er the less, no com pounds 3
wereobserved. Thepossiblemechanismforthistypeofreac-
tion is pro posed as de scribed in Scheme II, i.e. a nucleophilic
substitutionreactiontakesplacefirstfollowedbycyclization
thus re sult ing in the for ma tion of in ter me di ate7, which is
thenfollowedbyeliminationofS=C=Otogivecompounds3.
The same re sults were formed in the re ac tions of 2- mercapto-
benzimidazole 11b and 2-mercaptothiazoline 11c with com-
pounds 1. The yields are sum ma rized in Ta ble 2.
Inordertoexaminewhetherthereactionmechanismas
shown in Scheme II is ap pli ca ble in the thiourea type of com-
pounds, thioureas 4were used to re act with com pounds 1 un-
der the same con di tion (Scheme III) and we have ob tained the
ex pected prod ucts, 2-arylhydrazinecarboximidamides 5 and
4-aryl-2-amino-1,3,4-thiadiazolin-5-ones 6, showing the
proposedreactionmechanism(SchemeII)isplausible.Inthe
Fur ther study of thiols re act ing with com pounds1 has
been ex tended to more com pli cated com pounds, such as 2-
mercaptobenzothiazole11a. The ex pected prod ucts, 1- aryl-
hydrazinecarbothioates 2 , a prod uct ob tained through a di-
rectnucleophilicsubstitutionreaction, did not form (Scheme
II). In stead, com pounds 3 were ob tained show ing a more
complicatedreactionthanjustasimplesubstitutionone. In
ordertofindoutwhetherthisproductcanbeobtaineddirectly
Table 1. Preparation of Compounds 2 from Compounds 1 with Thiols
Compound Ar Reaction time (hr)
2a
R
Yield (%)
C6H5
n-C4H9
1
88
78
95
74
68
65
2b
2c
2d
2e
2f
p-CH3C6H4
p-ClC6H4
C6H5
p-CH3C6H4
p-ClC6H4
n-C4H9
n-C4H9
C6H5
C6H5
C6H5
1
1
5
5
5

-Chloroformylarylhydrazines with Thioureas
J. Chin. Chem. Soc., Vol. 48, No. 2, 2001 217
Table 2. Preparation of Compounds 3 from Compounds 1
Reacted with Compounds 11
Scheme III
O
C
Compound
Ar
Reaction time (hr) Yield (%)
O
C
S
NHR Cl
NHR
Ar
N
Cl
Ar
N
S
C
3a
3b
3c
3d
3e
3f
p-CH3C6H4
p-ClC6H4
C6H5
p-CH3C6H4
p-ClC6H4
C6H5
1
1
36
34
76
70
62
53
30
30
RHN
C
NHR
NH2 HCl
NH2
4a R = H
0.5
0.5
0.5
4
1
4b
4c
R = CH3
R = ph
O
O
3g
3h
p-CH3C6H4
p-ClC6H4
4
4
Ar
Ar
N
S
-
N
S
HCl
Cl
+ HCl
N
NH2R
NHR
N
NHR
H
H
NR
H
re ac tions of com pounds1 with thiourea 4a, 1,3- dimethyl-
thiourea 4b, and diphenylthiourea 4c (Scheme III), com-
pounds 5a~5h were the ma jor prod ucts (40~60%) ob tained
throughtheeliminationofS=C=Oaftercyclization,whereas
compounds6a~6h were the mi nor prod ucts (10~20%) ob-
tained through deaminonation after cyclization. Further
study shows that for the reactions of N,N-tetra methyl-
thiourea 4d with com pounds 1, the step of S=C=O elim i na-
tion (Scheme IV, path a) did not proceed; however, the
deamination step was ob served to give com pounds6 (6i~6k)
(Scheme IV, path b). One pos si ble ex pla na tion is that pro-
tonation on the elec tron-rich dimethylamino group pre vailed
and the large steric ef fects be tween the two dimethylamino
groups re sulted in the elim i na tion of the dimethylamino
-
HCl
NH2R
-
HCl COS
O
NR
Ar
N
S
Ar NH
NH C NHR
HCl
N
NHR
6a - 6h
5a - 5h
group to give com pounds 6 ( 6i~6k),insteadofeliminationof
S=C=O to give the more un sta ble com pounds 5i~5k.
In the re ac tions of 1-methylthiourea 4e (Scheme V)
with com pounds1, elim i na tion of S=C=O (Scheme VI, path
Scheme IV
path (a)
5i - 5k
O
(a)
S
C
Ar
(a)
O
N
S
+ Me2N
NMe2
1
Ar
N
NHMe2
N
S
4d
(b)
H
path (b)
6i -6k
NMe2
N
NMe2
Scheme V
NH HCl
path (a)
path (b)
Ar NH
Ar
C
NH
N
NHMe 5l - 5m
O
O
(a)
Ar
S
(a)
S
N
S
+ H
+
1
H2N
NHMe
C
N
(b,c)
N
NHMe
NHMe
4e
(C)
O
H
(a)
N
(b)
Ar
path (c)
H
H
N
S
6l - 6m
N
NH2

218 J. Chin. Chem. Soc., Vol. 48, No. 2, 2001
Kuo et al.
Scheme VI
path (a)
path (b)
5n - 5p
O
(a)
(a)
S
Ar
O
+ H
N
S
(b)
1
HN
NH
+
H
Ar
(b)
N
N
N
S
H
6n -6p
N
H
4f
H
N
(a)
NHCH2CH2NH2
HCl
Table 3. Preparation of Compounds 5 and 6 from Compounds 1 Reacted with Compounds 4
Starting
Material
Ar
Reaction
Time (hr)
Comp’d 5
Yield (%)
Comp’d 6
Yield (%)
4a
4a
4a
4b
4b
4b
4c
4c
4d
4d
4d
4e
4e
4f
Ph
10
8
9
5
5
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
44
49
41
60
66
68
58
52
-
-
-
24
17
-
6a
6b
6c
6d
6e
6f
6g
6h
6i
15
13
20
15
20
12
12
10
27
20
45
16
20
31
33
24
p-MeC6H4
p-ClC6H4
Ph
p-MeC6H4
p-ClC6H4
p-MeC6H4
p-ClC6H4
Ph
p-MeC6H4
p-ClC6H4
Ph
p-ClC6H4
Ph
6
48
48
48
48
24
4
6j
6k
6l = 6a
6m = 6c
6n
6o
6p
3
20
24
14
4f
4f
p-MeC6H4
p-ClC6H4
-
-
a) gives N-methyl-2-arylhydrazinecarboximidamide 5 (5l,
5m). In the step of deamination, only com pounds 6 (6l, 6m)
(through path c), not the com pounds through path b, were ob-
tained, show ing that the methylamino group is more likely to
give protonation than the amino group, then to be elim i nated.
This is ex plain able since the methylamino group bears a
higher elec tron den sity than the amino group. In ad di tion,
compounds 1 re acted with ethylenethiourea 4f to give 2-
( -aminoethyl)amino-1,3,4-thiadiazolin-5-ones 6 (6n~ 6p)
as the only prod ucts (Scheme VI). The struc tures of com-
pounds 5 were con firmed by X-ray crys tal log ra phy. Fig. 1
and Ta ble 5, 6, 7 and 8 are the X-ray struc ture and var i ous
spec tral data of com pound 5d. The re ac tion yields of these
typesreactionsaresummarizedinTable3.
Table 4. Preparation of Compounds 9 from Compounds 1
Reacted with Compounds 8
Starting
material
Ar
Reaction
time (hr)
Compound 9 Yield (%)
8a
8a
8b
8b
8b
8c
8c
8c
8d
8d
8d
8e
8e
8e
Ph
p-ClC6H4
Ph
p-MeC6H4
p-ClC6H4
Ph
p-MeC6H4
p-ClC6H4
Ph
p-MeC6H4
p-ClC6H4
Ph
p-MeC6H4
p-ClC6H4
3
3
1
1
1
2
3
3
4
4
4
5
5
5
9a
9b
9c
9d
9e
9f
9g
9h
9i
9j
9k
9l
9m
9n
21
17
61
60
62
36
44
44
80
72
68
70
68
79
Thereactionsofcompounds1 with -cyclodiketones 8
to form compounds 9 are well understood. The reaction
mechanismisasfollows:nucleophilicadditionofnitrogenof

-Chloroformylarylhydrazines with Thioureas
J. Chin. Chem. Soc., Vol. 48, No. 2, 2001 219
Table 5. Crystal Data of 5d
Table 6. Bond Distances/Å of 5d
Formula
C9H15ClN4
Cl-H(N2)(a)
Cl-H(N4)
2.1846(10)
2.1280(10)
1.419(4)
1.403(5)
0.962(3)
1.349(5)
1.029(3)
1.326(5)
1.455(5)
1.040(3)
1.319(5)
1.449(5)
1.070(3)
1.081(4)
1.093(4)
1.092(4)
C(3)-H(3)
C(3)-H(3’)
1.097(4)
1.099(4)
1.081(4)
1.378(6)
1.396(5)
1.370(6)
1.080(4)
1.376(6)
1.081(5)
1.372(7)
1.081(4)
1.384(6)
1.080(4)
1.081(4)
2.1846(10)
Formula weight
Cryst system
Space group
a/Å
214.70
Orthorhombic
P cab
9.7956 (16)
12.8591 (21)
18.059 (4)
2274.8 (7)
8
N(1)-N(2)
N(1)-C(1A)
N(1)-H(N1)
N(2)-C(1)
N(2)-H(N2)
N(3)-C(1)
N(3)-C(2)
N(3)-H(N3)
N(4)-C(1)
N(4)-C(3)
N(4)-H(N4)
C(2)-H(2)
C(2)-H(2’)
C(2)-H(2’’)
C(3)-H(3’’)
C(1A)-C(2A)
C(1A)-C(6A)
C(2A)-C(3A)
C(2A)-H(2A)
C(3A)-C(4A)
C(3A)-H(3A)
C(4A)-C(5A)
C(4A)-H(4A)
C(5A)-C(6A)
C(5A)-H(5A)
C(6A)-H(6A)
H(N2)-Cl(b)
b/Å
c/Å
V/Å3
Z
Dc/g cm3
F000
1.254
911.77
0.70930
0.30
23.26-24.44
2
(Mo-K ) Å
/cm-1
Range/deg
Scan type
2
49.8
max
Reflections measured
Unique reflections
Observed reflections
Refined parameters
Rf for significant reflections
Rw for significant reflections
GoF
1993
1993
1287
127
0.048
0.046
2.92
Scheme VII
(a)
O
C
O
C
O
O
Ar
Ar
Ar
Cl
N
N
N
Cl
O
O
O
N
N
N
OH
1
+
amine to car bonyl car bon, then loss of wa ter to form imine to-
gether with a nucleophlic sub sti tu tion of the chlo ride by
hydroxyl group (see Scheme VII). The re ac tion yields for
these types of re ac tions are gen er ally high and are shown in
Ta ble 4. As for the re ac tion yield of 9a and9b, in which R1 is
H, are lower than av er age, which can be at trib uted to a com-
parativehydrolysistakingplacefromintermediate12, be-
cause com pounds13 (2-arylhydrazino-1-cyclohexanones)
R1
Y
R1
Y
R1
Y
12
8
R1
Y
9a ~ 9h
H2O
8a
= CH CH R1 = H
2 2
Y
Y
= CH2 R1 = CH3
8b
8c
Ar
H
N
Y = CH2
R1 = CH2CH3
O
N
= CH CH
Y
2
2
13
R1 = H
R1
24 %
Y
(b)
Ar
O
O
O
OH
N
1
+
N
9i ~ 9n
R2
O
R2
O
8d R2 = CH3
8e
R2 = Ph
were ob tained. In or der to im prove the re ac tion yields of
compounds 9, in which R1 is H, var i ous alkyl type sub stitu-
ents were in tro duced into -cyclodiketones, with which enol
for ma tion is in creased to in crease the cyclization through
nucleophlic sub sti tu tion of the chlo ride by the hydroxyl
group to give com pounds 9. With this, it is also found that the
yieldsofsideproducts, compounds13, were re duced to about
5%. We also used com pounds 1 to re act with 4-hydroxy- 5-
Fig. 1. Molecular structure of N,N’-Dimethyl-2-
phenylhydrazinecarboximidamide hy dro-
chloride(5d).

220 J. Chin. Chem. Soc., Vol. 48, No. 2, 2001
Table 7. Bond Angles/deg of 5d
Kuo et al.
H(N2)(a)-Cl-H(N4)
N(2)-N(1)-C(1A)
N(2)-N(1)-H(N1)
C(1A)-N(1)-H(N2)
N(1)-N(2)-C(1)
N(1)-N(2)-H(N2)
C(1)-N(2)-H(N2)
C(1)-N(3)-C(2)
C(1)-N(3)-H(N3)
C(2)-N(3)-H(N3)
C(1)-N(4)-C(3)
C(1)-N(4)-H(N4)
C(3)-N(4)-H(N4)
N(2)-C(1)-N(3)
N(2)-C(1)-N(4)
N(3)-C(1)-N(4)
N(3)-C(2)-H(2)
N(3)-C(2)-H(2’)
N(3)-C(2)-H(2’’)
H(2)-C(2)-H(2’)
H(2)-C(2)-H(2’’)
H(2’)-C(2)-H(2’’)
N(4)-C(3)-H(3)
C(4)-C(3)-C(3’)
125.03(5)
N(4)-C(3)-H(3’’)
H(3)-C(3)-H(3’)
H(3)-C(3)-H(3’’)
108.1(3)
106.8(3)
110.0(4)
109.8(4)
123.8(3)
117.1(4)
119.1(4)
120.3(4)
119.9(4)
119.8(4)
121.2(4)
119.3(4)
119.5(4)
118.8(4)
120.4(5)
120.8(4)
121.1(4)
119.4(4)
119.5(4)
119.4(4)
120.3(4)
120.3(4)
163.56(17)
152.11(16)
115.5(3)
107.9(3)
118.8(3)
117.5(3)
118.4(3)
122.2(3)
123.8(3)
114.0(3)
121.7(3)
125.3(3)
117.9(3)
116.8(3)
119.2(3)
119.3(3)
121.5(3)
110.4(3)
109.7(3)
107.7(3)
108.4(3)
110.8(3)
109.8(4)
111.0(3)
111.0(3)
H(3’)-C(3)-H(3’’)
N(1)-C(1A)-C(2A)
N(1)-C(1A)-C(6A)
C(2A)-C(1A)-C(6A)
C(1A)-C(2A)-C(3A)
C(1A)-C(2A)-H(2A)
C(3A)-C(2A)-H(2A)
C(2A)-C(3A)-C(4A)
C(2A)-C(3A)-H(3A)
C(4A)-C(3A)-H(3A)
C(3A)-C(4A)-C(5A)
C(3A)-C(4A)-H(4A)
C(5A)-C(4A)-H(4A)
C(4A)-C(5A)-C(6A)
C(4A)-C(5A)-H(5A)
C(6A)-C(5A)-H(5A)
C(1A)-C(6A)-C(5A)
C(1A)-C(6A)-H(6A)
C(5A)-C(6A)-H(6A)
Cl(b)-H(N2)-N(2)
Cl-H(N4)-N(4)
CONCLUSION
Scheme VIII
Four heterocyclic com pounds, 3, 5, 6 and 9 have been
syn the sized by the re ac tions of -chloroformylaryl hydra-
zines hy dro chlor ides 1 with thiol, thioureas and -cyclo-
diketone,respectively.Theseresultsmanifestthatwhencom-
pounds 1re acted with sul fur-containing re agents, which pos-
sessed ei ther a N=C-S or a N-C=S frag ment, they would pro-
ceed through more com pli cated re ac tion routes in clud ing
nucleophilicsubstitution,cyclization,andeliminationreac-
tions, lead ing to the for ma tion of prod ucts 5 and 6. In the re-
ac tions of com pounds 1 with -cyclodiketone, the 1,3,4-
oxdiazinetypecompounds9were ob tained through a sim ple
condensationandsubstitutionreaction.Theseresultsreveal
that one of the car bonyl groups in -cyclodiketoneundergoes
enolizationbeforeproceedingtothesubstitutionreaction.
We have shown that when -alkylated -cyclodiketones,
whichhaveahigherpotentialtoundergoenolization, reacted
with com pounds 1, it leads to a higher re ac tion yield of com-
pounds 9.However, - and -dialkylated -cyclodiketones
undergoenolizationtoformamorestablearomatictypecom-
poundasnoreactiontakesplace. Also, themethodswedevel-
opedtopreparecompounds 5, 6, and 9 andtheirderivatives
are better meth ods when com pared with those pre vi ously re-
ported.4-7,11-13
O
OH
O
O
OH
Ar
N
C Cl
+
or
9
Ph
Ph
S
CH3
O
H3C
NH2 HCl
O
O
15
14
1
HO
OH
HO
OH
dimer
Ph
Ph
S
CH3
H3C
O
O
O
substituted-4-cyclopentene-1,3-diones,compounds 8d and
8e, anenolformtypecompound(SchemeVII, b). Thesereac-
tions do ob vi ously in crease the re ac tion yield. As shown in
Ta ble 4 prod ucts9i~9n have a yield in the range of 68%~
80%, whereas it is in the range of 17%~62% for prod ucts
9a~9e. How ever, when 2,5-dimethyl-4-hydroxy-3-furanone,
14, and 4-hydroxy-2,5-diphenyl-3(2H)-thiophenone-1,1-
dioxide, 15, were used to re act with com pounds1, the ex-
pected prod ucts, 1,3,4-oxadiazine type of prod uct9 were not
ob served. In stead, the self-dimerization of com pounds1 re-
ac tion was ob served. This is be cause com pound14 un der-
goes enolization to be come a more sta ble ar o matic type com-
poundresultinginnoreactiontakingplace(SchemeVIII).

-Chloroformylarylhydrazines with Thioureas
J. Chin. Chem. Soc., Vol. 48, No. 2, 2001 221
Table 8. Atomic Coordinates of 5d
gel packed open col umn (Kieselgel 100, 230-400 mesh, E.
Merck).
Atom
X
Y
Z
Cl
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(1A)
C(2A)
C(3A)
C(4A)
C(5A)
C(6A)
H(N1)
H(N2)
H(N3)
H(N4)
H(2)
0.11944
0.06848
0.15245
-0.02154
0.17182
0.10013
-0.08037
0.30996
0.13144
0.23793
0.29045
0.24029
0.13378
0.07907
0.01833
0.23750
-0.06681
0.12303
-0.10369
-0.00750
-0.17272
0.31320
0.37718
0.34664
0.28025
0.37263
0.28459
0.09165
-0.00343
0.26250
(0.500-X)
0.38056
(0.500-X)
0.29382
-0.19899
-0.11596
-0.00467
0.05950
-0.01903
0.09718
0.05263
-0.27069
-0.24602
-0.31941
-0.41933
-0.44428
-0.37162
-0.22465
-0.13340
-0.07257
0.13377
0.13641
0.14468
0.08562
0.00769
0.01274
0.13073
-0.16847
-0.29818
-0.47707
-0.52186
-0.39281
0.36660
(0.500 + Y)
-0.20672
(-0.500 + Y)
0.02494*
0.10746
0.08289
0.11675
0.05982
0.08618
0.13138
0.03151
0.15501
0.20170
0.24872
0.24982
0.20380
0.15569
0.06543
0.05179*
0.13609
0.05625
0.08000
0.16234
0.16422
-0.02008
0.07113
0.02184
0.20121
0.28572
0.28614
0.20535
0.11891
0.05179
(-Z)
Preparation of 1-arylhydrazine carbonylthioate 2a~2f
0.3 g (1.45 mmol) of -chloroformylphenylhydrazine
hydrochloride1 in 5 mL of EtOH was added to 0.2 mL of
butylthiol(orthiophenol). Thereactionmixturewasstirredat
roomtemperature.Afterabout1hr,thereactionmixturewas
poured into ice wa ter, then was stirred for 10 min. The pre cip-
i ta tion was fil tered, then recrystallized with 95% EtOH to
give 0.29 g of com pound 2a (88%).Thephysicalproperties
andspectroscopicdataofcompounds2 are as fol lows:
S-Butyl 1-phenylhydrazinecarbothioate (2a)
Colorlessneedles;mp58~59 C, IR (KBr): 3358, 3286,
3058, 2950, 2926, 2896, 2866, 1620 cm-1; 1H NMR, = 0.81~
0.96 (m, 3H), 1.27~1.61 (m, 4H), 2.68 (t, J = 7.0 Hz, 2H),
5.57 (s, 2H), 7.08~7.66 (m, 5H). 13C NMR (DMSO-d6):
=
171.5, 143.8, 128.8, 125.3, 122.2, 32.1, 29.6, 21.9, 13.9.
EIMS (70 eV),m/z (%): 224 (M+, 60), 135 (14), 107 (100), 77
(34). Anal. Calcd. for C11H16N2OS: C: 58.90, H: 7.12, N:
12.29, S: 14.29. found C: 58.96, H: 7.17, N: 12.33, S: 14.26.
H(2’)
H(2’’)
H(3)
H(3’)
H(3’’)
H(2A)
H(3A)
H(4A)
H(5A)
H(6A)
H(N2)(a)
S-Butyl 1-(4-methylphenyl)hydrazinecarbothioate (2b)
Colorlessneedles;mp75~76 C, IR (KBr): 3358, 3280,
1
2956, 2920, 2866, 1662 cm-1; H NMR, = 0.79~0.94 (m,
3H), 1.25~1.61 (m, 4H), 2.27 (s, 3H), 2.61 (t, J = 7.1 Hz, 2H),
5.50 (s, 2H), 7.15 (d, J = 8.4 Hz, 2H), 7.45 (d,J = 8.4 Hz, 2H).
EIMS (70 eV), m/z (%): 238 (M+, 42), 222 (5), 149 (6), 121
(100), 91 (24). Anal. Calcd. for C12H18N2OS: C: 60.47, H:
7.60, N: 11.75, S: 13.45. found C: 60.50, H: 7.61, N: 11.74, S:
13.48.
Cl(b)
0.02494
(-Z)
*Indicates that there are Symmetry Equivalents of an atom.
H(N2)(a) and Cl(b) are the Symmetry Equivalents.
S-Butyl 1-(4-chlorophenyl)hydrazinecarbothioate (2c)
Colorlessneedles;mp70~71 C, IR (KBr): 3346, 3280,
3220, 2962, 2926, 2866, 1650 cm-1; 1H NMR, = 0.82~0.96
(m, 3H), 1.33~1.53 (m, 4H), 2.86 (t, J = 7.0 Hz, 2H), 5.61 (s,
2H), 7.42 (d, J = 9.1 Hz, 2H), 7.65 (d, J = 9.1 Hz, 2H). EIMS
(70 eV), m/z (%): 260 (M++2, 7), 258 (M+, 20), 169 (3), 141
(100), 111 (8). Anal. Calcd. for C11H15ClN2OS: C: 51.06, H:
5.84, N: 10.83, Cl: 13.70, S: 12.39. found C: 50.91, H: 5.85,
N: 10.82, Cl: 13.68, S: 12.36.
EXPERIMENTALSECTION
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-
trom e ter. NMR spec tra were mea sured on a Bruker AMX-
200 NMR spec trom e ter with tetramethylsilane (TMS) as in-
ter nal stan dard and the 1H NMR spec tra were mea sured in
DMSO-d6 for all sam ples. The mass spec tra were mea sured
onaFinniganMATTSQ-46Cspectrometeratanionizingpo-
tential of 70 eV. Elemental analyses were performed on
Heraeus CHN-O-Rapid and Tacussel Coulomax 78 an a lyz-
ers. X-rayanalysiswasmadewithaNoniusCAD-4diffracto-
meter. Columnchromatographywascarriedoutwithasilica
S-Phenyl 1-phenylhydrazinecarbothioate (2d)
Col or less nee dles; mp 121~122 C, IR (KBr): 3358,
3286, 3058, 1662 cm-1; 1H NMR, = 5.79 (br, 2H), 7.14~7.64
(m, 10H). 13C NMR (DMSO-d6): = 169.8, 143.5, 135.6,
132.0, 129.1, 129.0, 128.9, 125.4, 121.9. EIMS (70 eV), m/z
(%): 244 (M+, 100), 135 (15), 107 (98), 77 (75). Anal. Calcd.

222 J. Chin. Chem. Soc., Vol. 48, No. 2, 2001
Kuo et al.
for C 13H12N2OS: C: 63.91, H: 4.95, N: 11.47, S: 13.12. found
C: 63.74, H: 4.94, N: 11.53, S: 13.15.
146.3, 130.6, 129.8, 128.8, 126.0, 121.6, 121.4, 118.8, 113.1,
20.6. EIMS (70 eV), m/z (%): 225 (M+, 100), 239 (11), 222
(19), 150 (48), 149 (20), 106 (97), 91 (29), 77 (42). Anal.
Calcd. for C14H13N3S: C: 65.85, H: 5.13, N: 16.46, S: 12.56.
found C: 65.84, H: 5.19, N: 16.39, S: 12.51.
S-Phenyl 1-(4-methylphenyl)hydrazinecarbothioate (2e)
Colorlessneedles;mp75~76 C, IR (KBr): 3352, 3286,
1662 cm-1 ; 1H NMR, = 2.27 (s, 3H), 5.71 (s, 2H), 7.15 (d,J =
8.5 Hz, 2H), 7.33~7.51 (m, 5H), 7.47 (d, J = 8.5 Hz, 2H).
EIMS (70 eV),m/z (%): 258 (M+, 58), 149 (15), 121 (100), 91
(54), 77 (48). Anal. Calcd. for C14H14N2OS: C: 65.09, H:
5.46, N: 10.84, S: 12.41. found C: 64.95, H: 5.45, N: 10.82, S:
12.39.
2-[2-(4-Chlorophenyl)hydrazino]benzothiazole (3b)
Pale or ange nee dles; mp 247~248 C, IR (KBr): 3292,
1
3076~2830 cm-1; H NMR, = 6.81 (d, J = 8.8 Hz, 2H),
7.01~7.71 (m, 4H), 7.22 (d,J = 8.8 Hz, 2H), 8.60 (s, 1H), 9.87
(s, 1H). EIMS (70 eV), m/z (%): 277 (M++2, 35), 275 (M+,
100), 259 (8), 242 (19), 150 (44), 149 (84), 129 (20), 127
(59), 113 (12), 111 (43). Anal. Calcd. for C13H10ClN3S: C:
56.62, H: 3.65, N: 15.24, Cl: 12.86, S: 11.63. found C: 56.62,
H: 3.68, N: 15.14, Cl: 12.88, S: 11.62.
S-Phenyl 1-(4-chlorophenyl)hydrazinecarbothioate (2f)
Col or less nee dles; mp 151~152 C, IR (KBr): 3358,
3238, 1653 cm-1; 1H NMR, = 5.83 (s, 2H), 7.38~7.49 (m,
5H), 7.42 (d, J = 9.1 Hz, 2H), 7.65 (d, J = 9.1 Hz, 2H). EIMS
(70 eV),m/z (%): 280 (M++2, 15), 278 (M+, 40), 141 (100), 77
(37). Anal. Calcd. for C13H11ClN2OS: C: 56.01, H: 3.98, N:
10.05, Cl: 12.72, S: 11.50. found C: 55.97, H: 3.96, N: 10.00,
Cl: 12.70, S: 11.49.
2-(2-Phenylhydrazinobenzimidazole hydrochloride(3c)
Pale yel low nee dles; mp 234~235 C, IR (KBr): 3262~
2908 cm-1; 1H NMR, = 6.37~6.47 (m, 3H), 6.75~6.82 (m,
4H), 6.91~6.95 (m, 2H), 8.67 (s, 1H), 11.67 (s, 1H), 13.18 (br,
2H). EIMS (70 eV), m/z (%): 224 (M+, 100), 208 (6), 194 (5),
193 (22), 150 (12), 133 (49), 132 (78), 105 (46), 93 (98), 91
(21), 77 (49). Anal. Calcd. for C13H13ClN4: C: 59.89, H: 5.03,
N: 21.49, Cl: 13.60. found C: 59.82, H: 5.04, N: 21.39, Cl:
13.61.
The preparation of compounds 3a~3h
0.3 g (1.45 mmol) of com pounds 1 in 8 mL of i-PrOH
was added to 0.24 g (1.45 mmol) of 2-mercaptobenzothiazole
11a.Thereactionmixturewasstirredat80 C for 1 hr. The re-
ac tion sol vent was re moved by vac uum, then 10 mL of ac e-
tone was added and was stirred for an other 10 min. The pre-
cip i ta tion was fil tered and crys tal lized with EtOH to give
0.133 g of com pound3a(36%). For the prep a ra tion of com-
pounds 3c~3e, 2-mercaptobenzimidazole 11bwas used to re-
act with com pounds 1at the same re ac tion con di tion for 0.5
hr.Thecrudeproductobtainedbydirectfiltrationwasfurther
crys tal lized with EtOH to give pure prod ucts 3c~3e.
2-[2-(4-Methylphenyl)hydrazino]benzimidazole hy dro-
chlo ride (3d)
Pale yel low nee dles; mp 211~212 C, IR (KBr): 3260~
2914 cm-1; 1H NMR, = 2.21 (s, 3H), 6.81 (d,J = 8.3 Hz, 2H),
7.06 (d, J = 8.3 Hz, 2H), 7.22~7.28 (m, 2H), 7.34~7.40 (m,
2H), 8.48 (s, 1H), 11.05 (s, 1H), 13.11 (br, 2H). EIMS (70
eV), m/z (%): 238 (M+, 83), 222 (20), 208 (13), 207 (42), 150
(7), 133 (7), 132 (67), 107 (100), 91 (61), 77 (46). Anal.
Calcd. for C 14H15ClN4: C: 61.20, H: 5.50, N: 20.39, Cl: 12.90.
found C: 61.17, H: 5.55, N: 20.45, Cl: 12.94.
The preparation of compounds 3f~3h were as follows:
Compounds 1 (0.3 g, 1.45 mmol) in 8 mL of 1,4-
dioxane were added to 0.17 g (1.45 mmol) of 2-mercapto-
thiazoline 11c. The re ac tion mix ture was stirred at 100 C for
4hr.Thecrudeproductthatprecipitatedoutaftercoolingwas
collectedbydirectfiltration,thenwascrystallizedwithEtOH
to give pure com pounds 3f~3h.Thephysicalpropertiesand
spectroscopicdataareasfollowing:
2-[2-(4-Chlorophenyl)hydrazino]benzimidazole hydro-
chlo ride (3e)
Col or less nee dles; mp 228~229 C, IR (KBr): 3250~
2908 cm-1; 1H NMR, = 6.93 (d, J = 8.8 Hz, 2H), 7.21~7.30
(m, 2H), 7.26 (d,J = 8.8 Hz, 2H), 7.36~7.41 (m, 2H), 8.87 (s,
1H), 11.25 (s, 1H), 13.22 (br, 2H).13C NMR (DMSO-d6): =
152.3, 146.6, 129.8, 128.8, 128.7, 123.8, 123.3, 122.8, 114.8,
114.2, 111.7. EIMS (70 eV), m/z (%): 260 (M++2, 13), 258
(M+, 43), 242 (3), 228 (4), 227 (13), 133 (51), 132 (100), 127
(75), 111 (28), 105 (52). Anal. Calcd. for C13H12Cl2N4: C:
52.90, H: 4.10, N: 18.98, Cl: 24.02. found C: 52.94, H: 4.15,
2-[2-(4-Methylphenyl)hydrazino]benzothiazole (3a)
Col or less nee dles; mp 238~239 C, IR (KBr): 3292,
3052~2854 cm-1; 1H NMR, = 2.18 (s, 3H), 6.70 (d, J = 8.4
Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 6.97~7.69 (m, 4H), 8.29 (s,
1H), 9.77 (s, 1H). 13C NMR (DMSO-d6): = 173.6, 153.5,

-Chloroformylarylhydrazines with Thioureas
N: 19.06, Cl: 24.03.
J. Chin. Chem. Soc., Vol. 48, No. 2, 2001 223
2-Phenylhydrazinecarboximidamide hydrochloride (5a)
Col or less nee dles; mp 227~228 C, IR (KBr): 3442~
2836 cm-1; 1H NMR, = 6.72~6.87, 7.19~7.27 (m, 5H), 7.57
(br, 2H), 8.11 (s, 1H), 9.68 (s, 1H). EIMS (70 eV), m/z (%):
150 (M+, 90), 133 (40), 91 (61), 77 (35). Anal. Calcd. for
C7H11ClN4: C: 45.05, H: 5.94, N: 30.02, Cl: 19.00. found C:
45.06, H: 5.96, N: 29.97, Cl: 18.99.
2-(2-Phenylhydrazino)thiazolinehydrochloride(3f)
Pale yel low nee dles; mp > 250 C, IR (KBr): 3190~
1
2752 cm-1; H NMR, = 3.51~3.76 (br, 2H), 3.78~4.11 (br,
2H), 6.59~7.56 (m, 5H), 8.68~9.10 (br, 2H), 10.23~11.75 (br,
1H). EIMS (70 eV), m/z (%): 193 (M+, 100), 133 (15), 105
(13), 92 (36), 77 (63). Anal. Calcd. for C9H12ClN3S: C: 47.05,
H: 5.26, N: 18.29, Cl: 15.43, S: 13.96. found C: 47.24, H:
5.32, N: 18.35, Cl: 15.50, S: 13.93.
2-(4-Methylphenyl)hydrazinecarboximidamide hydro-
chlo ride (5b)
Col or less nee dles; mp 199~200 C, IR (KBr): 3460~
3034 cm-1; 1H NMR, = 2.21 (s, 3H), 6.66 (d,J = 8.4 Hz, 2H),
7.06 (d, J = 8.4 Hz, 2H), 7.51 (br, 4H), 7.93 (s, 1H), 9.62 (s,
1H). 13C NMR (DMSO-d6): = 159.2, 145.2, 129.4, 129.1,
113.0, 20.2. EIMS (70 eV), m/z (%): 164 (M+, 80), 147 (32),
105 (100), 91 (48), 77 (38). Anal. Calcd. for C8H13ClN4: C:
47.88, H: 6.53, N: 27.92, Cl: 17.69. found C: 47.71, H: 6.40,
N: 27.96, Cl: 17.71.
2-[2-(4-Methylphenyl)hydrazino]thiazolinehydrochloride
(3g)
Col or less nee dles; mp > 250 C, IR (KBr): 3184~2740
cm-1; 1H NMR, = 2.21 (s, 3H), 3.41~3.73 (br, 2H), 3.75~
4.18 (br, 2H), 6.70 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 8.4 Hz,
2H), 7.53~8.90 (br, 2H), 10.08~11.90 (br, 1H). EIMS (70
eV), m/z (%): 207 (M+, 100), 147 (70), 106 (50), 91 (44), 77
(24). Anal. Calcd. for C10H14ClN3S: C: 49.27, H: 5.79, N:
17.24, Cl: 14.54, S: 13.15. found C: 49.36, H: 5.80, N: 17.33,
Cl: 14.44, S: 13.10.
2-(4-Chlorophenyl)hydrazinecarboximidamidehydrochlo-
ride (5c)
Col or less nee dles; mp 228~229 C, IR (KBr): 3466~
2854 cm-1; 1H NMR, = 6.74 (d, J = 9.0 Hz, 2H), 7.28 (d, J =
9.0 Hz, 2H), 7.58 (br, 4H), 8.30 (s, 1H), 9.74 (s, 1H). EIMS
(70 eV), m/z (%): 186 (M++2, 32), 184 (M+, 100), 167 (36),
125 (99), 111 (25). Anal. Calcd. for C7H10Cl2N4: C: 38.03, H:
4.56, N: 25.34, Cl: 32.07. found C: 37.94, H: 4.55, N: 25.20,
Cl: 32.10.
2-[2-(4-Chlorophenyl)hydrazino]thiazoline hydrochloride
(3h)
Col or less nee dles; mp > 250 C, IR (KBr): 3184~2764
cm-1; 1H NMR, = 3.40~3.72 (br, 2H), 3.75~4.10 (br, 2H),
6.81 (d, J = 8.8 Hz, 2H), 7.30 (d, J = 8.8 Hz, 2H), 8.81~9.23
(br, 2H), 10.21~11.78 (br, 1H). EIMS (70 eV), m/z (%): 229
(M++2, 36), 227 (M+, 100), 167 (7), 125 (14), 113 (8), 111
(24). Anal. Calcd. for C9H11Cl2N3S: C: 40.92, H: 4.20, N:
15.91, Cl: 26.84, S: 12.14. found C: 40.87, H: 4.22, N: 15.49,
Cl: 26.84, S: 12.10.
2-Amino-4-phenyl-1,3,4-thiadiazolin-5-one (6a)
Col or less nee dles; mp 171~172 C, IR (KBr): 3394,
3304, 3196, 1677 cm -1 ; 1H NMR, = 6.98 (s, 2H), 7.18~7.25,
7.38~7.43, 7.69~7.74 (m, 5H). EIMS (70 eV), m/z (%): 193
(M+, 77), 133 (49), 91 (100), 77 (47). Anal. Calcd. for
C8H7N3OS: C: 49.73, H: 3.65, N: 21.75, S: 16.59. found C:
49.73, H: 3.56, N: 21.75, S: 16.40.
The preparation of compounds 5 and 6
(A)Preparationof5a~5c and6a~6cbyreactingcompounds1
with thiourea 4a
-Chloroformylphenylhydrazinehydrochloride1 (1.5
g, 7.25 mmol) in 12 mL of EtOH was added to 0.55 g (7.25
mmol) of thiourea 4a. The re ac tion mix ture was stirred at
room tem per a ture for 10 hr. The re ac tion sol vent was re-
moved under reduced pres sure, then 10 mL of THF was
addedandstirredfor10min. Theprecipitationwascollected
by fil tra tion to give 0.59 g of pure com pound 5a (44%). The
filtratewassubjectedtochromatography(EtOAc:n-hexane=
1:1). The eluted frac tions were pooled and the sol vent was re-
moved un der re duced pres sure to give pure prod uct6a (0.22
g, 15%). The phys i cal prop er ties and spec tro scopic data of
com pounds5 and 6are as fol lows:
2-Amino-4-(4-methylphenyl)-1,3,4-thiadiazolin-5-one (6b)
Col or less nee dles; mp 151~152 C, IR (KBr): 3538~
3196, 1671 cm-1; 1H NMR, = 2.29 (s, 3H), 6.94 (s, 2H), 7.20
(d, J = 8.5 Hz, 2H), 7.58 (d, J = 8.5 Hz, 2H). EIMS (70 eV),
m/z (%): 207 (M+, 96), 147 (12), 119 (2), 105 (100), 91 (27).
Anal. Calcd. for C9H9N3OS: C: 52.17, H: 4.35, N: 20.29, S:
15.47. found C: 52.11, H: 4.32, N: 20.31, S: 15.45.
2-Amino-4-(4-chlorophenyl)-1,3,4-thiadiazolin-5-one (6c)
Col or less nee dles; mp 151~152 C, IR (KBr): 3466~
3190, 1674 cm-1; 1H NMR, = 7.03 (s, 3H), 7.48 (d, J = 9.0

224 J. Chin. Chem. Soc., Vol. 48, No. 2, 2001
Kuo et al.
Hz, 2H), 7.76 (d,J = 9.0 Hz, 2H). EIMS (70 eV), m/z (%): 229
(M++2, 30), 227 (M+, 92), 167 (57), 139 (7), 127 (54), 125
(100), 111 (31). Anal. Calcd. for C8H6ClN3OS: C: 42.20, H:
2.66, N: 18.46. found C: 42.38, H: 2.61, N: 18.56.
(B) Prep a ra tion of 5d~5f and 6d~6f by re act ing of com-
pounds 1 with re agent4b
(77), 77 (37). Anal. Calcd. for C 9H9N3OS: C: 52.16, H: 4.38,
N: 20.27, S: 15.47. found C: 52.15, H: 4.43, N: 20.12, S:
15.41.
2-Methylamino-4-(4-methylphenyl)-1,3,4-thiadiazolin-5-
one (6e)
-Chloroformylphenylhydrazinehydrochloride1 (1.5
g, 7.25 mmol) in 12 mL of i-PrOH was added to 0.75 g (7.25
mmol) of 1,3-dimethylthiourea4b.Thereactionmixturewas
stirred at room tem per a ture for 5 hr. The work-up to give pure
prod ucts was the same as in step (A).
Col or less nee dles; mp 128~129 C, IR (KBr): 3334,
1659 cm-1; 1H NMR, = 2.30 (s, 3H), 2.80 (d,J = 4.8 Hz, 3H),
7.22 (d, J = 8.4 Hz, 2H), 7.26~7.48 (br, 1H), 7.64 (d, J = 8.4
Hz, 2H). 13C NMR (DMSO-d6): = 165.1, 151.3, 135.9,
134.8, 129.2, 120.6, 28.9, 20.5. EIMS (70 eV), m/z (%): 221
(M+, 100), 161 (7), 119 (2), 105 (65), 91 (16). Anal. Calcd. for
C10H11N3OS: C: 54.28, H: 5.01, N: 18.99, S: 14.49. found C:
54.39, H: 5.06, N: 19.04, S: 14.39.
N,N’-Dimethyl-2-phenylhydrazinecarboximidamide hy-
drochloride(5d)
Col or less nee dles; mp 215~216 C, IR (KBr): 3370~
2944 cm-1; 1H NMR, = 2.78 (br, 6H), 6.78~6.88, 7.19~7.27
(m, 5H), 7.94 (br, 2H), 8.16 (s, 1H), 9.67 (s, 1H). EIMS (70
eV), m/z (%): 178 (M+, 56), 147 (13), 108 (8), 91 (29), 77
(33), 71 (100). Anal. Calcd. for C 9H15ClN4: C: 50.35, H: 7.04,
N: 26.10, Cl: 16.51. found C: 50.32, H: 7.08, N: 25.97, Cl:
16.44.
2-Methylamino-4-(4-chlorophenyl)-1,3,4-thiadiazolin-5-
one (6f)
Pale yel low pow der; mp 140~141 C, IR (KBr): 3418,
1659 cm-1; 1H NMR, = 2.80 (d, J = 4.8 Hz, 3H), 7.44~7.45
(br, 1H), 7.49 (d, J = 9.0 Hz, 2H), 7.82 (d, J = 9.0 Hz, 2H).
EIMS (70 eV), m/z (%): 243 (M++2, 37), 241 (M+, 100), 181
(26), 139 (3), 125 (89), 111 (20). Anal. Calcd. for
C9H8ClN3OS: C: 44.87, H: 3.34, N: 17.39, Cl: 14.59, S:
13.27. found C: 44.86, H: 3.38, N: 17.36, Cl: 14.59, S: 13.20.
(C)Preparationof5g~5h and 6g~6hbyreactingcompounds
1with re agent 4c
-Chloroformyl-(4-methylphenyl)hydrazines hy dro-
chloride1 (1 g, 4.25 mmol) in 12 mL of ac e tone was added to
1 g (7.25 mmol) of 1,3-diphenylthiourea 4c. The re ac tion
mix ture was stirred at room tem per a ture for 48 hr. The pre-
cip i ta tion was col lected by fil tra tion to give 0.93 g of pure
prod uct5g (58%). The fil trate was poured into ice wa ter and
stirred for 10 min. The pre cip i ta tion was col lected by fil tra-
tion and crys tal lized with EtOAc to give 0.15 g of prod uct6g
(12%). The phys i cal prop er ties and spec tro scopic data of
compounds5g~5h and6g~6h areasfollowing:
N,N’-Dimethyl-2-(4-methylphenyl)hydrazinecarboximid-
amide hydrochloride(5e)
Pale yel low pow der; mp 199~200 C, IR (KBr): 3466~
3130 cm-1; 1H NMR, = 2.22 (s, 3H), 2.79 (br, 6H), 6.70 (d, J
= 8.4, 2H), 7.04 (d, J = 8.4, 2H), 7.90 (br, 4H), 7.99 (s, 1H),
9.61 (s, 1H). EIMS (70 eV), m/z (%): 192 (M+, 80), 164 (38),
147 (32), 105 (100), 91 (48), 77 (38). Anal. Calcd. for
C10H17ClN4qH2O: C: 48.68, H: 7.76, N: 22.71, Cl: 14.37.
found C: 48.66, H: 7.77, N: 22.64, Cl: 14.41.
N,N’-Dimethyl-2-(4-chlorophenyl)hydrazinecarboximid-
amide hydrochloride(5f)
Col or less nee dles; mp 230~231 C, IR (KBr): 3472~
1
3118 cm-1; H NMR, = 2.79 (br, 6H), 6.81 (d, J = 8.8 Hz,
2H), 7.25 (d,J = 8.8 Hz, 2H), 7.94 (br, 2H), 8.33 (s, 1H), 9.70
(s, 1H). 13C NMR (DMSO-d6): = 156.9, 146.7, 128.6,
123.5, 114.7, 27.9. EIMS (70 eV), m/z (%):214 (M++2, 29),
212 (M+, 89), 181 (20), 142 (7), 125 (59), 111 (21), 71 (100).
Anal. Calcd. for C9H14Cl2N4: C: 43.35, H: 5.64, N: 22.49, Cl:
28.39. found C: 43.35, H: 5.64, N: 22.38, Cl: 28.39.
N,N’-Diphenyl-2-(4-methylphenyl)hydrazinecarboximid-
amide hydrochloride (5g)
Col or less nee dles; mp 227~228 C, IR (KBr): 3220~
2926 cm-1; 1H NMR, = 2.21 (s, 3H), 6.85 (d,J = 8.4 Hz, 2H),
7.08 (d, J = 8.4 Hz, 2H), 7.15~7.38 (m, 10H), 8.23 (s, 1H),
10.26 (br, 3H). 13C NMR (DMSO-d6): = 155.2, 145, 129.4,
129.3, 129.1, 126.0, 124.1, 113.5, 20.2. EIMS (70 eV), m/z
(%): 316 (M+, 47), 195 (100), 122 (29), 105 (11), 92 (21), 77
(21). Anal. Calcd. for C20H21ClN4: C: 68.08, H: 6.00, N:
15.88, Cl: 10.05. found C: 67.99, H: 6.00, N: 15.83, Cl:
10.00.
2-Methylamino-4-phenyl-1,3,4-thiadiazolin-5-one (6d)
Colorlessneedles;mp88~89 C, IR (KBr): 3316, 1674
cm-1; 1H NMR, = 2.80 (d, J = 4.8 Hz, 3H), 7.39~7.46 (br,
1H), 7.19~7.26, 7.39~7.46, 7.75~7.79 (m, 6H). EIMS (70
eV), m/z (%): 207 (M+, 100), 147 (19), 132 (3), 119 (10), 91

-Chloroformylarylhydrazines with Thioureas
J. Chin. Chem. Soc., Vol. 48, No. 2, 2001 225
N,N’-Diphenyl-2-(4-chlorophenyl)hydrazinecarboximid-
amide hydrochloride(5h)
2-Dimethylamino-4-(4-methylphenyl)-1,3,4-thiadiazolin-5-
one (6j)
Col or less nee dles; mp 213~214 C, IR (KBr): 3250~
2974 cm-1; 1H NMR, = 6.95 (d, J = 9.0 Hz, 2H), 7.27 (d, J =
9.0 Hz, 2H), 7.18~7.41 (m, 10H), 8.49 (s, 1H), 10.26 (br, 3H).
EIMS (70 eV), m/z (%): 338 (M++2, 32), 336 (M+, 100), 195
(100), 142 (33), 125 (26), 111 (13), 92 (27), 77 (32). Anal.
Calcd. for C19H18Cl2N4: C: 61.14, H: 4.86, N: 15.01, Cl:
19.00. found C: 61.11, H: 4.75, N: 15.07, Cl: 18.95.
Col or less nee dles; mp 103~104 C, IR (KBr): 1665
cm-1; 1H NMR, = 2.30 (s, 3H), 2.93 (s, 6H), 7.23 (d, J = 8.4
Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H). 13C NMR (CDCl3):
=
166.7, 153.7, 136.1, 135.5, 129.2, 121.1, 39.1, 20.9. EIMS
(70 eV), m/z (%): 235 (M+, 100), 175 (3), 132 (13), 105 (50),
91 (12), 88 (57). Anal. Calcd. for C11H13N3OS: C: 56.15, H:
5.57, N: 17.86, S: 13.63. found C: 56.08, H: 5.62, N: 17.90, S:
13.62.
2-Phenylamino-4-(4-methylphenyl)-1,3,4-thiadiazolin-5-
one (6g)
2-Dimethylamino-4-(4-chlorophenyl)-1,3,4-thiadiazolin-5-
one (6k)
Col or less nee dles; mp 209~210 C, IR (KBr): 3304,
1668 cm-1; 1H NMR, = 2.32 (s, 3H), 6.95~7.02, 7.25~7.37,
7.46~7.50 (m, 5H), 7.28 (d, J = 8.4 Hz, 2H), 7.66 (d, J = 8.4
Hz, 2H), 10.01 (s, 1H). EIMS (70 eV), m/z (%): 283 (M+,
100), 222 (10), 136 (30), 105 (71), 91 (19), 77 (31). Anal.
Calcd. for C15H13N3OS: C: 63.56, H: 4.62, N: 14.83, S: 11.32.
found C: 63.56, H: 4.70, N: 14.87, S: 11.30.
Colorlessneedles;mp91~92 C, IR (KBr): 1698 cm-1;
1H NMR, = 2.94 (s, 6H), 7.48 (d, J = 8.8 Hz, 2H), 7.81 (d, J
= 8.9 Hz, 2H). EIMS (70 eV), m/z (%): 257 (M++2, 35), 255
(M+, 100), 195 (7), 160 (18), 125 (47), 111 (9), 88 (58). Anal.
Calcd. for C10H10ClN3OS: C: 46.97, H: 3.94, N: 16.43, Cl:
13.86, S: 12.54. found C: 47.07, H: 3.93, N: 16.38, Cl: 13.74,
S: 12.54.
2-Phenylamino-4-(4-chlorophenyl)-1,3,4-thiadiazolin-5-
one (6h)
(E)Preparationof5l~5m and 6l~6mbyreactingcompounds
1 with re agent4e
Col or less nee dles; mp 212~213 C, IR (KBr): 3310,
1668 cm-1; 1H NMR, = 6.98~7.39, 7.46~7.51 (m, 5H), 7.55
(d, J = 9.0 Hz, 2H), 7.85 (d, J = 9.0 Hz, 2H), 10.07 (s, 1H).
EIMS (70 eV), m/z (%): 305 (M++2, 38), 303 (M+, 100), 243
(14), 125 (66), 111 (13), 77 (30). Anal. Calcd. for
C14H10ClN3OS: C: 55.36, H: 3.32, N: 13.85, Cl: 11.67, S:
10.56. found C: 55.40, H: 3.37, N: 13.85, Cl: 11.59, S: 10.47.
(D) Prep a ra tion of6i~6k by re act ing com pounds 1 with re-
agent 4d
-Chloroformylphenylhydrazinehydrochloride 1 (1.5
g, 7.25 mmol) in 12 mL of i-PrOH was added to 0.65 g (7.25
mmol) of methylthiourea 4e. The reaction mixture was
stirred at room tem per a ture for 4 hr. The work-up was the
same as in step (A) and gave 5l (0.34 g, 24%) and 6l (0.22 g,
16%).
N-Methyl-2-phenylhydrazinecarboximidamide hydrochlo-
ride (5l)
-Chloroformylphenylhydrazinehydrochloride1 (1.5
g, 7.25 mmol) in 12 mL of i-PrOH was added to 0.96 g (7.25
mmol) of tetramethylthiourea 4d. Thereactionmixturewas
stirred at room tem per a ture for 48 hr. The re ac tion so lu tion
was added to cool wa ter drop by drop, then was stirred for an-
other 10 min. The pre cip i ta tion was col lected by fil tra tion
and crys tal lized with EtOAc to give 0.43 g of prod uct 6i
(27%). The phys i cal prop er ties and spec tro scopic data of
com pounds6i~6k are as fol lows:
Col or less nee dles; mp 153~154 C, IR (KBr): 3340~
2974 cm-1; 1H NMR, = 2.78 (d, J = 4.8 Hz, 3H), 6.73~6.87,
7.18~7.26 (m, 5H), 7.73 (s, 2H), 7.94 (br, 1H), 8.07 (s, 1H),
9.57 (s, 1H). EIMS (70 eV),m/z (%): 164 (M+, 100), 147 (17),
108 (33), 91 (57), 77 (38), 57 (63). Anal. Calcd. for
C8H13ClN4: C: 47.88, H: 6.53, N: 27.92, Cl: 17.67. found C:
47.66, H: 6.60, N: 27.75, Cl: 17.63.
N-Methyl-2-(4-chlorophenyl)hydrazinecarboximidamide
hydrochloride (5m)
2-Dimethylamino-4-phenyl-1,3,4-thiadiazolin-5-one (6i)
Colorlessneedles;mp65~66 C, IR (KBr): 1677 cm-1;
1H NMR, = 2.95 (s, 6H), 7.21~7.28, 7.40~7.47, 7.75~7.80
(m, 5H). EIMS (70 eV), m/z (%): 221 (M+, 100), 161 (4), 118
(22), 91 (32), 88 (61), 77 (21). Anal. Calcd. for C10H11 N3OS:
C: 54.28, H: 5.01, N: 18.99, S: 14.49. found C: 54.30, H:
5.04, N: 18.96, S: 14.44.
Col or less nee dles; mp 202~203 C, IR (KBr): 3370~
2902 cm-1; 1H NMR, = 2.77 (d, J = 4.8 Hz, 3H), 6.76 (d, J =
8.8 Hz, 2H), 7.27 (d, J = 8.8 Hz, 2H), 7.77 (s, 2H), 7.97 (br,
1H), 8.27 (s, 1H), 9.66 (s, 1H). 13C NMR (CDCl3): = 158.7,
145.1, 129.0, 126.5, 114.8, 27.5. EIMS (70 eV),m/z (%): 200
(M++2, 32), 198 (M+, 100), 181 (13), 125 (78), 111 (27), 57
(53). Anal. Calcd. for C8H12Cl2N4: C: 40.87, H: 5.14, N:

226 J. Chin. Chem. Soc., Vol. 48, No. 2, 2001
Kuo et al.
23.83, Cl: 30.16. found C: 40.87, H: 5.15, N: 23.89, Cl:
30.15.
-Chloroformylphenylhydrazinehydrochloride 1 (1.5
g, 7.25 mmol) in 12 mL of i-PrOH was added to 0.81 g (7.25
mmol) of 1,2-cyclohexanedione 8a. The re ac tion mix ture
was stirred at room tem per a ture for 3 hours. The re ac tion sol-
vent was then re moved un der re duced pres sure. The crude
solidwasfurtherpurifiedthroughchromatography(EtOAc:
n- hexane = 1:1). The eluted frac tions were pooled and the
sol vent was re moved un der re duced pres sure to give 0.35 g
(21%) of com pound9a and 0.35 g (24%) of 2-phenyl hydra-
zino-1-cyclohexanone 13.
(F)Preparationof 6n~6p by re act ing com pounds 1 with re-
agent 4f
-Chloroformylphenylhydrazinehydrochloride1 (1.5
g, 7.25 mmol) in 12 mL of EtOH was added to 0.74 g (7.25
mmol) of ethylenethiourea 4f. The re ac tion mix ture was
stirred at room tem per a ture for 20 hr. The pre cip i tated out
product was collected by filtration and crystallizedwith
EtOAc to give 0.61 g of prod uct6n (31%).
2-( -aminoethyl)amino-4-phenyl-1,3,4-thiadiazolin-5-one
(6n)
2-Phenyl-3-oxo-6,7,8-trihydrocyclohex[e][1,3,4]oxadiazine
(9a)
Pale yel low nee dles; mp 217~218 C, IR (KBr): 3262,
Pale yel low nee dles; mp 57~58 C, IR (KBr): 1731
cm-1; 1H NMR, = 1.72~1.84 (m, 2H), 2.23~2.31 (m, 2H),
2.48~2.54 (m, 2H), 5.79 (t, J = 4.6 Hz, 1H), 7.26~7.50 (m,
5H). EIMS (70 eV), m/z (%): 228 (M+, 70), 130 (100), 119
(79), 91 (50), 77 (59), 55 (50). Anal. Calcd. for C13H12N2O2:
C: 68.41, H: 5.30, N: 12.27. found C: 68.42, H: 5.35, N:
12.24.
1
3154, 3010, 2884, 1668 cm-1; H NMR, = 3.00~3.08 (m,
2H), 3.44~3.53 (m, 2H), 7.21~7.28, 7.40~7.47, 7.75~7.80
(m, 6H), 8.05 (br, 3H). EIMS (70 eV),m/z (%): 236 (M+, 60),
207 (31), 193 (100), 119 (69), 105 (23), 91 (56), 77 (99).
Anal. Calcd. for C 10H13ClN4OS: C: 44.04, H: 4.80, N: 20.54,
Cl: 13.00, S: 11.76. found C: 44.08, H: 4.85, N: 20.51, Cl:
12.99, S: 11.75.
2-(4-Chlorophenyl)-3-oxo-6,7,8-trihydrocyclohex[e][1,3,4]-
oxadiazine (9b)
2-( -aminoethyl)amino-4-(4-methylphenyl)-1,3,4-
thiadiazolin-5-one (6o)
Pale yel low nee dles; mp 68~69 C, IR (KBr): 1731
cm-1; 1H NMR, = 1.75~1.84 (m, 2H), 2.23~2.32 (m, 2H),
2.48~2.55 (m, 2H), 5.81 (t, J = 4.6 Hz, 1H), 7.54~7.39 (m,
4H). EIMS (70 eV), m/z (%): 264 (M++2, 23), 262 (M+, 75),
183 (9), 166 (29), 164 (94), 155 (23), 153 (66), 125 (58), 113
(23), 111 (64), 55 (100). Anal. Calcd. for C13H11ClN2O2: C:
59.44, H: 4.22, N: 10.66, Cl: 13.50. found C: 59.33, H: 4.32,
N: 10.54, Cl: 13.55.
Col or less nee dles; mp > 250 C, IR (KBr): 3268, 3010,
1674 cm-1; 1H NMR, = 2.30 (s, 3H), 3.00~3.06 (m, 2H),
3.43~3.51 (m, 2H), 7.23 (d, J = 8.4 Hz, 2H), 7.64 (d, J = 8.4
Hz, 2H), 7.75 (t, J = 5.4 Hz, 1H), 8.04 (br, 3H). 13C NMR
(DMSO-d6): = 165.1, 150.7, 135.8, 135.0, 129.3, 120.6,
40.1, 37.6, 20.5. EIMS (70 eV), m/z (%): 250 (M+, 100), 221
(57), 207 (71), 133 (51), 105 (40), 91 (60). Anal. Calcd. for
C11H15ClN4OS: C: 46.07, H: 5.27, N: 19.54, Cl: 12.36, S:
11.18. found C: 46.04, H: 5.30, N: 19.52, Cl: 12.37, S: 11.14.
2-Phenylhydrazino-1-cyclohexanone (13)
Col or less nee dles; mp 188~189 C, IR (KBr): 3250,
1662 cm-1; 1H NMR, = 1.79~1.88 (m, 4H), 2.40~2.57 (m,
4H), 6.87~6.91, 7.21~7.28 (m, 5H), 9.81 (s, 1H). EIMS (70
eV), m/z (%): 202 (M+, 100), 173 (9), 145 (15), 110 (9), 93
(82), 82 (38), 77 (24), 55 (62), 41 (52). Anal. Calcd. for
C12H14N2O: C: 71.26, H: 6.98, N: 13.85. found C: 71.25, H:
7.01, N: 13.83.
(B) Preparation of compounds 9c~9e, 9f~9h, 9i~9k and
9l~9nbyreactingcompounds1 with 8b, 8c, 8d and 8e,
respectively
2-( -aminoethyl)amino-4-(4-chlorophenyl)-1,3,4-
thiadiazolin-5-one (6p)
Col or less nee dles; mp > 250 C, IR (KBr): 3262, 3154,
3004, 1668 cm-1; 1H NMR, = 3.00~3.07 (m, 2H), 3.45~3.51
(m, 2H), 7.49 (d, J = 9.0 Hz, 2H), 7.82 (d, J = 9.0 Hz, 2H),
7.95 (t, J = 5.3 Hz, 1H), 8.12 (br, 3H). EIMS (70 eV), m/z (%):
272 (M++2, 34), 270 (M+, 91), 243 (23), 241 (64), 229 (35),
227 (93), 155 (14), 153 (40), 127 (13), 125 (40), 113 (16), 111
(49), 69 (100). Anal. Calcd. for C 10H12Cl2N4OS: C: 39.10, H:
3.94, N: 18.23, Cl: 23.08, S: 10.44. found C: 38.99, H: 3.93,
N: 18.14, Cl: 23.07, S: 10.43.
-Chloroformylphenylhydrazinehydrochloride1 (1 g,
4.83 mmol) in 12 mL of EtOH was added to 0.54 g (4.83
mmol) of 3-methyl-1,2-cyclopentanedione 8b. In preparing
products9f~9h, 9i~9k and 9l~9n, 0.61 g of 8c, 0.61 g of 8d,
and 0.91 g of 8e were used, re spec tively, to re act with 1 g of
-chloroformylphenylhydrazinehydrochloride 1. The re ac-
Prep a ra tion of compounds 9a~9h
(A)Preparationofcompounds 9a and 9b by re act ing com-
pounds 1with 1,2-cyclohexanedione 8a

-Chloroformylarylhydrazines with Thioureas
J. Chin. Chem. Soc., Vol. 48, No. 2, 2001 227
tion mix ture was stirred at room tem per a ture for 1 hr. The
pre cip i ta tion was col lected by fil tra tion, then was washed
with cool i-PrOH and fi nally was crys tal lized with EtOH to
give 0.67 g of pure prod uct9c (61%).
cm-1; 1H NMR, = 1.11 (t, J = 7.7 Hz, 3H), 2.30 (s, 3H), 2.33
(q, J = 7.7 Hz, 2H), 2.55~2.71 (m, 4H), 7.19 (d, J = 8.4 Hz,
2H), 7.36 (d, J = 8.4 Hz, 2H). EIMS (70 eV), m/z (%): 256
(M+, 45), 133 (98), 105 (15), 91 (28), 83 (91), 77 (25), 55
(100). Anal. Calcd. for C15H16N2O2: C: 70.29, H: 6.29, N:
10.93. found C: 70.25, H: 6.28, N: 11.07.
5-Methyl-2-phenyl-3-oxo-6,7-dihydrocyclopent[e][1,3,4]-
oxadiazine (9c)
Pale yel low pow der; mp 90~91 C, IR (KBr): 1746
cm-1; 1H NMR, = 1.81 (s, 3H), 2.49~2.65 (m, 4H), 7.27~
7.31, 7.38~7.47 (m, 5H). EIMS (70 eV), m/z (%): 228 (M+,
76), 119 (57), 91 (41), 77 (30), 69 (100), 41 (60). Anal. Calcd.
for C13H12N2O2: C: 68.41, H: 5.30, N: 12.27. found C: 68.45,
H: 5.35, N: 12.24.
5-Ethyl-2-(4-chlorophenyl)-3-oxo-6,7-dihydrocyclopent[e]-
[1,3,4]oxadiazine (9h)
Pale yel low nee dles; mp 53~54 C, IR (KBr): 1740
1
cm-1; H NMR, = 1.12 (t, J = 7.7 Hz, 3H), 2.32 (q, J = 7.7
Hz, 2H), 2.52~2.72 (m, 4H), 7.35 (d, J = 9.0 Hz, 2H), 7.47 (d,
J = 9.0 Hz, 2H). EIMS (70 eV), m/z (%): 278 (M++2, 6), 276
(M+, 20), 155 (4), 153 (13), 127 (5), 125 (13), 113 (4), 111
(12), 83 (100), 55 (83). Anal. Calcd. for C14H13ClN2O2: C:
60.77, H: 4.73, N: 10.12, Cl: 12.81. found C: 60.57, H: 4.70,
N: 10.13, Cl: 12.83.
5-Methyl-2-(4-methylphenyl)-3-oxo-6,7-dihydrocyclopent-
[e][1,3,4]oxadiazine (9d)
Col or less nee dles; mp 134~135 C, IR (KBr): 1734
cm-1; 1H NMR, = 1.80 (s, 3H), 2.30 (s, 3H), 2.49~2.65 (m,
4H), 7.19 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H). EIMS
(70 eV), m/z (%): 242 (M+, 57), 133 (100), 91 (10), 69 (49),
41 (12). Anal. Calcd. for C14H14N2O2: C: 69.41, H: 5.82, N:
11.56. found C: 69.48, H: 5.80, N: 11.51.
5-Methyl-2-phenyl-3,6-dioxo-6H-cyclopent[e][1,3,4]-
oxadiazine (9i)
Pale yel low nee dles; mp 170~171 C, IR (KBr): 1761,
1722 cm-1; 1H NMR, = 1.76 (s, 3H), 3.29 (s, 2H), 7.36~7.54
(m, 5H). EIMS (70 eV), m/z (%): 242 (M+, 50), 119 (100), 91
(29), 83 (38), 77 (35). Anal. Calcd. for C 13H10N2O3: C: 64.45,
H: 4.16, N: 11.56. found C: 64.47, H: 4.15, N: 11.52.
2-(4-Chlorophenyl)-5-methyl-3-oxo-6,7-dihydrocyclopent-
[e][1,3,4]oxadiazine (9e)
Col or less nee dles; mp 118~119 C, IR (KBr): 1731
cm-1; 1H NMR, = 1.80 (s, 3H), 2.40~2.71 (m, 4H), 7.43 (d, J
= 9.0 Hz, 2H), 7.49 (d,J = 9.0 Hz, 2H).13C NMR (CDCl3): =
157.3, 143.7, 141.2, 139.8, 132.1, 128.9, 128.6, 125.7, 30.7,
24.4, 12.2. EIMS (70 eV), m/z (%): 264 (M++2, 20), 262 (M+,
63), 155 (15), 153 (48), 127 (9), 125 (29), 113 (4), 111 (12),
69 (100), 41 (62). Anal. Calcd. for C13H11 ClN2O2: C: 59.44,
H: 4.22, N: 10.66, Cl: 13.50. found C: 59.37, H: 4.23, N:
10.58, Cl: 13.51.
5-Methyl-2-(4-methylphenyl)-3,6-dioxo-6H-cyclopent[e]-
[1,3,4]oxadiazine (9j)
Pale yel low nee dles; mp 177~178 C, IR (KBr): 1764,
1716 cm-1; 1H NMR, = 1.76 (s, 3H), 2.33 (s, 3H), 3.28 (s,
2H), 7.26 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H). EIMS
(70 eV), m/z (%): 256 (M+, 70), 133 (100), 105 (17), 91 (36),
83 (36). Anal. Calcd. for C14H12N2O3: C: 65.62, H: 4.72, N:
10.93. found C: 65.68, H: 4.75, N: 10.83.
5-Ethyl-2-phenyl-3-oxo-6,7-dihydrocyclopent[e][1,3,4]-
oxadiazine (9f)
2-(4-Chlorophenyl)-5-mthyl-3,6-dioxo-6H-cyclopent[e]-
[1,3,4]oxadiazine (9k)
Colorlessneedles;mp88~89 C, IR (KBr): 1737 cm-1;
1H NMR, = 1.12 (t, J = 7.7 Hz, 3H), 2.33 (q,J = 7.7 Hz, 2H),
2.56~2.72 (m, 4H), 7.27~7.31, 7.36~7.53 (m, 5H). 13C NMR
(CDCl3): = 157.2, 143.9, 141.3, 140.5, 133.6, 128.7, 126.9,
124.7, 28.3, 24.3, 19.9, 11.4. EIMS (70 eV), m/z (%): 242
(M+, 85), 119 (38), 91 (29), 83 (100), 77 (21), 55 (67). Anal.
Calcd. for C 14H14N2O2: C: 69.41, H: 5.82, N: 11.56. found C:
69.31, H: 5.97, N: 11.53.
Col or less pow der; mp 200~201 C, IR (KBr): 1743,
1716 cm-1; 1H NMR, = 1.76 (s, 3H), 3.30 (s, 2H), 7.54 (s,
4H). 13C NMR (CDCl3): = 195.8, 160.7, 146.6, 141.5,
138.6, 133.5, 129.0, 125.6, 124.8, 36.1, 6.1. EIMS (70 eV),
m/z (%): 278 (M++2, 16), 276 (M+, 48), 155 (100), 127 (8),
125 (28), 113 (8), 111 (26), 83 (44). Anal. Calcd. for
C13H9ClN2O3: C: 56.43, H: 3.28, N: 10.12, Cl: 12.81. found
C: 56.45, H: 3.28, N: 10.09, Cl: 12.88.
5-Ethyl-2-(4-methylphenyl)-3-oxo-6,7-dihydrocyclopent-
[e][1,3,4]oxadiazine (9g)
2,5-Diphenyl-3,6-dioxo-6H-cyclopent[e][1,3,4]oxadiazine
(9l)
Pale yel low nee dles; mp 102~103 C, IR (KBr): 1737
Pale yel low nee dles; mp 209~210 C, IR (KBr): 1761,

228 J. Chin. Chem. Soc., Vol. 48, No. 2, 2001
Kuo et al.
1713 cm-1; 1H NMR, = 3.45 (s, 2H), 7.39~7.57, 7.90~7.95
(m, 10H). EIMS (70 eV), m/z (%): 304 (M+, 59), 185 (11),
145 (100), 119 (45), 117 (27), 91 (28), 89 (85), 77 (37). Anal.
Calcd. for C18H12N2O3: C: 71.05, H: 3.97, N: 9.21. found C:
71.07, H: 3.98, N: 9.21.
Received April 19, 2000.
Key Words
-Chloroformylarylhydrazine;
1-Arylhydrazinecarbothioate;
2-Arylhydrazinecarboximidamide;
2-(4-Methylphenyl)-5-phenyl-3,6-dioxo-6H-cyclopent[e]-
[1,3,4]oxadiazine (9m)
1,3,4-Thiadiazolin-5-one; 1,3,4-Oxadiazine.
Pale yel low nee dles; mp 160~161 C, IR (KBr): 1755,
1713 cm-1 ; 1H NMR, = 2.34 (s, 3H), 3.45 (s, 2H), 7.29 (d,J =
8.4 Hz, 2H), 7.39~7.56, 7.90~7.95 (m, 7H). 13C NMR
(CDCl3): = 194.8, 159.1, 145.5, 141.6, 138.2, 137.7, 130.0,
129.8, 129.6, 128.6, 127.5, 124.4, 122.4, 36.8, 21.1. EIMS
(70 eV), m/z (%): 318 (M+, 80), 185 (10), 145 (81), 133 (100),
117 (22), 91 (22), 89 (77), 77 (21). Anal. Calcd. for
C19H14N2O3: C: 71.69, H: 4.43, N: 8.80. found C: 71.64, H:
4.47, N: 8.78.
REFERENCES
1. Kuo, C. N.; Wu, M. H.; Chen, S. P.; Li, T. P.; Huang, C. Y.;
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5. Busch, M. J. Prakt. Chem. ,1906, 539.
2-(4-Chlorophenyl)-5-phenyl-3,6-dioxo-6H-cyclopent[e]-
[1,3,4]oxadiazine (9n)
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Pale yel low nee dles; mp 187~188 C, IR (KBr): 1773,
1704 cm-1; 1H NMR, = 3.49 (s, 2H), 7.43~7.56, 7.90~7.95
(m, 5H), 7.58 (s, 4H). EIMS (70 eV), m/z (%): 340 (M++2,
16), 338 (M+, 49), 185 (11), 155 (10), 153 (33), 145 (100),
127 (14), 125 (21), 117 (27), 113 (5), 111 (14), 89 (91), 77
(11). Anal. Calcd. for C18H11ClN2O3: C: 63.82, H: 3.27, N:
8.27, Cl: 10.47. found C: 63.88, H: 3.30, N: 8.24, Cl: 10.36.
11. Dao, L.; Mackay, D. Can. J. chem. 1978, 56, 1724.
12. Wil son, R. M.; Chow, T. J. TetrahedronLett. 1983, 24,
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ACKNOWLEDGMENT
13. Perez, S.; Lasheras, B.; Oset, C.; Monge, A. J. Hetero-
cyclic Chem. 1997, 34, 1527.
We would like to thank the Na tional Sci ence Coun cil of
the Re pub lic of China for fi nan cial sup port of this work.