Acyl Carbamoyl Selenides and Related Sulfur Isologues: Synthesis and X-Ray Structural Analyses

Article abstract of DOI:10.1002/hc.1040

Selenocarboxylic acids [RC(=O)SeH] were found to readily react with aryl, acyl, and arenesulfonyl isocyanates to give the corresponding acyl carbamoyl selenides 3 [RC(=O)SeC(=O)NHR', R'= aryl, C6H5CO, and 4-MeC6H4SO2] in good yields. Their tautomers [RC(=O)SeC(=NR')OH] were also detected by 1H, 13C, and 77Se NMR spectroscopies. The structure of 3 [R = 2,6-(MeO)2C6H3, R' = 4-MeC6H4] was characterized by X-ray crystallography, which showed that this molecule is stabilized by an intramolecular hydrogen bond between the carbonyl oxygen and the NH hydrogen to form a planar six-membered ring and by nonbonded interaction of ortho methoxy oxygen with the carbonyl oxygen or the selenium atoms. 4-Methoxybenzoyl and 4-methoxythiobenzoyl N-(4-methylphenyl)carbamoyl sulfides (4 and 5) were shown by X-ray crystallography to similarly have a planar intramolecular six-membered ring formed by a hydrogen bond between the carbonyl oxygen or thiocarbonyl sulfur and NH hydrogen atoms. The tautomers [RC(=E)SC(=NR')OH; E = O or S] of 4 and 5 also were detected spectroscopically. The recations of 3h (R = 4-MeOC6H4, R' = Ph) with sodium methoxide and p-toluidine gave sodium selenocarboxylate and the corresponding amides and urea as main products, respectively.

Full text of DOI:10.1002/hc.1040

Heteroatom Chemistry
Volume 12, Number 4, 2001
Acyl Carbamoyl Selenides and Related Sulfur
Isologues: Synthesis and X-Ray Structural
Analyses
Hideki Kageyama, Kazuyasu Tani, Shinzi Kato, and Takahiro Kanda
Department of Chemistry, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193,
Japan; shinzi@apchem.gifu-u.ac.jp
Received 12 December 2000; revised 18 January 2001
p-toluidine gave sodium selenocarboxylate and the
corresponding amides and urea as main products, re-
spectively. ᭧ 2001 John Wiley & Sons, Inc. Hetero-
atom Chem 12:250–258, 2001
ABSTRACT: Selenocarboxylic acids [RC(סO)SeH]
were found to readily react with aryl, acyl, and arene-
sulfonyl isocyanates to give the corresponding acyl
carbamoyl selenides 3 [RC(סO)SeC(סO)NHRЈ, RЈ ס
aryl, C6H5CO, and 4-MeC6H4SO2] in good yields. Their
tautomers [RC(סO)SeC(סNRЈ)OH] were also de-
tected by H, 13C, and 77Se NMR spectroscopies. The
structure of 3 [R ס 2,6-(MeO)2C6H3, RЈ ס 4-MeC6H4]
was characterized by X-ray crystallography, which
showed that this molecule is stabilized by an intra-
molecular hydrogen bond between the carbonyl oxygen
and the NH hydrogen to form a planar six-membered
ring and by nonbonded interaction of the ortho meth-
oxy oxygen with the carbonyl oxygen or the selenium
atoms. 4-Methoxybenzoyl and 4-methoxythiobenzoyl
N-(4-methylphenyl)carbamoyl sulfides (4 and 5) were
shown by X-ray crystallography to similarly have a pla-
nar intramolecular six-membered ring formed by a hy-
drogen bond between the carbonyl oxygen or thiocar-
bonyl sulfur and NH hydrogen atoms. The tautomers
[RC(סE)SC(סNRЈ)OH; E ס O or S] of 4 and 5 also
were detected spectroscopically. The reactions of 3h (R
ס 4-MeOC6H4, RЈ ס Ph) with sodium methoxide and
1
INTRODUCTION
In general, the isolation of carbamic carboxylic
mixed acid anhydrides I (E ס EЈ ס O) is difficult
due to the easy equilibrium between the starting
compounds (RCOOH and RЈNCO) and product
[RC(סO)OC(סO)NHRЈ] [1,2] (Figure 1).
Previously, we reported the isolation of a series
of dithiocarboxylic carbamic mixed acid anhydrides
I (E ס EЈ ס S) as crystals by reacting dithiocarbox-
ylic acids with aryl isocyanates [3]. Since then, sev-
eral carbamic thiocarboxylic mixed acid anhydrides
I (E ס O, EЈ ס S) have been reported by Motoki et
al. [4]. However, the synthesis of other carbamic
chalcogenocarboxylic mixed acid anhydrides have
not been reported in the literature. This is most likely
Correspondence to: Shinzi Kato.
Contract Grant Sponsor: Ministry of Education, Science, Sports
and Culture of Japan.
Contract Grant Number: Grant-in-Aid for Scientific Research
on Priority Areas No. 10133221.
Contract Grant Sponsor: Ministry of Education, Science, Sports
and Culture of Japan.
Contract Grant Number: Grants-in-Aid for Scientific Research
No. 09355032.
᭧ 2001 John Wiley & Sons, Inc.
FIGURE 1
250

Acyl Carbamoyl Selenides and Related Sulfur Isologues 251
due to the difficulty of synthesizing chalcogenocar-
boxylic acids themselves [5]. Our successful isola-
tion of selenocarboxylic acids [6] prompted us to
synthesize carbamic selenocarboxylic mixed acid
anhydrides. We report here the first isolation of car-
bamic selenocarboxylic mixed acid anhydrides and
their structures which were determined by X-ray
structural analyses.
iphatic derivatives (3a–c) appear to be more labile
than the aromatic derivatives (3d–n). Acetyl N-phen-
ylcarbamoyl selenide 3a decomposed at room tem-
perature even under an argon atmosphere. There-
fore, these aliphatic derivatives were not subjected
to elemental analysis.
Spectra
Previously, we reported that the NH proton chemical
shifts in thioacyl carbamoyl sulfides (I, E ס EЈ ס S)
appeared at unusually low fields, below d 12, indi-
cating the presence of an intramolecular CסS•••HN
hydrogen bond [3]. As shown in Table 1, the chemi-
cal shifts of the NH proton appear in the range of d
9–12, indicative of an intramolecular hydrogen bond
between the carbonyl oxygen and the NH hydrogen.
The carbonyl and carbamoyl carbon chemical shifts
are observed in the ranges of d 194–216 and d 156–
160, respectively. The 77Se NMR signals appear at d
630–730. Thus, these spectral data indicate that 3
exists as structure IIa (Figure 2).
RESULTS AND DISCUSSION
When a diethyl ether solution of phenyl isocyanate
was added to an equimolar amount of 4-methoxy-
benzenecarboselenoic acid in the same solvent at
room temperature, the orange solution of the selen-
ocarboxylic acid quickly changed to a colorless sus-
pension. Removal of the solvent and recrystalliza-
tion of the resulting residue from dichloromethane/
hexane gave the expected 4-methoxybenzoyl
N-phenylcarbamoyl selenide 3h in 95% yield as col-
orless crystals. Similarly, the reactions of other se-
lenocarboxylic acids with aryl isocyanates gave the
corresponding acyl carbamoyl selenides (3a–g, k–n)
in isolated yields of 35–99% (Scheme 1). In addition,
the reactions with benzoyl and p-tosyl isocyanates
proceeded more quickly to give the corresponding N-
benzoyl-3i and N-(p-tosyl)carbamoyl selenides 3j.
The structures of the products reported herein were
1
However, in the H NMR spectrum of 3a, two
broad signals at d 9.15 and d 9.91 (proton ratio ס
1:10) was observed, which are attributable to OH
and NH protons, respectively. No appreciable
change in the proton ratio was observed in the range
20ꢀC to מ60ꢀC. The 13C NMR spectra, except for the
signals at d 156.2 (CONH) and d 202.7 (COSe) in IIaa
(Table 2), also show small signals at d 160.9 and d
194.6, which are attributable to the CסN and COSe
groups, respectively. In addition, in 77Se NMR spec-
troscopy, a small sharp signal is observed at d 835.
These results apparently indicate the existence of a
1
established by IR and H and 13C NMR spectra and
by elemental and X-ray structural analyses.
The resulting mixed acid anhydrides 3 are col-
orless crystals or colorless oils and are relatively sta-
ble thermally and insensitive toward oxygen. The al-
1
tautomer (IIab) of IIaa. In the H NMR spectra of
other selenides (3b, d, h–l), small or negligible sig-
nals of the corresponding tautomers IIb are ob-
served. Table 2 shows the proton ratios of NH in IIa
1
and OH in IIb. We also obtained H and 13C NMR
spectra, which indicate the existence of the tauto-
mers IIIb and IVb for the previously reported sulfur
isologues (I, E ס O, EЈ ס S [4] and E, EЈ ס S [3]):
4-methoxybenzoyl 4 and 4-methoxythiobenzoyl N-
(4-methylphenyl)carbamoyl sulfides 5 (Figure 3).
The proton ratios of IIIa and IIIb in 4 and IVa and
IVb in 5 were 4:1 and 20:1, respectively.
SCHEME 1
RC(O)SeC(O)NHRЈ
No.
R
RЈ
Yield [%]
3a
3b
3c
3d
3e
3f
3g
3h
3i
CH3
i-C4H9
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5CO
4-CH3C6H4SO2
4-CH3C6H4
C6H5
35
95
78
99
93
93
92
95
61
97
100
97
92
93
1-Adamantyl
C6H5
2-CH3C6H4
4-CH3C6H4
2-CH3OC6H4
4-CH3OC6H4
X-Ray Structure
To confirm the intramolecular hydrogen bond, the
X-ray structural analysis of 3 was carried out. To our
knowledge, no structural analysis of acyl or thioacyl
carbamoyl chalcogenides has been described in the
literature. After several attempts to obtain acyl car-
bamoyl selenides 3 as single crystals, 2,6-dimethox-
3j
3k
3l
3m
3n
2,6-(CH3O)2C6H3
3-Cl-2,6-(CH3O)2C6H2
4-C6H5C6H4
C6H5
C6H5
1-C10H7

252 Kageyama et al.
TABLE 1 Spectral Data of Acyl Carbamoyl Selenides 3
RC(O)SeC(O)NHRЈ
NMR (CDCl3) [d]
No.
R
RЈ
1H (NH)
13C(O)N
13C(O)Se
77Se
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
CH3
t-C4H9
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5CO
4-CH3C6H4SO2
4-CH3C6H4
C6H5
9.91
10.05
10.10
10.41
10.27
10.45
10.61
10.51
10.51
11.54
10.07
10.05
10.46
10.36
156.2
156.4
156.8
156.0
157.0
156.3
159.3
156.4
157.4
157.3
156.5
157.6
156.1
157.1
202.7
215.6
215.3
199.7
201.8
198.9
197.4
197.1
197.6
194.8
199.9
199.3
198.9
201.9
687.5
639.1
—
648.4
678.4
642.6
708.1
632.7
—
—
—
726.1
—
—
1-Adamantyl
C6H5
2-CH3C6H4
4-CH3C6H4
2-CH3OC6H4
4-CH3OC6H4
2,6-(CH3O)2C6H3
3-Cl-2,6-(CH3O)2C6H2
4-C6H5C6H4
C6H5
C6H5
1-C10H7
FIGURE 2
TABLE 2 Ratio of Tautomers IIa and IIb
FIGURE 3
No.
R
RЈ
IIa
IIb
respectively, and the O1–H1–N1 bond angle is 173.0ꢀ,
indicating the presence of a hydrogen bond between
the carbonyl oxygen (O1) and the NH hydrogen (H1).
Torsion angles [3.2(9)ꢀ for N1–C11–Se1–C1, 0.5(9)ꢀ
for O1–C1–Se1–C11 and 8ꢀ for Se1–C11–N1–H1] in-
dicate that the selenocarboxyl group and carbamoyl
group are in approximately the same plane to give a
planar intramolecular six-membered ring. In addi-
3a
3b
3d
3e
3f
3g
3h
3i
CH3
t-C4H9
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
8 (IIaa)
12 (IIba)
20 (IIda)
9 (IIea)
30 (IIfa)
50 (IIga)
30 (IIha)
12 (IIla)
1 (IIab)
1 (IIbb)
1 (IIdb)
1 (IIeb)
1 (IIfb)
1 (IIgb)
1 (IIhb)
1 (IIlb)
2-CH3C6H4
4-CH3C6H4
2-CH3OC6H4
4-CH3OC6H4
3-Cl-2,6-(CH3O)2C6H2
˚
tion, the O3–O1 [2.722(7) A] and O4–Se1 [2.959(7)
˚
A] distances are remarkably short compared with
˚
˚
the sum [3.04 A for O–O; 3.42 A for O–Se [7]) of the
van der Waals radii of both the atoms, respectively,
suggesting the presence of nonbonded repulsion and
nonbonded attraction.
ybenzoyl N-(4-methylphenyl)carbamoyl selenide 3k
afforded suitable crystals for X-ray analysis. The mo-
lecular structure is shown in Figure 4. The final
atomic positional parameters are listed in Table 3.
Selected bond distances and angles are shown in Ta-
For comparison with the structures of previously
isolated sulfur isologues [RC(סO/S)SC(סO)RЈ], the
X-ray structural analyses of 4-methoxybenzoyl 4 and
˚
ble 4. The C1–O1 [1.204(10) A] and C11–O2 [1.20(1)
˚
A] distances indicate double bonds. The C11–N1
4-methoxythiobenzoyl
N-(4-methylphenyl)carba-
˚
˚
[1.34(1) A], C12–N1 [1.436(9) A], C1–Se1 [1.935(10)
moyl sulfides 5 were carried out. Their molecular
structures are shown in Figure 4 (b and c). Selected
bond lengths and angles are shown in Table 3. As
expected, they have an intramolecular six-mem-
˚
˚
A], and C11–Se1 distances [1.965(9) A] are normal,
indicating single bonds. The O1–N1, N1–H1, and
˚
˚
˚
O1–H1 distances are 2.76(2) A, 0.88 A, and 1.89 A,

Acyl Carbamoyl Selenides and Related Sulfur Isologues 253
EXPERIMENTAL
The melting points were determined by a Yanagi-
moto micromelting point apparatus and are uncor-
rected. The IR spectra were measured on a PERKIN
1
ELMER FT-IR 1640 instrument. The H NMR spec-
tra were recorded on JEOL JNM-GX-270 (270 MHz)
and JEOL ␣-400 (399.7 MHz) instruments with
Me4Si as an internal standard. The 13C NMR spectra
were obtained by use of JEOL JNM-GX-270 (68
MHz) and JEOL ␣-400 (100.4 MHz) instruments
with CDCl3 as an internal standard. The 77Se NMR
spectra were obtained by use of a JEOL ␣-400 (76.2
MHz) instrument with Me2Se as an external stan-
dard. Elemental analyses were performed by the El-
emental Center of Kyoto University.
Materials
The following reagents were of commercial grade
and used without further purification: phenyl, 4-
methylphenyl, and p-toluenesulfonyl isocyanates,
and p-toluidine (from Tokyo Kasei) and hydrogen
chloride (1.0 M solution in diethyl ether) (from Al-
drich). Benzoyl isocyanate [8], selenocarboxylic ac-
ids [5,6], 4-methoxybenzenecarbothioic acid [9], and
4-methoxybenzenecarbodithioic acid [10] were pre-
pared according to the literature. Dichloromethane
was distilled from diphosphorus pentaoxide and de-
gassed. Diethyl ether was distilled from sodium di-
phenylketyl and degassed. Hexane was distilled from
sodium metal prior to use and degassed. All of the
manipulations were carried out under argon.
FIGURE 4 The structures of 2,6-dimethoxybenzoyl N-(4-
methylphenyl)carbamoyl selenide 3k, 4-methoxybenzoyl N-
(4-methylphenyl)carbamoyl sulfide 4, and 4-methoxythiob-
enzoyl N-(4-methylphenyl)carbamoyl sulfide 5. The atoms
are drawn with 50% probability thermal ellipsoids.
bered ring structure formed by a hydrogen bond be-
tween the carbonyl oxygen or thiocarbonyl sulfur
and the NH hydrogen atoms, respectively. Presum-
ably, this might contribute to the overall stability of
the molecules. Attempts to obtain single crystals of
the tautomers, IIb, IIIb, and IVb failed.
3-Chloro-2,6-dimethoxybenzenecarboselenoic
Acid (1l)
1
Yellow oil; H NMR (CDCl3): d 3.29 (br, 1H, SeH),
3.85 (s, 3H, CH3O), 3.91 (s, 3H, CH3O), 6.67 (d, J ס
8.1 Hz, 1H), 7.35 (d, J ס 8.1 Hz, 1H); 13C NMR
(CDCl3): d 56.3 (CH3O), 62.5 (CH3O), 108.1, 119.8,
128.4, 132.2, 152.0, 154.4, 189.7 (CO).
Reactions
The reaction of 3h with sodium methoxide in diethyl
ether readily proceeded at room temperature to give
sodium 4-methoxybenzenecarboselenoate 6 and
methyl N-phenylcarbamate 7 in good yields (Scheme
2).
The reaction with two equimolar amounts of p-
toluidine under similar conditions gave N-4-meth-
ylphenyl 4-methoxybenzamide 8 and N-4-methyl-
phenyl NЈ-phenyl urea 9 in moderate yields (Scheme
2). Compound 8 may be formed by decomposi-
tion of 4-methoxyselenocarboxylic acid 4-meth-
4-Biphenylcarboselenoic Acid (1m)
Red solid; IR (KBr): 2290 (SeH) cmמ1 [15], dec.: 54–
1
56ꢀC; H NMR (CDCl3): d 4.85 (br, 1H, SeH), 7.38–
8.24 (m, 9H); 13C NMR (CDCl3): d 127.8, 127.9, 128.0,
128.9, 129.1, 129.7, 129.8, 131.1, 203.2 (CO).
X-Ray Structure Analysis
מ
ylphenylammonium salt [4-MeOC6H4C(סO)Se
ם
NH2C6H4Me-4]. These results indicate that nucleo-
All measurement were carried out on a Rigaku
AFC7R diffractometer with graphite monochro-
philes, such as alkoxides and amines, preferentially
attack the carbamoyl carbon rather than the car-
bonyl carbon in 3.
˚
mated MoK␣ radiation (k ס 0.71069 A). All of the
structures were solved and refined using the teXsan

254 Kageyama et al.
TABLE 3 Crystal Data and Experimental Crystallographic Details for Compounds 3k, 4, and 5
Compound
3k
4
5
Empirical formula
M
C17H17NO4Se
378.29
0.34 ן 0.13 ן 0.13
colorless/needle
orthorhombic
Pna21
13.976(1)
8.520(1)
13.753(2)
C16H15NO3S
301.36
0.20 ן 0.20 ן 0.30
colorless/needle
triclinic
C16H15NO2S2
317.42
0.34 ן 0.13 ן 0.13
orange/needle
monoclinic
P21/n
4.101(4)
21.076(3)
17.731(3)
Crystal size
Color/shape
Crystal system
Space group
P1
˚
a/A
12.389(3)
15.489(3)
4.132(2)
91.19(3)
90.80(3)
112.89(1)
730.1(4)
2
˚
b/A
˚
c/A
␣/ꢀ
b/ꢀ
c/ꢀ
94.65(4)
3
˚
V/A
1637.6(3)
4
1527(1)
4
Z
F(000)
D0/g cm
l(MoK␣)/cm
Temp (ꢀC)
2h max (ꢀ)
768.00
1.534
23.12
23 ע 1
55.0
316.00
1.371
2.31
23 ע 1
55.0
16.0
664.00
1.380
3.51
23 ע 1
55.0
מ3
מ1
מ1
Scan Rate (ꢀ min
)
16.0
16.0
Data collected
Total data collected, unique,
observed
םh, םk, םl
2170, 1954, 1170
(l ꢁ 2r(l))
209
0.086, 0.125
1.02
םh, עk, עl
3502, 3344, 1681
(l ꢁ 2r(l))
190
0.060, 0.066
1.28
םh, םk, עl
4112, 3624, 1158
(l ꢁ 2r(l))
190
0.092, 0.220
1.09
No. of variable
Residuals: R1: wRa
Goodness of fit
מ3
˚
Final diff. map max, min (e A
)
מ0.60, 0.55
מ0.24, 0.23
מ0.58, 0.58
aR1 ס R࿣F0| מ |F0࿣/R |F0| (for l ꢁ 2.0r(l) data), wR ס [(Rw(F20 מ F2c)2/Rw(F02)2)]1/2, where w ס 1/r2(F02).
crystallographic software package. The cell dimen-
sions were determined by a least-squares refinement
of the diffractometer angles for 25 automatically
centered reflections. Three standard reflections were
measured every 150 reflections, and no decay was
detected. An empirical absorption correction (W
Scan) was applied. The structures were solved by di-
rect methods (SHELXS86) [11] and expanded using
DIRDIF94 [12]. Scattering factors for neutral atoms
were from Cromer and Waber [13], and anomalous
dispersion [14] was used. A full-matrix least-squares
refinement was executed with nonhydrogen atoms
being anisotropic. The final least-squares cycle in-
cluded fixed hydrogen atoms at calculated positions
of which each isotropic thermal parameter was set
to 1.2 times that of the connecting atom. Crystal data
and measurement description are summarized in
Table 3.
sulfide 4 was crystallized from CH2Cl2/hexane (1:5)
at 23ꢀC for three days. 4-Methoxythiobenzoyl N-(4-
methylphenyl)carbamoyl sulfide 5 was crystallized
from CHCl3/hexane (1:2) at 23ꢀC for two days. These
crystal samples were cut from grown crystals, coated
with an epoxy resin, and mounted on a glass fiber.
Synthesis of Acyl Carbamoyl Selenides (3)
The synthesis of 4-methoxybonzoyl N-phenylcarba-
moyl selenide 3h is described in detail as a typical
procedure.
To a solution of sodium 4-methoxybenzenecar-
boselenoate (0.89 g, 3.0 mmol) in diethyl ether (10
mL), contained in a 20 mL two-necked round-bot-
tom flask, 1.0 M hydrogen chloride in diethyl ether
(2.6 mL) was added. The mixture was stirred at 0ꢀC
for 10 minutes. Filtration of the precipitates (NaCl
and excess of sodium 4-methoxybenzenecarbosele-
noate) and removal of the solvent under reduced
pressure (22ꢀC/53.3Pa) gave 0.56 g (2.6 mmol) of 4-
methoxybenzene-carboselenoic acid as yellow solid)
[5]. The solid was dissolved in diethyl ether (10 mL).
A solution of phenylisothiocyanate (0.30 g, 2.6
mmol) in diethyl ether (5.0 mL) was added and
Preparation of Single Crystals
2,6-Dimethoxylbenzoyl N-(4-methylphenyl)carba-
moyl selenide 3k was crystallized from diethyl ether/
hexane (1:1) at 18ꢀC during a period of four days.
4-Methoxybenzoyl
N-(4-methylphenyl)carbamoyl

Acyl Carbamoyl Selenides and Related Sulfur Isologues 255
˚
TABLE 4 Selected Bond Lengths (A) and Bond Angles (ꢀ) of 3k, 4, and 5
3k
Bond Lengths
Se1–C1
Se1–C11
O1–C1
O2–C11
N1–C11
N1–C12
1.935(10)
1.965(9)
1.204(10)
1.20(1)
N1–H1
0.88
2.76(2)
1.89
2.959(7)
2.722(7)
N1•••O1
O1•••H1
Se1•••O4
O1•••O3
1.34(1)
1.436(9)
Angles
Se1–C1–O1
C1–Se1–C11
Se1–C11–N1
121.9(6)
106.0(4)
116.2(6)
O2–C11–N1
C11–N1–C12
N1–H1•••O1
127.8(8)
124.7(8)
173.0
Torsion Angles
O1–C1–C2–C3
Se1–C1–C2–C7
N1–C11–Se1–C1
O1–C1–Se1–C11
48(1)
3.2(8)
0.5(9)
42(1)
0(1)
8
O2–C11–N1–C12
Se1–C11–N1–H1
4
5
Bond Lengths
1.791(3) N1–C11
1.817(4) N1–C12
1.218(4) N1–H1
1.202(4) N1•••O1
Bond Lengths
1.744(6) N1–C11
1.844(6) N1–C12
1.632(7) N1–H1
1.197(7) N1•••S2
S1–C1
1.334(4) S1–C1
1.422(4) S1–C11
1.322(8)
1.448(8)
0.95
S1–C11
O1–C1
O2–C11
0.85
S2–C1
2.705(3) O1–C11
3.062(5)
Angles
Angles
S1–C1–O1
C1–S1–C11
S1–C11–N1
122.8(3)
109.3(2)
117.2(3)
O2–C11–N1
C11–N1–C12
N1–H1•••O1
128.4(3)
127.5(3)
146.0
S1–C1–S2
C1–S1–C11
S1–C11–N1
128.0(4)
114.5(3)
117.3(5)
O1–C11–N1
C11–N1–C12
N1–H1•••S2
130.3(6)
126.6(6)
111.8
Torsion Angles
Torsion Angles
S1–C1–C2–C7
N1–C11–S1–C1
O1–C1–S1–C11
5.0(5)
3.9(3)
2.0(4)
O1–C1–C2–C3
O2–C11–N1–C12
S1–C11–N1–H1
4.8(5)
2.2(6)
10
S1–C1–C2–C7
N1–C11–S1–C1
S2–C1–S1–C11
20.6(8)
2.4(7)
6.3(6)
S2–C1–C2–C3
O1–C11–N1–C12
S1–C11–N1–H1
19.6(9)
5(1)
54
orless needles (35% yield); dec.: 81ꢀC; IR (KBr): 3252
מ1
(NH), 1715 (COSe), 1682 (CONH), 1557 (NH) cm
;
1H NMR (CDCl3): IIaa, d 2.50 (s, 3H, CH3), 7.15 (t, J
ס 7.6 Hz, 1H, NHPh), 7.35 (t, J ס 7.6 Hz, 2H,
NHPh), 7.53 (d, J ס 7.6 Hz, 2H, NHPh), 9.91 (br, 1H,
NH); IIab, d 2.54 (s, 3H, CH3), 9.15 (br, 1H, OH); 13
C
NMR (CDCl3): IIaa, d 35.0 (CH3), 119.9, 125.0, 129.2,
137.1, 156.2 (CONH), 203.7 (COSe); IIab, d 35.8
(CH3), 119.9, 124.8, 129.6, 137.4, 160.9 (CסN), 194.6
(COSe); 77Se NMR (CDCl3): IIaa, d 687.5; IIab, d
835.9. This compound is too unstable to subject in
elemental analysis.
SCHEME 2
stirred at 20ꢀC for 10 minutes (The color of the so-
lution changed from red to colorless). Removal of
the solvent under reduced pressure (22ꢀC/53.3Pa)
gave 0.81 g (95%) of crude 4-methoxybenzoyl N-
phenylcarbamoyl selenide 3h as a colorless solid. Re-
crystallization of the solid from a mixed solvent of
dichloromethane (3 mL) and hexane (1 mL) at
מ20ꢀC during 1 hour yielded 0.46 g (59%) of 3h as
colorless needles.
1,1-Dimethylethanecarbonyl N-Phenylcarbamoyl
Selenide (3b). Colorless oil (95% yield); IR (Neat):
3246 (NH), 1718 (COSe), 1670 (CONH), 1549 (NH)
cmמ1; 1H NMR (CDCl3): IIba, d 1.30 (s, 9H, CH3), 7.14
(t, J ס 7.9 Hz, 1H, NHPh), 7.34 (t, J ס 7.9 Hz, 2H,
NHPh), 7.53 (d, J ס 7.9 Hz, 2H, NHPh), 10.05 (br,
1H, NH); IIbb, d 1.32 (s, 9H, CH3), 7.07 (t, J ס 8.3
Hz, 2H), 7.27 (t, J ס 8.3 Hz, 1H), 7.53 (d, J ס 8.3
Acetyl N-Phenylcarbamoyl Selenide (3a). Col-

256 Kageyama et al.
Hz, 2H); 13C NMR (CDCl3): IIba, d 26.0 (CH3C), 50.8
(CH3C), 119.8, 124.9, 129.1, 137.1, 156.4 (CONH),
215.6 (COSe); 77Se NMR (CDCl3): IIba: d 639.1. This
compound is too unstable to be subject to elemental
analysis.
642.6. Anal. calcd for C15H13NO2Se: C, 56.61; H, 4.12.
Found: C, 56.60; H, 3.90.
2-Methoxybenzoyl N-Phenylcarbamoyl Selenide
(3g). Colorless crystals (92% yield); dec.: 95–97ꢀC;
IR (KBr): 3257 (NH), 1707 (COSe), 1614 (CONH),
1
1556 (NH) cmמ1; H NMR (CDCl3): IIga, d 4.00 (s,
1-Adamantanecarbonyl N-Phenylcarbamoyl Se-
3H, CH3O), 7.04 (d, J ס 7.7 Hz, 1H, C6H4CO), 7.08
(t, J ס 7.7 Hz, 1H, C6H4CO), 7.15 (t, J ס 7.5 Hz, 1H,
NHPh), 7.36 (t, J ס 7.5 Hz, 2H, NHPh), 7.59 (t, J ס
7.7 Hz, 1H, C6H4CO), 7.63 (d, J ס 7.5 Hz, 2H, NHPh),
7.87 (d, J ס 7.7 Hz, 1H, C6H4CO), 10.61 (br, 1H, NH):
IIgb, d 3.93 (s, 3H, CH3O); 13C NMR (CDCl3): IIga, d
55.7 (CH3O), 112.4, 120.1, 121.1, 124.8, 126.7, 129.2,
129.4, 135.9, 137.4, 159.3 (CONH), 160.2, 197.4
(COSe); 77Se NMR (CDCl3): IIga, d 708.1. Anal. calcd
for C15H13NO3Se: C, 53.90; H, 3.92. Found: C, 53.98;
H, 4.08.
lenide (3c).
Colorless crystals (78% yield); dec.:
103–105ꢀC; IR (KBr): 3229 (NH), 1715 (COSe), 1664
(CONH), 1555 (NH) cmמ1; H NMR (CDCl3): d 1.75
1
(br, 6H, Ad), 1.97 (br, 6H, Ad), 2.11 (br, 3H, Ad), 7.14
(t, J ס 7.7 Hz, 1H, NHPh), 7.34 (t, J ס 7.7 Hz, 2H,
NHPh), 7.55 (d, J ס 7.7 Hz, 2H, NHPh), 10.10 (br,
1H, NH); 13C NMR (CDCl3): d 28.0 (Ad), 36.2 (Ad),
38.9 (Ad), 53.1 (Ad), 119.9, 124.9, 129.2, 137.2, 156.8
(CONH), 215.3 (COSe). This compound is too unsta-
ble to be subject to elemental analysis.
Benzoyl N-Phenylcarbamoyl Selenide (3d). Col-
orless crystals (99% yield); dec.: 97–99ꢀC; IR (KBr):
3222 (NH), 1728 (COSe), 1645 (CONH), 1554 (NH)
4-Methoxybenzoyl N-Phenylcarbamoyl Selenide
(3h).
Colorless crystals (95% yield); dec.: 106–
108ꢀC; IR (KBr): 3224 (NH), 1728 (COSe), 1645
1
cmמ1; H NMR (CDCl3): IIda, d 7.18 (t, J ס 7.6 Hz,
1
(CONH), 1572 (NH) cmמ1; H NMR (CDCl3): IIha, d
1H, NHPh), 7.38 (t, J ס 7.6 Hz, 2H, NHPh), 7.53 (t,
J ס 7.9 Hz, 2H, PhCO), 7.61 (d, J ס 7.6 Hz, 2H,
NHPh), 7.69 (t, J ס 7.9 Hz, 1H, PhCO), 7.94 (d, J ס
7.9 Hz, 2H, PhCO), 10.41 (br, 1H, NH); IIdb, d 7.31
(t, J ס 7.3 Hz); 13C NMR (CDCl3): IIda, d 120.0, 125.1,
127.6, 129.2, 129.3, 135.2, 137.2, 138.0, 156.0
(CONH), 199.7 (COSe); 77Se NMR (CDCl3): IIda: d
648.4. Anal. calcd for C14H11NO2Se: C, 55.28; H, 3.64.
Found: C, 55.20; H, 3.57.
3.90 (s, 3H, CH3O), 6.98 (d, J ס 9.0 Hz, 2H, C6H4CO),
7.16 (t, J ס 7.8 Hz, 1H, NHPh), 7.37 (t, J ס 7.8 Hz,
2H, NHPh), 7.60 (d, J ס 7.8 Hz, 2H, NHPh), 7.91 (d,
J ס 9.0 Hz, 2H, C6H4CO), 10.51 (br, 1H, NH); IIhb,
d 3.86 (s, 3H, CH3O); 13C NMR (CDCl3): IIha, d 55.8
(CH3O), 114.5, 119.9, 124.9, 129.2, 130.2, 130.6,
137.3, 156.4 (CONH), 165.3, 197.1 (COSe); 77Se NMR
(CDCl3): IIha, d 632.7. Anal. calcd for C15H13NO3Se:
C, 53.90; H, 3.92. Found: C, 53.65; H, 4.02.
4-Methoxybenzoyl N-(Benzoyl)carbamoyl Selen-
ide (3i). Colorless crystals (61% yield); dec.: 81–
83ꢀC; IR (KBr): 3373 (NH), 1769 (COSe), 1642
2-Methylbenzoyl N-Phenylcarbamoyl Selenide
(3e). Colorless crystals (93% yield); dec.: 65–66ꢀC;
IR (KBr): 3225 (NH), 1718 (COSe), 1662 (CONH),
1
(CONH), 1574 (NH) cmמ1; H NMR (CDCl3): d 3.91
1
1549 (NH) cmמ1; H NMR (CDCl3): IIea: d 2.55 (s,
(s, 3H, CH3O), 7.00 (d, J ס 8.0 Hz, 2H, C6H4CO), 7.45
(t, J ס 7.8 Hz, 1H, NHPh), 7.58 (t, J ס 7.8 Hz, 2H,
NHPh), 7.93 (d, J ס 7.8 Hz, 2H, NHPh), 8.15 (d, J ס
8.0 Hz, 2H, C6H4CO), 10.51 (br, 1H, NH); 13C NMR
(CDCl3): d 55.8 (CH3O), 114.7, 128.3, 128.6, 130.0,
130.5, 131.1, 133.5, 157.4 (SeCONH), 162.7 (Ph-
CONH), 165.8, 197.6 (COSe).
3H, CH3), 7.10–7.80 (m, 9H), 10.27 (br, 1H, NH);
IIeb: d 2.51 (s, 3H, CH3), 9.04 (br, 1H, OH); 13C NMR
(CDCl3): IIea: d 20.9 (CH3), 120.0, 124.8, 125.1, 126.4,
129.2, 129.6, 132.3, 133.4, 137.0, 137.1, 157.0
(CONH), 201.8 (COSe); 77Se NMR (CDCl3): IIea: d
678.7. Anal. calcd for C15H13NO2Se: C, 56.61; H, 4.12.
Found: C, 56.36; H, 4.21.
4-Methoxybenzoyl N-(Tosyl)carbamoyl Selenide
(3j). Colorless crystals (97% yield); dec.: 99–100ꢀC;
IR (KBr): 3365 (NH), 1719 (COSe), 1646 (CONH),
4-Methylbenzoyl N-Phenylcarbamoyl Selenide
(3f). Colorless crystals (93% yield); dec.: 97–99ꢀC;
IR (KBr): 3219 (NH), 1693 (COSe), 1645 (CONH),
1547 (NH) cmמ1; 1H NMR (CDCl3): IIfa, d 2.43 (s, 3H,
CH3), 7.17 (t, J ס 7.9 Hz, 1H, NHPh), 7.31 (d, J ס
8.3 Hz, 2H, C6H4CO), 7.37 (t, J ס 7.9 Hz, 2H, NHPh),
7.61 (d, J ס 7.9 Hz, 2H, NHPh), 7.83 (t, J ס 8.3 Hz,
2H, C6H4CO), 10.45 (br, 1H, NH); IIfb, d 2.42 (s, 3H,
CH3); 13C NMR (CDCl3): IIfa, d 21.9 (CH3), 120.0,
125.0, 127.7, 129.2, 130.0, 135.5, 137.2, 146.7, 156.3
(CONH), 198.9 (COSe); 77Se NMR (CDCl3): IIfa, d
1
1509 (NH) cmמ1; H NMR (CDCl3): d 2.44 (s, 3H,
CH3), 3.90 (s, 3H, CH3O), 6.98 (d, J ס 8.5 Hz, 2H,
C6H4CO), 7.35 (d, J ס 8.0 Hz, 2H, C6H4SO2), 7.84 (d,
J ס 8.0 Hz, 2H, C6H4SO2), 8.00 (d, J ס 8.5 Hz, 2H,
C6H4CO), 11.54 (br, 1H, NH); 13C NMR (CDCl3): d 21.7
(CH3), 55.8 (CH3O), 114.7, 128.5, 128.6, 129.7, 129.8,
135.5, 145.5, 157.3 (CONH), 165.9, 194.8 (COSe).
Anal. calcd for C16H15NO5SSe: C, 46.61; H, 3.67.
Found: C, 46.74; H, 3.46.

Acyl Carbamoyl Selenides and Related Sulfur Isologues 257
2,6-Dimethoxybenzoyl N-(4-Methylphenyl)carba-
moyl Selenide (3k). Colorless needles (100% yield);
dec.: 118–122ꢀC; IR (KBr): 3231 (NH), 1695 (COSe),
Hz, 2H), 7.10 (d, J ס 8.3 Hz, 2H), 7.88 (d, J ס 7.7
Hz, 2H), 8.05 (d, J ס 7.7 Hz, 2H); 13C NMR (CDCl3):
IIIa, d 21.0 (CH3), 55.7 (CH3O), 114.4, 120.2, 124.5,
128.5, 129.7, 130.2, 134.7, 158.3 (CONH), 165.2,
191.9 (COS)
1
1654 (CONH), 1593, 1523 cmמ1; H NMR (CDCl3): d
2.33 (s, 3H, CH3), 3.83 (s, 6H, CH3O), 6.58 (d, J ס 7.3
Hz, 2H), 7.16 (d, J ס 6.7 Hz, 2H), 7.35 (t, J ס 6.7
Hz, 1H), 7.50 (d, J ס 7.3 Hz, 2H), 10.08 (br, 1H, NH);
13C NMR (CDCl3): d 20.9 (CH3), 56.2 (CH3O), 104.3,
120.0, 129.6, 133.1, 134.4, 134.9, 156.5, 158.3
(CONH), 199.9 (COSe). Anal. calcd for C17H17NO4Se:
C, 53.98; H, 4.53. Found: C, 53.84; H, 4.41.
4-Methoxythiobenzoyl N-(4-Methylphenyl)carba-
moyl Sulfide (5). Orange needles; dec.: 120–121ꢀC
[3]; IR (KBr): 3282 (NH), 1712 (CO), 1541 (NH),
1248 (CS) cmמ1; 1H NMR (CDCl3): IVa, d 2.34 (s, 3H,
CH3), 3.88 (s, 3H, CH3O), 6.91 (d, J ס 9.3 Hz, 2H),
7.17 (d, J ס 8.3 Hz, 2H), 7.49 (d, J ס 8.3 Hz, 2H),
8.05 (d, J ס 9.3 Hz, 2H), 11.51 (br, 1H, NH); IVb, d
2.31 (s, 3H, CH3), 3.86 (s, 3H, CH3O), 6.85 (d, J ס
8.8 Hz, 2H), 6.96 (d, J ס 8.3 Hz, 2H), 7.30 (d, J ס
8.3 Hz, 2H), 8.10 (d, J ס 8.8 Hz, 2H); 13C NMR
(CDCl3): IVa, d 21.0 (CH3), 55.7 (CH3O), 114.0, 120.3,
124.4, 129.5, 129.8, 130.1, 135.1, 158.2 (CONH),
165.0, 224.8 (CSS); IVb, d 20.8 (CH3), 55.7 (CH3O),
113.5, 120.1, 129.4, 129.5, 134.3, 138.2.
3-Chloro-2,6-dimethoxybenzoyl N-Phenylcarba-
moyl Selenide (3l). Colorless crystals (97% yield);
dec.: 84–86ꢀC; IR (KBr): 3240 (NH), 1714 (COSe),
1
1655 (CONH), 1547 (NH) cmמ1; H NMR (CDCl3):
IIIa, d 3.86 (s, 3H, CH3O), 3.95 (s, 3H, CH3O), 6.70
(d, J ס 9.3 Hz, 1H, C6H2CO), 7.18 (t, J ס 7.8 Hz, 1H,
NHPh), 7.38 (t, J ס 7.8 Hz, 2H, NHPh), 7.43 (d, J ס
7.8 Hz, 1H, C6H2CO), 7.61 (d, J ס 7.8 Hz, 2H, NHPh),
10.05 (br, 1H, NH); IIIb, d 3.87 (s, 3H, CH3O), 3.96
(s, 3H, CH3O); 13C NMR (CDCl3); IIIa, d 56.5 (CH3O),
62.7 (CH3O), 108.3, 119.9, 120.0, 125.1, 125.5, 129.2,
133.4, 137.2, 152.6, 155.0, 157.6 (CONH), 199.3
(COSe); 77Se NMR (CDCl3): IIIa, d 726.1. Anal. calcd
for C16H14ClNO4Se: C, 48.20; H, 3.54. Found: C,
48.29; H, 3.56.
Reactions of Acyl Carbamoyl Selenides (3) with
Sodium Methoxide and p-Toluidine
Reaction of 4-Methoxybenzoyl N-Phenylcarba-
moyl Selenide (3h) with Sodium Methoxide.
4-
Methoxybenzoyl N-phenylcarbamoyl selenide 3h
(0.17 g, 0.5 mmol) and sodium methoxide (0.03 g,
0.5 mmol) were stirred in diethyl ether (5 mL) at
24ꢀC for 1 hour. The solvent was evaporated under
reduced pressure to give a yellow solid containing
sodium 4-methoxybenzenecarboselenoate 6. To the
solid, iodomethane (1 mL) was added, and the mix-
ture was stirred at 24ꢀC for 1 hour. To the reaction
mixture was added diethyl ether (3 mL). The result-
ing precipitates (NaI containing methyl N-phenyl-
carbamate 7) was filtered off. Evaporation of the sol-
vent from the filtrate under reduced pressure gave
0.11 g (98%) of Se-methyl 4-methoxybenzenecarbo-
selenoate, which was identified by comparison of the
4-Biphenylcarbonyl N-Phenylcarbamoyl Selenide
(3m).
Colorless crystals (92% yield); dec.: 106–
108ꢀC; IR (KBr): 3223 (NH), 1693 (COSe), 1655
(CONH), 1517 (NH) cmמ1; 1H NMR (CDCl3): d 7.17–
7.99 (m, 14H), 10.46 (br, 1H, NH); 13C NMR (CDCl3):
d 120.0, 125.0, 127.2, 127.3, 127.8, 128.2, 128.8,
129.0, 129.1, 137.1, 139.2, 148.0, 156.1 (CONH),
198.9 (COSe).
1-Naphthalenecarbonyl N-Phenylcarbamoyl Se-
lenide (3n). Colorless crystals (93% yield); dec.: 87–
90ꢀC; IR (KBr): 3234 (NH), 1725 (COSe), 1655
(CONH), 1555 (NH) cmמ1; 1H NMR (CDCl3): d 7.20–
8.57 (m, 12H), 10.36 (br, 1H, NH); 13C NMR (CDCl3):
d 120.0, 124.5, 124.7, 125.1, 127.2, 128.2, 128.7,
129.0, 129.3, 129.4, 134.0, 134.9, 135.5, 137.2, 157.1
(CONH), 201.9 (COSe). Anal. calcd for C18H13NO2Se:
C, 61.03; H, 3.70. Found: C, 61.02; H, 3.92.
1
IR and H NMR spectra with those of the authentic
sample.
Methyl N-phenylcarbamate 7. m.p.: 43–45ꢀC; IR
(KBr): 3321 (NH), 1714 (CO) cmמ1; 1H NMR (CDCl3):
d 3.72 (s, 3H, CH3), 7.02 (t, J ס 7.8 Hz, 1H), 7.02 (br,
1H, NH), 7.25 (t, J ס 7.8 Hz, 2H), 7.38 (d, J ס 7.8
Hz, 2H); 13C NMR (CDCl3): d 52.1 (CH3), 123.3, 129.5,
128.8, 137.9, 154.3 (CO).
4-Methoxybenzoyl N-(4-Methylphenyl)carbamoyl
Sulfide (4). Colorless crystals; dec.: 136–142ꢀC; IR
(KBr): 3209 (NH), 1714 (COS), 1705 (CONH), 1542
1
(NH) cmמ1; H NMR (CDCl3): IIIa, d 2.34 (s, 3H,
Reaction of 3h with p-Toluidine. To a solution
of 4-methoxybenzoyl N-phenylcarbamoyl selenide
3h (0.26 g, 0.8 mmol) in dichloromethane (10 mL)
p-toluidine (0.17 g, 1.6 mmol) was added and the
mixture was stirred at room temperature for 7 h. Af-
CH3), 3.90 (s, 3H, CH3O), 6.98 (d, J ס 8.8 Hz, 2H),
7.17 (d, J ס 8.6 Hz, 2H), 7.48 (d, J ס 8.6 Hz, 2H),
7.98 (d, J ס 8.8 Hz, 2H), 10.82 (br, 1H, NH); IIIb, d
2.32 (s, 3H, CH3), 3.87 (s, 3H, CH3O), 6.94 (d, J ס 8.3

258 Kageyama et al.
ter evaporation of the solvent under reduced pres-
sure, diethyl ether (5 mL) was added. Collection of
the resulting precipitates by filtration gave 0.16 g
(85% yield) N-4-methylphenyl NЈ-phenyl urea 9 as
colorless needles. Removal of the diethyl ether from
the filtrate under reduced pressure gave 0.11 g (57%
yield) of N-4-methylphenyl 4-methoxybenzamide 8
as colorless crystals.
assistance with crystallography and Mr. Kohji Mae-
shima for assistance of the experiment.
REFERENCES
[1] Naegeli, C.; Tyabji, A. Helv Chim Acta 1935, 18, 142–
160.
[2] Colankiewicz, K.; Dezor-Mazur, M. Bull Acad Pol Soc
Ser Sci Chim 1969, 17, 575–578.
[3] Kato, S.; Mitani, T.; Mizuta, M. Bull Chem Soc Jpn
1972, 45, 3653–3657.
[4] Motoki, S.; Saito, T.; Kagami, H. Bull Chem Soc Jpn
1974, 47, 775–776.
[5] Kageyama, H.; Murai, T.; Kanda, T.; Kato, S. J Am
Chem Soc 1994, 116, 2195–2196.
[6] Kato, S.; Kawahara, Y.; Kageyama, H.; Yamada, R.;
Niyomura, O.; Murai, T.; Kanda, T. J Am Chem Soc
1996, 118, 1262–1267.
N-4-Methylphenyl
4-Methoxybenzamide (8).
Colorless crystals; m.p.: 156–157ꢀC; IR (KBr): 3340
1
(NH), 1651 (CO) cmמ1; H NMR (CDCl3): d 2.31 (s,
3H, CH3), 3.83 (s, 3H, CH3O), 6.90 (d, J ס 8.8 Hz,
2H), 7.12 (d, J ס 8.3 Hz, 2H), 7.50 (d, J ס 8.3 Hz,
2H), 7.80 (d, J ס 8.8 Hz, 2H), 7.95 (br, 1H, NH); 13
C
[7] Bondi, A. J Phys Chem 1964, 68, 441–451.
[8] Arcus, C. L.; Prydal, B. S. J Chem Soc 1954, 4018–
4020.
[9] Bloch, L.; Bergaman, M. Ber Dtsch Chem Ges 1920,
53, 924–930.
NMR (CDCl3): d 20.9 (CH3), 55.4 (CH3O), 113.8,
120.4, 127.2, 128.9, 129.5, 133.9, 135.6, 162.3 (CO),
165.3.
N-4-Methylphenyl NЈ-Phenyl Urea (9). Colorless
needles; m.p.: 204–205ꢀC; IR (KBr): 3303 (NH), 1635
[10] Kato, S.; Kitaoka, N.; Niyomura, O.; Kitoh, Y.; Kanda,
T.; Ebihara, M. Inorg Chem 1999, 38, 496–506.
[11] Sheldrick, G. M. In Crystallographic Computing 3;
Sheldrick, G. M.; Kruger, C.; Goddard, R. Eds.; Ox-
ford University Press, 1985, 175–189.
[12] Beukskens, P. T.; Admiraal, G.; Beukskens, G.; Bos-
man, W. P.; Gelder, R. de; Israel, R.; Smits, J. M. M.
The DIRDIF-94 program system Technical Report of
the Crystallography Laboratory, University of Nij-
megen, The Netherlands, 1994.
[13] Cromer, D. T.; Waber, J. T. In International Tables for
X-ray Crystallography; Ibers, J. A., Hamilton, W. C.,
Eds.; The Kynoch Press: Birmingham, England,
1974; Vol. IV, Table 2.2A.
1
(CO) cmמ1; H NMR (CDCl3 ם DMSO-d6): d 2.27 (s,
3H, CH3), 6.94 (t, J ס 7.7 Hz, 1H), 7.05 (d, J ס 8.3
Hz, 2H), 7.24 (t, J ס 7.7 Hz, 2H), 7.32 (d, J ס 8.3
Hz, 2H), 7.43 (d, J ס 7.7 Hz, 2H), 8.42 (br, 1H, NH),
8.49 (br, 1H, br); 13C NMR (CDCl3 ם DMSO-d6): d
20.4 (CH3), 118.1, 118.3, 121.5, 128.5, 129.0, 130.6,
137.0, 139.7, 152.6 (CO).
ACKNOWLEDGMENTS
[14] Creagh, D. C.; Hubell, J. H. In International Tables
for X-ray Crystallography; Wilson, A. C., Ed.; Kluwer
Academic Publishers: Boston, 1992; Vol. C, Table
4.2.4.3, pp 200–206.
S. K. thanks Prof. Takashi Kawamura and Dr.
Masahiro Ebihara (Gifu University) for invaluable