Preparation of New Nitrogen-Bridged Heterocycles. 43.1 Synthesis and Reaction of 5aH-Pyrido[1,2-d][1,3,4]thiadiazepine Derivatives

Article abstract of DOI:10.1021/jo971066o

Reactions of some 1-pyridinio- and 1-(4-methylpyridinio)(arenethiocarbonyl)amidates with dimethyl acetylenedicarboxylate in chloroform afforded neither the expected dimethyl 2-aryl-5aH-pyrido-[1,2-d][1,3,4]thiadiazepine-4,5-dicarboxylates nor their intramolecular Diels-Alder adducts, but gave novel rearranged products, dimethyl 4-aryl-5-thia-2,3-diazatricyclo[4.3.2.0 ^2,7]undeca-3,8,10-triene-6,11-dicarboxylates in low to moderate yields. On the other hand, similar reactions of 1-(3-methylpyridinio)- and 1-(2-methylquinolinio)(arenethiocarbonyl)amidates with the same reagent provided 1:1 primary adducts, dimethyl 2-aryl-6-methyl-5aH-pyrido[1,2-d][1,3,4]thiadiazepine-4,5-dicarboxylates and dimethyl 2-aryl-5a-methyl-5aH-[1,3,4]thiadiazepino[4,5-α]quinoline-4,5- dicarboxylates, respectively.

Full text of DOI:10.1021/jo971066o

7788
J . Org. Chem. 1997, 62, 7788-7793
P r ep a r a tion of New Nitr ogen -Br id ged Heter ocycles. 43.1
Syn th esis a n d Rea ction of 5a H-P yr id o[1,2-d ][1,3,4]th ia d ia zep in e
Der iva tives
Akikazu Kakehi,*,† Suketaka Ito,† Fumihito Ishida,† and Yoshinori Tominaga‡
Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University,
Wakasato, Nagano 380, J apan, and Faculty of Pharmaceutical Science, Nagasaki University,
1-14, Bunkyo-machi, Nagasaki 852, J apan
Received J une 12, 1997X
Reactions of some 1-pyridinio- and 1-(4-methylpyridinio)(arenethiocarbonyl)amidates with dimethyl
acetylenedicarboxylate in chloroform afforded neither the expected dimethyl 2-aryl-5aH-pyrido-
[1,2-d][1,3,4]thiadiazepine-4,5-dicarboxylates nor their intramolecular Diels-Alder adducts, but
gave novel rearranged products, dimethyl 4-aryl-5-thia-2,3-diazatricyclo[4.3.2.02,7]undeca-3,8,10-
triene-6,11-dicarboxylates in low to moderate yields. On the other hand, similar reactions of 1-(3-
methylpyridinio)- and 1-(2-methylquinolinio)(arenethiocarbonyl)amidates with the same reagent
provided 1:1 primary adducts, dimethyl 2-aryl-6-methyl-5aH-pyrido[1,2-d][1,3,4]thiadiazepine-4,5-
dicarboxylates and dimethyl 2-aryl-5a-methyl-5aH-[1,3,4]thiadiazepino[4,5-a]quinoline-4,5-dicar-
boxylates, respectively.
Previously, we reported on smooth formation of 10aH-
pyrido[1,2-d][1,4]thiazepine derivatives and/or their in-
tramolecular Diels-Alder adducts in the reactions of
various 1-pyridinio[(alkylthio)thiocarbonyl]methylides with
dimethyl acetylenedicarboxylate (DMAD).2 In the con-
tinuation of our work for exploring new reactivities of
pyridinium N-ylides, we were interested in the extension
of this reaction to 1-pyridinio(substituted thiocarbonyl)-
amidates, because such types of heterocycles cannnot be
obtained by other methods and because some potential
pharmaceutical activities can be expected for them.
However, all of our preliminary attempts to obtain any
significant products such as 5aH-pyrido[1,2-d][1,3,4]-
thiadiazepines B and the intramolecular Diels-Alder
adducts, 4-thia-1,2-diazatetracyclo[5.4.0.0.5,1106,8]undeca-
2,9-dienes C, from the reactions of some 1-pyridinio-
[(methylthio)thiocarbonyl]amidates3 and DMAD were
unsuccessful (see Figure 1). As a reason for our inac-
cessibility to these products described above, we pre-
F igu r e 1.
sumed an extremely high reactivity of the isocyanate
dithioacetal moiety in the zwitterionic intermediate A
and/or pyrido[1,2-d][1,3,4]thiadiazepines B toward mois-
ture and nucleophiles. So, we next examined the use of
1-pyridinio(aryl-substituted thiocarbonyl)amidates whose
reactivity at the thioimidate moiety has been lowered by
the stabilizing effect of the aromatic substituent and
found that their reactions with DMAD gave unexpected
products, dimethyl 4-aryl-5-thia-2,3-diazatricyclo[4.3.2.02,7]-
undeca-3,8,10-triene-6,11-dicarboxylates,4 together with
some title compounds. In this paper we wish to report
on the isolation and the novel rearrangement of 5aH-
pyrido[1,2-d][1,3,4]thiadiazepine derivatives.
† Shinshu University.
‡ Nagasaki University.
X Abstract published in Advance ACS Abstracts, October 1, 1997.
(1) For part 42 of this series, see Kakehi, A.; Ito, S.; Hashimoto, Y.
Bull. Chem. Soc. J pn. 1996, 69, 1769.
(2) (a) Kakehi, A.; Ito, S.; Hakui, J . Chem. Lett. 1992, 777. (b)
Kakehi, A.; Ito, S. Heterocycles 1993, 36, 1195. (c) Kakehi, A.; Ito, S.;
Hakui, J . Bull. Chem. Soc. J pn. 1993, 66, 3475. (d) Kakehi, A.; Ito, S.;
Mitani, M.;Kanaoka, M. Bull. Chem. Soc. J pn. 1994, 67, 1646. (e)
Kakehi, A.; Ito, S.; Fujita, S. Bull. Chem. Soc. J pn. 1995, 68, 1473.
(3) (a) Kakehi, A.; Ito, S.; Watanabe, K. Bull. Chem. Soc. J pn. 1980,
53, 1775. (b) Yoshida, H.; Urushibata, K.; Ogata, T. Bull. Chem. Soc.
J pn. 1983, 56, 1561.
(4) Kakehi, A.; Ito, S.; Ishida, F.; Tominaga, Y. Heterocycles, 1995,
41, 2657.
(5) Kakehi, A.; Ito, S.; Nagata, K.; Kinoshita, N.; Kakinuma, N.
Chem. Pharm. Bull. 1987, 35, 156.
Resu lts a n d Discu ssion
P r ep a r a tion of 1-P yr id in io(a r en eth ioca r bon yl)-
a m id a t es. These 1-pyridinio(arenethiocarbonyl)ami-
dates (3a -u ) were prepared in 34-93% yields through
the reactions of 1-aminopyridinium iodides (1a -c) or
1-amino-2-methylquinolinium p-toluenesulfonate (1d )
with methyl dithiobenzoates (2a ), methyl p-toluene-
dithiocarboxylate (2b), methyl p-methoxybenzenedithio-
carboxylate (2c), methyl o-methoxybenzenedithiocarbox-
ylate (2d ), methyl p-chlorobenzenedithiocarboxylate (2e),
methyl 2-thiophenedithiocarboxylate (2f), or methyl p-
(dimethylamino)benzenedithiocarboxylate (2g) in the
(6) For the crystal data for compound 7h , see ref 4.
(7) (a) Okamoto, T.; Hirobe, M.; Yabe, E. Chem. Pharm. Bull. 1966,
14, 506. (b) Sasaki, T.; Kanematsu, K.; Kakehi, A. J . Org. Chem. 1972,
36, 2978. (c) Sasaki, T.; Kanematsu, K.; Kakehi, A.; Ito, G. J . Chem.
Soc., Perkin Trans. 1 1973, 2089. (d) Tamura, Y.; Sumida, Y.; Miki,
Y.; Ikeda, M. J . Chem. Soc., Perkin Trans. 1 1975, 406.
(8) This situation is quite opposite to the relation (see ref 2b) in the
interaction between the 7-methyl group and 5-substituent in 7-methyl-
10aH-pyrido[1,2-d][1,4]thiazepine derivatives.
(9) According to the MM2 calculation for these pyrido[1,2-d]-
[1,3,4]thiadiazepine derivatives 5 and 5′, the angular conformation D
is more favorable than the planar one E. This fact may suggest a reason
for the inaccessibility and ready rearrangement of 6-unsubstituted
pyrido[1,2-d][1,3,4]thiadiazepine intermediates 5, because subsequent
rearrangement starts from this comformation D.
(10) Though our ring system is not normal di-π-methane ring system
such as 2,5-cyclohexadien-1-one, we used this word from the similari-
ties of the apparent electron demand and the structural transforma-
tion. For di-π-methane rearrangement, see Schaffner K. Adv. Photo-
chem. 1966 4, 81. Kropp P. J . Org. Photochem. 1967, 1, 1.
(11) Whether this reaction proceeds successfully or not is largely
dependent upon the exhaustive removal of the moisture and any
nucleophiles from the reaction system.
S0022-3263(97)01066-9 CCC: $14.00 © 1997 American Chemical Society

Preparation of New Nitrogen-Bridged Heterocycles
J . Org. Chem., Vol. 62, No. 22, 1997 7789
Sch em e 1
Sch em e 2
tion band at 1730∼1744 and 1703∼1718 cm-1, respec-
tively, and these values were clearly different from those
for the two R,â-unsaturated ester carbonyl groups in 5
and the two saturated ones in 6. Furthermore, the
chemical shifts of the skeletal protons derived from the
presence of alkali, according to our previous procedure
(Scheme 1).5
These amidates 3a -u were obtained as pale yellow
prisms having a characteristic sulfur odor, and their IR
spectra showed an absorption band attributable to the
1
pyridine moiety of amidates 3 in the H NMR spectra of
7a -c,e-s indicated that the arrangement of the skeletal
carbons attaching the corresponding protons is sp3-sp2-
sp2-sp3-sp2, which also is inconsistent with both the sp3-
sp2-sp2-sp2-sp2 in 5 and the sp3-sp2-sp2-sp3-sp3 in 6. In
particular, the appearance of the terminal proton (10-H)
as a doublet in a largely lowered region (δ 7.47-7.61)
suggested a proximity to an ester group with a strong
anisotropy effect. These spectral data and the mecha-
nistic consideration (see Mechanisms) strongly supported
the possibility of the ring contraction of the pyridine to
the pyrrole ring during this reaction. Eventually, a
single-crystal X-ray analysis on compound 7h 6 gave the
solution; the rearranged structures, dimethyl 4-aryl-5-
thia-2,3-diazatricyclo[4.3.2.02,7]undeca-3,8,10-triene-6,11-
dicarboxylates, were finally confirmed for 7a -c,e-s.
P r ep a r a tion of 5a H-P yr id o[1,2-d ][1,3,4]th ia d ia ze-
p in es a n d 5a H -[1,3,4]Th ia d ia zep in o[4,5-a ]q u in o-
lin es. The formation of dimethyl 4-aryl-8-methyl-5-thia-
2,3-diazatricyclo[4.3.2.02,7]undeca-3,8,10-triene-6,11-di-
carboxylates (7o-s) and the absence of one more possible
product, 1-methyl isomers such as 7′o-s, in the reactions
of the unsymmetrically substituted 1-pyridinioamidates
(3o-s) with DMAD (4) seemed very strange to us.
Mechanistically, the rearranged products 7o-s and
7′o-s are derived from 8-methyl-5aH-pyrido[1,2-d][1,3,4]-
thiadiazepines (5o-s) and their 6-methyl isomers (5′o-
s), respectively, as shown in Scheme 3. Since it is well-
known that thermal cycloaddition and cyclization of
unsymmetrical 3-substituted pyridinium N-ylides afford
the ring-closure isomers at the 2-position as major
products and those at the 6-position as minor ones,7 the
observed exclusive formation of 5o-s in these reactions
requires a new mechanistic consideration. We thought
carbon-sulfur double bond at near 1150 cm-1
.
R ea ct ion s of 1-P yr id in io(a r en et h ioca r b on yl)-
a m id a tes w ith DMAD. As described above, all of our
attempts were unsuccessful to obtain any other signifi-
cant products than small amounts of dimethyl fumarate
and hexamethyl benzenehexacarboxylate through the
reactions of some 1-pyridinio[(methylthio)thiocarbonyl]-
amidates3 and DMAD. So, the reactions of aryl-substi-
tuted pyridinium N-ylides (3a -u ) with the same reagent
were next investigated in expectation of the stabilization
of reaction intermediates and title compounds.
When a chloroform solution of 1-pyridinio(thiobenzoyl)-
amidate (3a ) and DMAD (4) was heated at 50-60 °C in
a water bath for 8-11 h and subjected to a chromato-
graphic separation, a product 7a was obtained in 30%
yield as colorless prisms. Similar treatments of amidates
3b-s and 4 gave the corresponding adducts 7b,c,e-s in
low to moderate yields (1-35%) except 7d (Scheme 2).
On the other hand, the reactions of some amidates 3 with
4 at room or low temperature (0 °C) were also examined,
but they gave only intractable tarry materials from which
no significant products could be isolated.
Elemental analyses for products 7a -c,e-s were in
good accord with the compositions proposed for 1:1
adducts between 1-pyridinio(arenethiocarbonyl)amidates
1
(3a -c,e-s) and DMAD (4). However, their IR and H
NMR spectral data were different largely from those for
both the expected 5aH-pyrido[1,2-d][1,3,4]thiadiazepines
(5) and the intramolecular Diels-Alder adducts, 4-thia-
1,2-diazatetracyclo[5.4.0.0.5,1106,8]undeca-2,9-dienes (6).
For example, the IR spectra of 7a -c,e-s exhibited a
saturated and an R,â-unsaturated ester carbonyl absorp-

7790 J . Org. Chem., Vol. 62, No. 22, 1997
Kakehi et al.
Sch em e 3
F igu r e 2.
Sch em e 4
that these reactions must first have given a mixture of
the corresponding bicyclic adducts 5o-s and 5′o-s,
whereas only the former must have rearranged smoothly
to products 7o-s, which were actually isolated. On the
other hand, the transformation of the other isomers
5′o-s to the corresponding compounds 7′o-s with a
bridgehead methyl group must be difficult because of
their severe intramolecular steric interaction between the
5-methoxycarbonyl and the 6-methyl group. According
to an examination of the Dreiding models for compound
5′o, the steric interactions between the 6-methyl and the
5-methoxycarbonyl group is stronger in the angular
conformation (D) than in the planar one (E) (see Figure
2).8,9 To confirm this idea and to isolate these adducts
5′o-s, we carefully reexamined the reactions of amidates
3o-s and succeeded in the isolation of the aimed
products 5′o-s from reaction mixtures.
When a reaction solution of amidates 3o-s and DMAD
(4) was allowed to react at 50-60 °C for a shortened time
(4 h), the corresponding dimethyl 2-aryl-6-methyl-5aH-
pyrido[1,2-d][1,3,4]thiadiazepine-4,5-dicarboxylates (5′o-
s) were obtained in trace-27% yields as red prisms or
needles, together with the rearranged products 7o-s (6-
11%). Similarly, the reactions of 1-(2-methylquinolinio)-
amidates 3t,u with 4 gave only the expected dimethyl
2-aryl-5a-methyl-5aH-1,3,4-thiadiazepino[4,5-a]quinoline-
4,5-dicarboxylates (8a ,b) in 41 and 43% yields, respec-
tively; these results are shown in Scheme 4. The
successful isolation of tricyclic compounds 8a ,b must be
due to both the stabilization by the fused benzene ring
and the resistance to the loss of the aromaticity of the
benzene ring during the rearrangement.
proton and methyl protons are possibly due to the
anisotropy effects of the lone pair on the adjacent
nitrogen atom and of the π orbital of the adjacent
carbon-carbon double bond. X-ray analyses on the two
compounds 5′o and 8a were also performed, and their
structures were finally confirmed. Interestingly, the
crystal structure of 5′o resembled to the planar comfor-
mation (E) and that of 8a the angular one (D). Further-
more, these crystal data also clarified that the bridgehead
nitrogen atom is almost trigonal planar. This fact may
explain well the abnormality of the chemical shifts for
the bridgehead hydrogen and methyl protons described
above.
Rea ction Mech a n ism s. Possible mechanisms for this
reaction are shown in Scheme 5. Since some primary
adducts 5′o-s were actually isolated, it may be consid-
ered that this rearrangement proceeds via the initial
formation of the corresponding 5aH-pyrido[1,2-d][1,3,4]-
thiadiazepine intermediate (5) (path a). The subsequent
ring closure between the 4- and 9-positions in the
molecule 5, leading to the construction of the 1,3,4-
thiadiazine ring, followed by the 1,2-cationic shift of a
nitrogen-carbon single bond in the resulting ionic in-
termediate 9 to the vicinal carbon atom, may produce the
rearranged products 7. Although there is an alternative
route (path b) via the intervention of the intramolecular
Diels-Alder type of adduct 6 from 5 and/or 9, this is not
likely because it is a thermally forbidden process (retro-
di-π-methane rearrangement).10 As already described by
us,2d no thermolyses of 4-thia-1-azatetracyclo[5.4.0.0.5,1106,8]-
The structures of these thiadiazepine derivatives 5′o-s
and 8a ,b were readily determined by their physical and
spectral properties. These compounds had the composi-
tions of the 1:1 adducts between amidates 3o-u and
DMAD (4), and their IR spectra exhibited characteristic
ester carbonyl absorption bands at 1722-1734 cm-1
.
Furthermore, the 1H NMR spectra of 5′o-s and 8a ,b
showed reasonable chemical shifts and signal patterns
for our proposed structures except for the considerably
lowered chemical shifts of the 5a-protons (δ 7.45-7.53)
in 5′o-s and the 5a-methyl protons (δ 1.74 and 1.76) in
8a ,b. The abnormally lowered shifts for the bridgehead

Preparation of New Nitrogen-Bridged Heterocycles
J . Org. Chem., Vol. 62, No. 22, 1997 7791
Anal. Calcd for C13H12N2OS: C, 63.91; H, 4.95; N, 11.47%.
Found: C, 64.17; H, 4.95; N, 11.21%.
Sch em e 5
1-P y r id in io (o-m e t h o x y b e n ze n e t h io c a r b o n y l)a m i-
d a te (3d ): 87% (from 1a and 2d ), mp 125-127 °C, IR (KBr)
1159 cm-1 1H NMR (CDCl3) δ 3.86(3H, s), 7.1-8.8 (9H, m).
,
Anal. Calcd for C13H12N2OS: C, 63.91; H, 4.95; N, 11.47%.
Found: C, 63.73; H, 5.02; N, 11.61%.
1-P yr id in io(p -ch lor ob e n ze n e t h ioca r b on yl)a m id a t e
(3e): 69% (from 1a and 2e), mp 143-145 °C, IR (KBr) 1159
cm-1 1H NMR (CDCl3) δ 7.2-8.7 (9H, m). Anal. Calcd for
,
C12H9ClN2S: C, 57.95; H, 3.65; N, 11.26%. Found: C, 57.95;
H, 3.55; N, 11.36%.
1-P yr idin io(2-th ioph en eth iocar bon yl)am idate (3f): 64%
(from 1a and 2f), mp 158-160 °C, IR (KBr) 1151 cm-1 1H
,
NMR (CDCl3) δ 7.0-9.0 (8H, m). Anal. Calcd for C10H8N2S2:
C, 54.52; H, 3.66; N, 12.72%. Found: C, 54.58; H, 3.64; N,
12.84%.
1-P yr id in io(p-(d im eth yla m in o)ben zen eth ioca r bon yl)-
a m id a te (3g): 59% (from 1a and 2g), mp 108-110 °C, IR
(KBr) 1174 cm-1, 1H NMR (CDCl3) δ 3.01 (6H, s), 7.6-8.7 (9H,
m). Anal. Calcd for C14H15N3S: C, 65.34; H, 5.88; N, 16.33%.
Found: C, 65.06; H, 6.17; N, 16.33%.
1-(4-Me t h ylp yr id in io)(p -t olu e n e t h ioca r b on yl)a m i-
d a te (3i): 72% (from 1b and 2b), mp 168-170 °C, IR (KBr)
1
1174 cm-1, H NMR (CDCl3) δ 2.42 (3H, s), 2.64 (3H, s), 7.1-
8.6 (8H, m). Anal. Calcd for C14H14N2S: C, 69.39; H, 5.82; N,
11.56%. Found: C, 69.41; H, 5.92; N, 11.44%.
1-(4-Me t h y lp y r id in io )(p -m e t h o x y b e n ze n e t h io c a r -
bon yl)a m id a te (3j): 92% (from 1b and 2c), mp 141-143 °C,
IR (KBr) 1174 cm-1, 1H NMR (CDCl3) δ 2.60 (3H, s), 3.87 (3H,
s), 6.8-8.8 (8H, m). Anal. Calcd for C14H14N2OS: C, 65.09;
H, 5.46; N, 10.84%. Found: C, 65.13; H, 5.46; N, 10.80%.
1-(4-Me t h y lp y r id in io )(o-m e t h o x y b e n ze n e t h io c a r -
bon yl)a m id a te (3k ): 89% (from 1b and 2d ), mp 132-134
undeca-2,9-dienes, which are the 2-deaza analogues of
6, afforded the corresponding tricyclic products.
The reason is unclear why the formation of dimethyl
3-aryl-4-thia-1,2-diazatetracyclo[5.4.0.0.5,1106,8]undeca-
2,9-diene-5,6-dicarboxylates (6) via the intramolecular
Diels-Alder reaction of 5 and/or the combination between
the ionic centers in 9 did not occur. However, the fact
that the inclusion of one nitrogen atom, as seen in
tetracycles 6, increases its ring strain more than in the
2-deaza analogues may be one reason, since the nitrogen-
nitrogen single bond and the nitrogen-carbon double
bond are considerably shorter than the nitrogen-carbon
single bond and the carbon-carbon double bond, respec-
tively. Eventually, tetracycles such as 6, even if formed,
must rapidly decompose under the reaction conditions
employed, leaving only the stabler tricycles 7 formed.
1
°C, IR (KBr) 1165 cm-1, H NMR (CDCl3) δ 2.59 (3H, s), 3.89
(3H, s), 6.8-8.8 (8H, m). Anal. Calcd for C14H14N2OS: C,
65.09; H, 5.46; N, 10.84%. Found: C, 64.92; H, 5.44; N,
11.02%.
1-(4-Meth ylp yr id in io)(p-ch lor oben zen eth ioca r bon yl)-
a m id a te 3l; 69% (from 1b and 2e), mp 160-162 °C, IR (KBr)
1
1167 cm-1, H NMR (CDCl3) δ 2.62 (3H, s), 7.2-8.5 (8H, m).
Anal. Calcd for C13H11ClN2S: C, 59.42; H, 4.22; N, 10.66%.
Found: C, 59.42; H, 4.22; N, 10.75%.
1-(4-Met h ylp yr id in io)(2-t h iop h en et h ioca r b on yl)a m i-
d a te (3m ): 69% (from 1b and 2f), mp 151-153 °C, IR (KBr)
1
1140 cm-1, H NMR (CDCl3) δ 2.60 (3H, s), 6.9-8.6 (7H, m).
Anal. Calcd for C11H10N2S2: C, 56.38; H, 4.30; N, 11.95%.
Found: C, 56.36; H, 4.37; N, 12.21%.
Exp er im en ta l Section
1-(4-Meth ylp yr id in io)(p-(d im eth yla m in o)ben zen eth io-
ca r bon yl)a m id a te (3n ): 87% (from 1b and 2g), mp 109-
1
Melting points are uncorrected. The H NMR spectra were
1
111 °C, IR (KBr) 1184 cm-1, H NMR (CDCl3) δ 2.55 (3H, s),
determined at 60 MHz in deuteriochloroform with TMS as an
internal standard; chemical shifts are expressed in δ values.
P r ep a r a tion of 1-P yr id in io(a r en eth ioca r bon yl)a m i-
d a tes. These amidates were prepared from the reactions of
1-aminopyridinium salt (1) and methyl arenedithiocarboxylate
(2) in the presence of an alkali according to the procedure
reported previously by us.5
Although 1-pyridinio- (3a -s) and 1-(2-methylquinolinio-
)(arenethiocarbonyl)amidates (3t,u ) were smoothly synthesized
by this method, the corresponding 1-quinolinio- and 2-iso-
quinolinio(arenethiocarbonyl)amidates could not be obtained
from the reactions of 1-aminoquinolinium and 2-aminoiso-
quinolinium mesitylenesulfonate with 2. Physical and spectral
data for known 1-pyridinio(thiobenzoyl)amidates (3a ,h ) were
in accord with those for authentic samples.5
3.00 (6H, s), 6.5-8.5 (8H, m). Anal. Calcd for C15H17N3S: C,
66.39; H, 6.31; N, 15.48%. Found: C, 66.17; H, 6.09; N,
15.32%.
1-(3-Meth ylp yr id in io)th ioben zoyla m id a te (3o): 73%
(from 1c and 2a ), mp 137139 °C, IR (KBr) 1169 cm-1, 1H NMR
(CDCl3) δ 2.55 (3H, s), 7.2-8.6 (9H, m). Anal. Calcd for
C13H12N2S: C, 68.39; H, 5.30; N, 12.27%. Found: C, 68.28;
H, 5.36; N, 12.32%.
1-(3-Me t h ylp yr id in io)(p -t olu e n e t h ioca r b on yl)a m i-
d a te (3p ): 70% (from 1c and 2b), mp 132-134 °C, IR (KBr)
1
1176 cm-1, H NMR (CDCl3) δ 2.41 (3H, s), 2.54 (3H, s), 7.1-
8.6 (8H, m). Anal. Calcd for C14H14N2S: C, 69.39; H, 5.82; N,
11.56%. Found: C, 69.20; H, 5.82; N, 11.75%.
1-(3-Me t h y lp y r id in io )(p -m e t h o x y b e n ze n e t h io c a r -
bon yl)a m id a te (3q): 93% (from 1c and 2c), mp 150-152 °C,
IR (KBr) 1163 cm-1, 1H NMR (CDCl3) δ 2.49 (3H, s), 3.82 (3H,
s), 6.8-8.5 (8H, m). Anal. Calcd for C14H14N2OS: C, 65.09;
H, 5.46; N, 10.84%. Found: C, 65.06; H, 5.50; N, 10.85%.
1-(3-Meth ylp yr id in io)(p-ch lor oben zen eth ioca r bon yl)-
a m id a te (3r ): 80% (from 1c and 2e), mp 127-129 °C, IR
(KBr) 1163 cm-1, 1H NMR (CDCl3) δ 2.57 (3H, s), 7.2-8.8 (8H,
m). Anal. Calcd for C13H11ClN2S: C, 59.42; H, 4.22; N,
10.66%. Found: C, 59.51; H, 4.22; N, 10.57%.
Some data for new 1-pyridinio(arenethiocarbonyl)amidates
(3b-g,i-u ) are as follows:
1-P yr id in io(p-tolu en eth ioca r bon yl)a m id a te (3b): 62%
(from 1a and 2b), mp 169-171 °C, IR (KBr) 1176 cm-1 1H
,
NMR (CDCl3) δ 2.42 (3H, s), 7.1-8.8 (9H, m). Anal. Calcd
for C13H12N2S: C, 68.39; H, 5.30; N, 12.27%. Found: C, 68.36;
H, 5.30; N, 12.19%.
1-P y r id in io (p -m e t h o x y b e n ze n e t h io c a r b o n y l)a m i-
d a te (3c): 93% (from 1a and 2c), mp 139-141 °C, IR (KBr)
1-(4-Met h ylp yr id in io)(2-t h iop h en et h ioca r b on yl)a m i-
d a te (3s): 90% (from 1c and 2f), mp 144-146 °C, IR (KBr)
1
1171 cm-1, H NMR (CDCl3) δ 3.86 (3H, s), 6.8-8.7 (9H, m).

7792 J . Org. Chem., Vol. 62, No. 22, 1997
Kakehi et al.
1
1143 cm-1, H NMR (CDCl3) δ 2.55 (3H, s), 7.0-8.6 (7H, m).
J ) 6.0, 7.0 Hz), 5.85 (1H, br d, J ) 6.0 Hz), 6.48 (1H, d, J )
7.0 Hz), 7.45 (1H, s), 6.7-7.9 (5H, m). Anal. Calcd for
C17H16N2O4S2: C, 54.24; H, 4.28; N, 7.44%. Found: C, 54.31;
H, 4.25; N, 7.40%.
Anal. Calcd for C11H10N2S2: C, 56.38; H, 4.30; N, 11.95%.
Found: C, 56.17; H, 4.26; N, 11.97%.
1-(2-Meth ylqu in olin io)(th ioben zoyl)a m id a te (3t): 42%
(from 1d and 2a ), mp 189-191 °C, IR (KBr) 1167 cm-1 1H
,
Dim eth yl 4-p h en yl-5-th ia -2,3-d ia za tr icyclo[4.3.2.02,7]-
NMR (CDCl3) δ 2.91 (3H, s), 7.3-8.7 (11H, m). Anal. Calcd
for C17H14N2S: C, 73.35; H, 5.07; N, 10.06%. Found: C, 73.36;
H, 5.16; N, 9.95%.
u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7a ): 30% (from
3a and 4), mp 175-177 °C, IR (KBr) 1733, 1709, 1614 cm-1
,
1H NMR (CDCl3) δ 3.73 (3H, s), 3.85 (3H, s), 4.18 (1H, d, J )
3.0 Hz), 4.64 (1H, q, J ) 3.0, 5.0 Hz), 6.23 (1H, q, J ) 3.0, 6.0
Hz), 6.76 (1H, q, J ) 3.0, 6.0 Hz), 7.50 (1H, d, J ) 5.0 Hz),
7.2-8.0 (5H, m). Anal. Calcd for C18H16N2O4S: C, 60.66; H,
4.53; N, 7.86%. Found: C, 60.56; H, 4.51; N, 7.83%.
1-(2-Meth ylqu in olin io)(2-th iop h en eth ioca r bon yl)a m i-
d a te (3u ): 34% (from 1d and 2f), mp 186-188 °C, IR (KBr)
1
1168 cm-1, H NMR (CDCl3) δ 2.92 (3H, s), 7.0-8.7 (9H, m).
Anal. Calcd for C15H12N2S2: C, 63.35; H, 4.25; N, 9.05%.
Found: C, 63.09; H, 4.27; N, 9.75%.
Dim eth yl 4-(p-tolyl)-5-th ia -2,3-d ia za tr icyclo[4.3.2.02,7]-
u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7b): 15% (from
R ea ct ion s of 1-P yr id in io- a n d 1-Qu in olin io(a r en e-
th ioca r bon yl)a m id a tes w ith DMAD. Gen er a l Meth od A.
A solution of amidate (3, 1 mmol) in 40 mL of dry CHCl3 was
concentrated to about 20 mL in order to completely remove
moisture and alcohol,11 and then DMAD (4, 0.143 g, 1.2 mmol)
was added. The resulting solution was heated at 50-60 °C
for 8-11 h. The reaction solution was concentrated, and the
residue was separated by column chromatography on alumina
using ether and then CHCl3. Concentration of the CHCl3
fraction and recrystallization of the crude crystals form
CHCl3-hexane gave dimethyl 4-aryl-5-thia-2,3-diazatricyclo-
[4.3.2.02,7]undeca-3,8,10-triene-6,11-dicarboxylates (7a -s) as
colorless prisms or dimethyl 2-aryl-5a-methyl-5aH-[1, 3,4]-
thiadiazepino[4,5-a]quinoline-4,5-dicarboxylates (8a ,b) as yel-
low prisms.
Gen a r a l Meth od B. The CHCl3 solution of 1-(3-methylpy-
ridinio)amidates (3o-s, 1 mmol) and DMAD (4, 0.143 g, 1.2
mmol) prepared by the above procedure was heated at 50-60
°C for 4 h. Usual workups of the resulting mixtures gave the
corresponding dimethyl 2-aryl-6-methyl-5aH-pyrido[1,2-d][1,3,4]-
thiadiazepine-4,5-dicarboxylates (5′o-s) as red prisms or
needles, together with dimethyl 4-aryl-5-thia-2,3-diazatricyclo-
[4.3.2.02,7]undeca-3,8,10-triene-6,11-dicarboxylates (7o-s).
Although the reactions of 1-pyridinio(arenethiocarbonyl)-
amidates (3) with 4 at rt or at 0 °C were also examined, any
significant products could not be isolated.
3b and 4), mp 225-227 °C, IR (KBr) 1741, 1714, 1612 cm-1
,
1H NMR (CDCl3) δ 2.37 (3H, s), 3.75 (3H, s), 3.86 (3H, s), 4.21
(1H, d, J ) 3.0 Hz), 4.66 (1H, q, J ) 3.0, 5.0 Hz), 6.27 (1H, q,
J ) 3.0, 6.0 Hz), 6.82 (1H, q, J ) 3.0, 6.0 Hz), 7.57 (1H, d, J
) 5.0 Hz), 7.0-7.9 (4H, m). Anal. Calcd for C19H18N2O4S: C,
61.61; H, 4.90; N, 7.56%. Found: C, 61.63; H, 4.94; N, 7.50%.
Dim eth yl 4-(p-m eth oxyph en yl)-5-th ia-2,3-diazatr icyclo-
[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7c):
30% (from 3c and 4), mp 185-187 °C, IR (KBr) 1738, 1712,
1
1605 cm-1, H NMR (CDCl3) δ 3.72 (3H, s), 3.84 (6H, s), 4.17
(1H, d, J ) 3.0 Hz), 4.62 (1H, q, J ) 3.0, 5.0 Hz), 6.24 (1H, q,
J ) 3.0, 6.0 Hz), 6.76 (1H, q, J ) 3.0, 6.0 Hz), 7.50 (1H, d, J
) 5.0 Hz), 6.8-7.9 (4H, m). Anal. Calcd for C19H18N205S: C,
59.06; H, 4.70; N, 7.25%. Found: C, 59.33; H, 4.76; N, 7.12%.
Dim eth yl 4-(p-ch lor op h en yl)-5-th ia -2,3-d ia za tr icyclo-
[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7e):
3% (from 3e and 4), mp 192-194 °C, IR (KBr) 1736, 1714,
1
1606 cm-1, H NMR (CDCl3) δ 3.73 (3H, s), 3.86 (3H, s), 4.16
(1H, d, J ) 3.0 Hz), 4.63 (1H, q, J ) 3.0, 5.0 Hz), 6.21 (1H, q,
J ) 3.0, 6.0 Hz), 6.77 (1H, q, J ) 3.0, 6.0 Hz), 7.49 (1H, d, J
) 5.0 Hz), 7.2-7.9 (4H, m). Anal. Calcd for C18H15ClN2O4S:
C, 55.32; H, 3.87; N, 7.17%. Found: C, 55.31; H, 3.82; N,
7.13%.
Dim eth yl 4-(2-th ien yl)-5-th ia-2,3-diazatr icyclo[4.3.2.02,7]-
u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7f): 28% (from
Some data for these products (5′o-s, 7a -s, and 8a ,b) are
as follows:
3f and 4), mp 220-222 °C, IR (KBr) 1732, 1709, 1614 cm-1
,
1H NMR (CDCl3) δ 3.72 (3H, s), 3.85 (3H, s), 4.19 (1H, d, J )
3.0 Hz), 4.64 (1H, q, J ) 3.0, 5.0 Hz), 6.21 (1H, q, J ) 3.0, 6.0
Hz), 6.75 (1H, q, J ) 3.0, 6.0 Hz), 6.9-7.7 (4H, m). Anal. Calcd
for C16H14N2O4S2: C, 53.02; H, 3.89; N, 7.73%. Found: C,
53.05; H, 3.95; N, 7.85%.
Dim eth yl 6-m eth yl-2-p h en yl-5a H-p yr id o[1,2-d ][1,3,4]-
th ia d ia zep in e-4,5-d ica r boxyla tes (5′o): 22% (from 3o and
4), mp 129-131 °C, IR (KBr) 1726, 1651, 1608 cm-1, 1H NMR
(CDCl3) δ 1.84 (3H, s), 3.84 (3H, s), 3.87 (3H, s), 4.87 (1H, q,
J ) 6.0, 7.0 Hz), 5.86 (1H, br d, J ) 6.0 Hz), 6.49 (1H, d, J )
7.0 Hz), 7.50 (1H, s), 7.2-8.0 (5H, m). Anal. Calcd for
C19H18N2O4S: C, 61.61; H, 4.90; N, 7.56%. Found: C, 61.64;
H, 4.88; N, 7.56%.
Dim eth yl 6-m eth yl-2-(p-tolyl)-5a H-p yr id o[1,2-d ][1,3,4]-
th ia d ia zep in e-4,5-d ica r boxyla tes (5′p ): 20% (from 3p and
4), mp 132-134 °C, IR (KBr) 1730, 1660, 1589 cm-1, 1H NMR
(CDCl3) δ 1.83 (3H, s), 2.39 (3H, s), 3.82 (3H, s), 3.86 (3H, s),
4.86 (1H, q, J ) 6.0, 7.0 Hz), 5.86 (1H, br d, J ) 6.0 Hz), 6.49
(1H, d, J ) 7.0 Hz), 7.48 (1H, s), 7.1-7.9 (5H, m). Anal. Calcd
for C20H20N2O4S: C, 62.48; H, 5.24; N, 7.29%. Found: C,
62.43; H, 5.18; N, 7.22%.
Dim et h yl 4-(p -(d im et h yla m in o)p h en yl)-5-t h ia -2,3-d i-
a za tr icyclo[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r box-
yla tes (7g): 13% (from 3g and 4), mp 115-117 °C, IR (KBr)
1
1736, 1716, 1606 cm-1, H NMR (CDCl3) δ 2.98 (6H, s), 3.71
(3H, s), 3.83 (3H, s), 4.16 (1H, d, J ) 3.0 Hz), 4.62 (1H, q, J )
3.0, 5.0 Hz), 6.20 (1H, q, J ) 3.0, 6.0 Hz), 7.47 (1H, d, J ) 5.0
Hz), 6.5-7.9 (5H, m). Anal. Calcd for C20H21N3O4S: C, 60.13;
H, 5.30; N, 10.52%. Found: C, 60.35; H, 5.21; N, 10.38%.
Dim eth yl 9-m eth yl-4-p h en yl-5-th ia -2,3-d ia za tr icyclo-
[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7h ):
30% (from 3h and 4), mp 216-218 °C, IR (KBr) 1732, 1705,
1645, 1616 cm-1, 1H NMR (CDCl3) δ 1.98 (3H, s), 3.71 (3H, s),
3.82 (3H, s), 4.11 (1H, d, J ) 3.0 Hz), 4.37 (1H, d, J ) 5.0 Hz),
5.75 (1H, br s), 7.55 (1H, d, J ) 5.0 Hz), 7.3-8.0 (5H, m). Anal.
Calcd for C19H18N2O4S: C, 61.61; H, 4.90; N, 7.56%. Found:
C, 61.63; H, 4.98; N, 7.68%.
Dim eth yl 2-(p-m eth oxyp h en yl)-6-m eth yl-5a H-p yr id o-
[1,2-d ][1,3,4]th ia d ia zep in e-4,5-d ica r boxyla tes (5′q): 27%
(from 3q and 4), mp 94-95 °C, IR (KBr) 1734, 1655, 1602 cm-1
,
1H NMR (CDCl3) δ 1.83 (3H, s), 3.81 (3H, s), 3.85 (6H, s), 4.84
(1H, q, J ) 6.0, 7.0 Hz), 5.85 (1H, br d, J ) 6.0 Hz), 6.48 (1H,
d, J ) 7.0 Hz), 7.45 (1H, s), 6.7-7.9 (5H, m). Anal. Calcd for
C20H20N205S: C, 59.99; H, 5.03; N, 7.00%. Found: C, 60.07;
H, 5.13; N, 6.93%.
Dim eth yl 9-m eth yl-4-(p-tolyl)-5-th ia -2,3-d ia za tr icyclo-
[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7i):
18% (from 3i and 4), mp 228-230 °C, IR (KBr) 1740, 1716,
1647, 1614 cm-1, 1H NMR (CDCl3) δ 2.00 (3H, s), 2.39 (3H, s),
3.74 (3H, s), 3.85 (3H, s), 4.12 (1H, d, J ) 3.0 Hz), 4.40 (1H, d,
J ) 5.0 Hz), 5.80 (1H, br s), 7.61 (1H, d, J ) 5.0 Hz), 7.0-7.9
(4H, m). Anal. Calcd for C20H20N2O4S: C, 62.48; H, 5.24; N,
7.29%. Found: C, 62.42; H, 5.37; N, 7.20%.
Dim eth yl 2-(p-ch lor op h en yl)-6-m eth yl-5a H-p yr id o[1,2-
d][1,3,4]th iadiazepin e-4,5-dicar boxylates (5′r ): Trace (from
1
3r and 4), H NMR (CDCl3) δ 1.82 (3H, s), 3.85 (3H, s), 3.87
(3H, s), 4.86 (1H, q, J ) 6.0, 7.0 Hz), 5.81 (1H, br d, J ) 6.0
Hz), 6.42 (1H, d, J ) 7.0 Hz), 7.56 (1H, s), 7.2-7.9 (5H, m).
The preparation of pure sample for 5′r was unsuccessful
because of its low yield.
Dim et h yl 4-(p -m et h oxyp h en yl)-9-m et h yl-5-t h ia -2,3-
d ia za t r icyclo[4.3.2.02,7]u n d eca -3,8,10-t r ien e-6,11-d ica r -
boxyla tes (7j): 22% (from 3j and 4), mp 250-252 °C, IR (KBr)
Dim eth yl 6-m eth yl-2-(2-th ien yl)-5aH-pyr ido[1,2-d][1,3,4]-
th ia d ia zep in e-4,5-d ica r boxyla tes (5′s): 22% (from 3s and
4), mp 146-148 °C, IR (KBr) 1722, 1653, 1564 cm-1, 1H NMR
(CDCl3) δ 1.83 (3H, s), 3.81 (3H, s), 3.85 (6H, s), 4.84 (1H, q,
1
1732, 1711, 1649, 1605 cm-1, H NMR (CDCl3) δ 1.99 (3H, s),
3.72 (3H, s), 3.82 (6H, s), 4.10 (1H, d, J ) 3.0 Hz), 4.36 (1H, d,
J ) 5.0 Hz), 5.77 (1H, br s), 7.55 (1H, d, J ) 5.0 Hz), 6.7-7.9

Preparation of New Nitrogen-Bridged Heterocycles
J . Org. Chem., Vol. 62, No. 22, 1997 7793
(4H, m). Anal. Calcd for C20H20N205S: C, 59.99; H, 5.03; N,
7.00%. Found: C, 59.96; H, 5.08; N, 7.05%.
yla tes (7r ): 11% (method A) or 6% (method B) (from 3r and
4), mp 244-246 °C, IR (KBr) 1732, 1716, 1643, 1620 cm-1, 1H
NMR (CDCl3) δ 1.85 (3H, s), 3.73 (3H,s), 3.86 (3H, s), 3.99 (3H,
s), 4.56 (1H, q, J ) 3.0, 5.0 Hz), 6.39 (1H, br s), 7.52 (1H, d, J
) 5.0 Hz), 7.2-7.9 (4H, m). Anal. Calcd for C19H17ClN2O4S:
C, 56.37; H, 4.23; N, 6.92%. Found: C, 56.45; H, 4.32; N,
6.74%.
Dim et h yl 4-(o-m et h oxyp h en yl)-9-m et h yl-5-t h ia -2,3-
d ia za t r icyclo[4.3.2.02,7]u n d eca -3,8,10-t r ien e-6,11-d ica r -
boxyla tes (7k ): 1% (from 3k and 4), mp 247-249 °C, IR (KBr)
1
1732, 1711, 1604 cm-1, H NMR (CDCl3) δ 1.99 (3H, s), 3.74
(3H, s), 3.85 (6H, s), 4.11 (1H, d, J ) 3.0 Hz), 4.38 (1H, d, J )
5.0 Hz), 5.77 (1H, br s), 7.53 (1H, d, J ) 5.0 Hz), 6.8-7.9 (4H,
m). Anal. Calcd for C20H20N205S: C, 59.99; H, 5.03; N, 7.00%.
Found: C, 60.17; H, 5.01; N, 6.84%.
Dim eth yl 8-m eth yl-4-(2-th ien yl)-5-th ia-2,3-diazatr icyclo-
[4.3.2.02,7
]u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7s):
16% (method A) or 11% (method B) (from 3s and 4), mp 199-
201 °C, IR (KBr) 1734, 1716, 1639, 1612 cm-1, 1H NMR (CDCl3)
δ 1.85 (3H, s), 3.71 (3H,s), 3.83 (3H, s), 4.01 (1H, s), 4.55 (1H,
q, J ) 3.0, 5.0 Hz), 6.37 (1H, br s), 6.9-7.7 (4H, m). Anal.
Calcd for C17H16N2O4S2: C, 54.24; H, 4.28; N, 7.44%. Found:
C, 54.29; H, 4.24; N, 7.50%.
Dim eth yl 5a-m eth yl-2-ph en yl-5aH-[1,3,4]th iadiazepin o-
[4,5-a ]qu in olin e-4,5-d ica r boxyla tes (8a ): 41% (from 3t and
4), mp 122-127 °C, IR (KBr) 1732, 1649, 1599 cm-1, 1H NMR
(CDCl3) δ 1.76 (3H, s), 3.86 (3H,s), 3.89 (3H, s), 5.99 (1H, d, J
) 10.0 Hz), 6.53 (1H, d, J ) 10.0 Hz), 6.5-8.6 (9H, m). Anal.
Calcd for C23H20N2O4S: C, 65.70; H, 4.79; N, 6.66%. Found:
C, 65.63; H, 4.87; N, 6.55%.
Dim et h yl 4-(p -ch lor op h en yl)-9-m et h yl-5-t h ia -2,3-d i-
a za tr icyclo[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r box-
yla tes (7l): 8% (from 3l and 4), mp 149-151 °C, IR (KBr)
1
1747, 1716, 1651, 1614 cm-1, H NMR (CDCl3) δ 2.00 (3H, s),
3.75 (3H, s), 3.87 (3H, s), 4.13 (1H, d, J )3.0 Hz), 4.40 (1H, d,
J ) 5.0 Hz), 5.80 (1H, br s), 7.61 (1H, d, J ) 5.0 Hz), 7.2-7.9
(4H, m). Anal. Calcd for C19H17ClN2O4S: C, 56.37; H, 4.23;
N, 6.92%. Found: C, 56.54; H, 4.25; N, 6.73%.
Dim eth yl 9-m eth yl-4-(2-th ien yl)-5-th ia-2,3-diazatr icyclo-
[4.3.2.02 ,7 ]u n d e c a -3,8,10-t r ie n e -6,11-d ic a r b o x y la t e s
(7m ): 35% (from 3m and 4), mp 209-211 °C, IR (KBr) 1730,
1
1703, 1645, 1614 cm-1, H NMR (CDCl3) δ 1.98 (3H, s), 3.73
(3H, s), 3.83 (3H, s), 4.14 (1H, d, J ) 3.0 Hz), 4.38 (1H, d, J )
5.0 Hz), 5.75 (1H, br s), 6.8-7.8 (4H, m). Anal. Calcd for
C17H16N2O4S2: C, 54.24; H, 4.28; N, 7.44%. Found: C, 54.16;
H, 4.34; N, 7.57%.
Dim et h yl 5a -m et h yl-2-(2-t h ien yl)-5a H -[1,3,4]t h ia d i-
azepin o[4,5-a ]qu in olin e-4,5-dicar boxylates (8b): 43% (from
3u and 4), mp 115-117 °C, IR (KBr) 1732, 1643, 1597 cm-1
,
1H NMR (CDCl3) δ 1.74 (3H, s), 3.80 (3H,s), 3.85 (3H, s), 5.87
(1H, d, J ) 10.0 Hz), 6.49 (1H, d, J ) 10.0 Hz), 6.5-7.4 (5H,
m), 7.59 (1H, d, J ) 5.0 Hz), 7.85 (1H, d, J ) 4.0 Hz). Anal.
Calcd for C21H18N2O4S2: C, 59.14; H, 4.25; N, 6.57%. Found:
C, 59.34; H, 4.41; N, 6.31%.
Dim et h yl 4-(p -(Dim et h yla m in o)p h en yl)-9-m et h yl-5-
th ia -2,3-d ia za tr icyclo[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-
d ica r boxyla tes (7n ): 27% (from 3n and 4), mp 219-221 °C,
1
IR (KBr) 1736, 1716, 1606 cm-1, H NMR (CDCl3) δ 1.98 (3H,
s), 2.98 (6H, s), 3.73 (3H, s), 3.81 (3H, s), 4.10 (1H, d, J ) 3.0
Hz), 4.33 (1H, d, J ) 5.0 Hz), 5.76 (1H, br s), 7.53 (1H, d, J )
5.0 Hz), 6.5-7.9 (4H, m). Anal. Calcd for C21H23N3O4S: C,
61.00; H, 5.61; N, 10.16%. Found: C, 60.94; H, 5.55; N,
10.28%.
Cr ysta llogr a p h y of Dim eth yl 6-Meth yl-2-p h en yl-5a H-
pyr ido[1,2-d][1,3,4]th iadiazepin e-4,5-dicar boxylate (5′o).12
A single crystal (0.46 × 0.78 × 1.00 mm) grown from CHCl3-
hexane was used for the unit-cell determinations and the data
collections of a Rigaku AFC5S four-circle diffractometer, with
graphite-monochromated Mo KR radiation (λ ) 0.71069 Å).
Crystal data of 5′o: C19H18N2O4S; M ) 370.42; monoclinic,
space group P21/c (no. 14), Z ) 4 with a ) 12.210(3) Å, b )
7.551 (4) Å, c ) 19.538(2) Å; b ) 94.29 (1)°; V ) 1796.2 (7) Å,3
and Dcalc ) 1.370 g/cm3. All calculations were performed using
the TEXSAN program.13 The structure was solved by a direct
method (MITHRIL).14 The non-hydrogen atoms were refined
anisotropically and the hydrogen atoms isotropically. The final
R- and Rw-factors after full-matrix least-squares refinements
were 0.045 and 0.050 for 2883 observed reflections.
Cr ysta llogr a p h y of Dim eth yl 5a -Meth yl-2-p h en yl-5a H-
[1,3,4]- th ia d ia zep in o[4,5-a ]qu in olin e-4,5-d ica r boxyla te
(8a ).12 A single crystal (0.04 × 0.22 × 0.64 mm) grown from
CHCl3-hexane was used for the unit-cell determinations and
the data collections of a Rigaku AFC5S four-circle diffracto-
meter, with graphite-monochromated Mo KR radiation (λ )
0.71069 Å). Crystal data of 8a : C23H20N2O4S; M ) 420.48;
orthorhombic, space group Pbca (no. 61), Z ) 8 with a )
19.18(3) Å, b ) 25.827(6) Å, c ) 8.694(6) Å; V ) 4307(7) Å,3
and Dcalc ) 1.297 g/cm3. All calculations were performed using
the TEXSAN program.13 The structure was solved by a direct
method (MITHRIL).14 The non-hydrogen atoms were refined
anisotropically, and the hydrogen atoms were not refined. The
final R- and Rw-factors after full-matrix least-squares refine-
ments were 0.055 and 0.063 for 866 observed reflections.
Dim eth yl 8-m eth yl-4-p h en yl-5-th ia -2,3-d ia za tr icyclo-
[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7o):
13% (method A) or 10% (method B) (from 3o and 4), mp 171-
173 °C, IR (KBr) 1734, 1718, 1639, 1616 cm-1, 1H NMR (CDCl3)
δ 1.85 (3H, s), 3.74 (3H, s), 3.86 (3H, s), 4.02 (1H, s), 4.54 (1H,
q, J ) 3.0, 5.0 Hz), 6.39 (1H, br s), 7.55 (1H, d, J ) 5.0 Hz),
7.3-8.0 (5H, m). Anal. Calcd for C19H18N2O4S: C, 61.61; H,
4.90; N, 7.56%. Found: C, 61.84; H, 4.94; N, 7.29%.
Dim eth yl 8-m eth yl-4-(p-tolyl)-5-th ia -2,3-d ia za tr icyclo-
[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r boxyla tes (7p ):
16% (method A) or 9% (method B) (from 3p and 4), mp 239-
241 °C, IR (KBr) 1734, 1716, 1639, 1612 cm-1, 1H NMR (CDCl3)
δ 1.87 (3H, s), 2.40 (3H,s), 3.74 (3H, s), 3.88 (3H, s), 4.02 (1H,
s), 4.58 (1H, q, J ) 3.0, 5.0 Hz), 6.41 (1H, br s), 7.57 (1H, d, J
) 5.0 Hz), 7.1-7.9 (4H, m). Anal. Calcd for C20H20N2O4S: C,
62.48; H, 5.24; N, 7.29%. Found: C, 62.41; H, 5.24; N, 7.28%.
Dim et h yl 4-(p -m et h oxyp h en yl)-8-Met h yl-5-t h ia -2,3-
d ia za t r icyclo[4.3.2.02,7]u n d eca -3,8,10-t r ien e-6,11-d ica r -
boxyla tes (7q): 27% (method A) or 11% (method B) (from
3q and 4), mp 215-217 °C, IR (KBr) 1744, 1717, 1641, 1605
cm-1 1H NMR (CDCl3) δ 1.84 (3H, s), 2.40 (3H,s), 3.71 (3H,
,
s), 3.82 (6H, s), 3.98 (1H, s), 4.53 (1H, q, J ) 3.0, 5.0 Hz), 6.41
(1H, br s), 7.50 (1H, d, J ) 5.0 Hz), 6.7-7.9 (4H, m). Anal.
Calcd for C20H20N205S: C, 59.99; H, 5.03; N, 7.00%. Found:
C, 60.14; H, 5.12; N, 6.84%.
Dim et h yl 4-(p -ch lor op h en yl)-8-m et h yl-5-t h ia -2,3-d i-
a za tr icyclo[4.3.2.02,7]u n d eca -3,8,10-tr ien e-6,11-d ica r box-
1
Su p p or tin g In for m a tion Ava ila ble: Copies of H NMR
spectra of compounds (3 pages). This material is contained
in libraries on microfiche, immediately follws this article in
the microfilm version of the journal, and can be ordered from
the ACS; see any current masthead page for ordering
information.
(12) The author has deposited atomic coordinates for this structure
with the Cambridge Crystallographic Data Centre. The coordinates
can be obtained, on request, from the Director, Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.
(13) “TEXSAN TEXRAY”, Structure Analysis Package," Molecular
Structure Corporation, 1985.
(14) Gilmore, C. J . J . Appl. Crystallogr. 1984, 17, 42.
J O971066O