First Preparation and X-ray Crystallographic Structure Determination of S,S,S-Triphenylthiazyne

Full text of DOI:10.1021/jo9703919

3
802
J . Org. Chem. 1997, 62, 3802-3803
F ir st P r ep a r a tion a n d X-r a y
Sch em e 1
Cr ysta llogr a p h ic Str u ctu r e Deter m in a tion
of S,S,S-Tr ip h en ylth ia zyn e
Toshiaki Yoshimura,* Kohki Hamada,
Masahiro Imado, Kouki Hamata, Kazumi Tomoda,
Takayoshi Fujii, Hiroyuki Morita,
Choichiro Shimasaki, Shin Ono, Eiichi Tsukurimichi,
†
†
Naomichi Furukawa, and Takeshi Kimura
chromatography and recrystallized from CH Cl -hexane
2
2
in 43% yield.5 H and C NMR, IR, and mass spectral
data and elemental analysis were consistent with the
structure of hydrated S,S,S-triphenylthiazyne (2)
1
13
Department of Chemical and Biochemical Engineering,
Faculty of Engineering, Toyama University,
Gofuku, Toyama 930, J apan, and Department of Chemistry,
University of Tsukuba, Tsukuba, Ibaraki 305, J apan
(Ph
3
2
StN‚H O), and elemental analysis of the dehydrated
-
2
product by heating at 80 °C (10
Torr) also gave
Received March 3, 1997
satisfactory results. 1H and C NMR spectra of 2 showed
13
the three equivalent phenyl groups. Furthermore, the
Formation of thiazyl fluoride (FStN) and thiazyl
trifluoride (F StN) bearing an SN triple bond was first
3
IR absorption of 2 due to the SN stretching band is
-
1
present at 1267 cm , which is higher than that of S,S-
suggested and their chemistry developed by Glemser et
-
1 6
1
diphenylsulfilimine (νSN, 940 cm ) and that of S,S-
al. Despite a long history of this class of compounds in
diphenylsulfoximine (νOSN, 1217 and 965 cm- ), clearly
suggesting that the SN bond of the thiazyne 2 has a
higher bond order than both sulfilimines and sulfox-
1
7
fluorine and inorganic chemistry, they had remained
unrecognized in the field of organic chemistry.2 The only
example of an organic thiazyne was S,S-diphenyl-S-
-
1
imines. The wavenumber 1267 cm is lower than that
fluorothiazyne, which was first reported and named
2
of any other type of thiazynes, S-alkoxy-S,S-diphenylthia-
“
thiazyne” by Clifford et al., although it was not isolated
-
1
3c
zynes (1322-1340 cm ), S-amino-S,S-diphenylthia-
in pure form. Recently, we prepared S,S-diphenyl-S-
fluorothiazyne (1) in pure crystalline form from N-bromo-
S,S-diphenylsulfilimine and further reported the forma-
zynes (1285-1300 cm 1),3b S,S-diphenyl-S-fluorothiazyne
-
-
1
3a
-1 1c
(
1361 cm ), or thiazyl trifluoride (1515 cm ), which
is considered to be due mainly to the effect of the lower
electronegativity of the carbon ligand of 2.
tion of S-alkoxy-S,S-diphenylthiazynes and S-amino-S,S-
diphenylthiazynes from the reaction of 1.3 However, the
The crystal structure of the new thiazyne 2 was
spectral data of the S-fluorothiazyne 1 were much
8
different from those reported by Clifford et al.2 One
determined by X-ray crystallographic analysis (Figure 1).
The X-ray analysis clearly reveals that the configuration
around the sulfur atom in 2 is a slightly distorted
tetrahedral structure with one SN bond and three SC
bonds. The bond length of S1-N1 is 1.462(3)°, which is
possible explanation for this discrepancy is that these
compounds might be their isomers, N-substituted sulfil-
imines, and our assignments of their characteristic IR
-
1
as νStN were tentative.3
bands at 1280-1360 cm
9
very close to that of thiazyl trifluoride (1.416 Å) deter-
Therefore, more definitive evidence for the structure
assignment has been required. Every thiazyne so far
prepared has at least one electronegative atom such as
mined by microwave spectroscopy and is shorter than
1
1
0
1
that of S,S-diphenyl-N-tosylsulfilimine (1.628 Å, X-ray),
S,S-dimethylsulfoximine (1.521 Å, electron diffraction),
1
-4
fluorine, oxygen, and nitrogen on the sulfur atom.
and S,S-dimethylsulfonediimine(1.533 Å, electron dif-
Since the electronegative atom on the sulfur atom is
considered to stabilize the SN multiple bond, a thiazyne
bearing three carbon ligands, S,S,S-triphenylthiazyne (2),
is an interesting target and will show three equivalent
phenyl groups on the NMR spectra to distinguish it from
the structure of N-phenylsulfilimine. Here, we report the
first preparation and X-ray crystallographic structure
determination of a new thiazyne 2 having three carbon
ligands.
fraction).12
The thiazyne 2 is thermally much more stable than
other organic thiazynes hitherto prepared and is not
hydrolyzed under either acidic or alkaline conditions,
(5) The side products were mainly biphenyl (24%) and diphenyl
sulfide (13%), which may be formed by ligand-coupling reaction. A
complex reaction mixture including some unidentified products was
1
also obtained. 2: mp 231-232 °C, 181-182 °C (monohydrate); H NMR
(
(
(
400 MHz, CDCl ) δ 7.48-7.52 (m, 6H), 7.54-7.58 (m, 3H), 7.74-7.77
3
The reaction of S-fluorothiazyne 1 with 1.1 equimolar
amount of phenyllithium in anhydrous THF under Ar
atmosphere at -78 °C gave a new thiazyne 2 (Scheme
13
3
m, 6H); C NMR (100 MHz, CDCl ) δ 127.2, 129.0, 132.0, 145.8; IR
+
-1
KBr) 1267 cm (SN); MS m/z 277 (M ). Anal. Calcd for C18
15 1 1
H N S :
C, 77.94; H, 5.45; N, 5.05. Found: C, 77.70; H, 5.42; N, 5.03.
Monohydrate. Anal. Calcd for C18 : C, 73.19; H, 5.80; N, 4.74.
Found: C, 73.34; H, 5.69; N, 4.93.
6) Yoshimura, T.; Omata, T,; Furukawa, N.; Oae, S. J . Org. Chem.
17 1 1 1
H N O S
1
). The compound 2 was isolated by silica gel column
(
†
University of Tsukuba.
1976, 41, 1728.
(
1) (a) Glemser, O.; Schr o¨ der, H. Allg. Chem. 1955, 279, 28. (b)
(7) Oae, S.; Harada, K.; Tsujihara, K.; Furukawa, N. Int. J . Sulfur
Chem. Part A 1972, 2, 49.
Glemer, O.; Richert, H.; Anorg, Z. Allg. Chem. 1961, 307, 313. (c)
Richert, H.; Glemser, O. Allg. Chem. 1961, 307, 328. (d) Glemser, O.;
Meyer, H.; Haas, A. Chem. Ber. 1964, 97, 1704. (d) Glemser, O.; Mews,
R. Angew. Chem., Int. Ed. Engl. 1980, 19, 883 and references therein.
(8) The crystal data for 2: C18
15 1 1 2 1
H N S ‚H O, monoclinic, P2 /n, a )
9.213(2) Å, b ) 16.486(4) Å, c ) 11.098(2) Å, â ) 111.64(1)°, V ) 1566.8
3
3
-1
Å , z ) 4, F ) 1.25 g/cm , µ(Mo KR) ) 1.9 cm , R ) 0.057 (R
w
) 0.056),
2
2
(
2) Clifford, A. F.; Howell, J . L.; Wooton, D. L. J . Fluorine Chem.
978, 11, 433.
3) (a) Yoshimura, T.; Kita, H.; Takeuchi, K.; Takata, E.; Hasegawa,
1911 with F > 3.0σ(F ). The author has deposited atomic coordinates
o
o
1
for this structure with the Cambridge Crystallographic Data Centre.
The coordinates can be obtained, on request, from the Director,
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge,
CB2 1EZ, UK.
(9) The S-N bond length of thiazyl trifluoride was determined by
microwave spectroscopy. Kirchhoff, W. H.; Wilson, E. B., J r. J .
Am.Chem. Soc. 1962, 84, 334.
(
K.; Shimasaki, C.; Tsukurimichi, E. Chem. Lett. 1992, 1433. (b)
Yoshimura, T.; Takata, E.; Miyake, T.; Shimasaki, C.; Hasegawa, K.;
Tsukurimichi, E. Chem. Lett. 1992, 2213. (c) Alkoxythiazyne was
prepared from S,S-diphenyl-N-halosulfilimine: Yoshimura, T.; Tsuku-
rimichi, E.; Kita, H.; Fujii, H.; Shimasaki, C. Tetrahedron Lett. 1989,
3
0, 6339.
4) (a) Shaaz, L. J .; Andes, B. A.; Carsky, P.; Zahradnik, R. Inorg.
(10) Kalman, A.; Duffin, B.; Kucsman, A. Acta. Crystallogr., Sect. B
1971, 27, 586.
(
Chem. 1984, 23, 2428. (b) Beach, D. B.; J olly, W,; Mews, R.; Waterfeld,
A. Inorg. Chem. 1984, 23, 4080.
(11) Oberhammer, H.; Zeil, W. Z. Naturforsch., A 1970, 25, 845.
(12) Oberhammer, H.; Zeil, W. Z. Naturforsch., A 1969, 24, 1612.
S0022-3263(97)00391-5 CCC: $14.00 © 1997 American Chemical Society

Communications
J . Org. Chem., Vol. 62, No. 12, 1997 3803
Sch em e 2a
F igu r e 1. Crystal structure of 2. For clarity, the monohydrate
is omitted. Selected bond distances (Å) and bond angles (deg):
S1-N1, 1.462(3); S1-C1, 1.810(4); S1-C2, 1.799(4); S1-C3,
a
Substrate 2 (0.5 mmol), electrophiles (3 mmol), benzene (10
b
mL). Isolated yield.
1
.812(3); N1-S1-C1, 116.6(2); N1-S1-C2, 116.0(2); N1-S1-
in the nucleophilicity at the nitrogen. Treatment of 2
with several alkyl halides such as methyl iodide, ethyl
iodide, and isopropyl iodide gave the corresponding
C3, 115.6(2); C1-S1-C2, 101.7(2), C1-S1-C3, 101.4(1); C2-
S2-C3, 103.3(2).
1
6
N-alkylated compounds 4 in good yields (Scheme 2).
though the corresponding S-fluoro- and S-alkoxy-thia-
zynes are readily hydrolyzed to S,S-diphenylsulfoximine
under acidic conditions. The thiazyne 2 is considerably
basic. Treatment of the compound 2 with hydrochloric
acid afforded quantitatively the corresponding S,S,S-
triphenyliminosulfonium chloride (3),13 which is also a
new type of compound and is of interest in relation to
the isoelectronic triphenyloxosulfonium salt.14 Measure-
ment of the basicity of 2 is important for estimating its
nucleophilicity and the character of the SN bond. The
N-Alkyliminosulfonium halides are also first examples
in the field of organosulfur chemistry. Further investiga-
tions are now in progress in this area.
Ack n ow led gm en t. This work was supported in part
by a Grant-in-Aid for Scientific Research (No. 04804035)
from the Ministry of Education, Science and Culture.
Su p p or tin g In for m a tion Ava ila ble: Experimental pro-
1
13
cedure and spectral data, including copies of H NMR and
C
NMR spectra, for compounds 2-4; structure determination
summaries and tables of X-ray structure data for 2 (27 pages).
pK
potentiometric titration using 0.1 M hydrochloric acid at
5 °C to be 7.44. This value is very close to that of S,S-
a
value of the conjugate acid of 2 was determined by
2
J O9703919
3
b
diphenyl-S-piperidinothiazyne (7.44) and is large com-
7
,15
pared to that of S,S-diphenylsulfoximine (2.60)
and
1
(
16) 4a : mp 222-223 °C; H NMR (400 MHz, CDCl
3
) δ 2.99 (s, 3H),
) δ
S,S-diphenylsulfonediimine (3.92).15 The high basicity
of 2 is attributable to polarization of the SN bond, which
is similar to the case of sulfilimines.15
13
7.85-7.95 (m, 9H), 8.03-8.06 (m, 6H); C NMR (100 MHz, CDCl
3
3
1.7, 129.0, 129.3, 131.5, 136.5; IR (KBr) 1197 cm- (SN). Anal. Calcd
for C19 : C, 54.42; H, 4.33; N, 3.34. Found: C, 54.38; H, 4.32;
N, 3.38. 4b: mp 197-198 °C; H NMR (400 MHz, CDCl
) 7.2 Hz, 3H), 3.17 (q, J ) 7.2 Hz, 2H), 7.84-7.94 (m, 9H), 8.05-8.07
1
18 1 1 1
H I N S
1
3
) δ 1.34 (t, J
The electron-rich nature of the nitrogen atom in
thiazyne 2 is manifest not only in the basicity but also
1
3
(
1
m, 6H); C NMR (100 MHz, CDCl
3
) δ 17.4, 40.8, 129.0, 129.7, 131.5,
36.5; IR (KBr) 1172 cm- (SN). Anal. Calcd for C20
: C, 55.43;
H, 4.65; N, 3.23. Found: C, 55.33; H, 4.52; N, 3.09. 4c: mp 196-197
1
20 1 1 1
H I N S
13) Experimental data: mp 219-222 °C; 1H NMR (400 MHz,
CDCl ) δ 7.72 (t, J ) 7.6 Hz, 6H), 7.83 (t, J ) 7.6 Hz, 3H), 7.96 (d, J
7.6 Hz, 6H); C NMR (100 MHz, CDCl
°C; H NMR(400 MHz, CDCl
) 7.2 Hz, 2H), 3.05 (t, J ) 7.2 Hz, 2H), 7.84-7.94 (m, 9H), 8.05-8.07
1
(
3
) δ 0.99 (t, J ) 7.2 Hz, 3H), 1.74 (sext, J
3
1
3
13
)
3
) δ 128.7, 130.5, 134.2, 135.6;
IR (KBr) 2950 (NH), 1077 cm (SN). Anal. Calcd for C18
C, 68.89; H, 5.14; N, 4.46. Found: C, 68.67; H, 5.02; N, 4.39.
14) Mori, M.; Takeuchi, H.; Minato, H.; Kobayashi, M.; Yoshida,
M.; Matsuyama, H.; Kamigata, N. Phosphorus, Sulfur, Silicon 1990,
(m, 6H); C NMR (100 MHz, CDCl
3
) δ 11.6, 25.0, 47.3, 129.0, 129.7,
131.4, 136.5; IR (KBr) 1166 cm (SN). Anal. Calcd for C21
C, 56.38; H, 4.96; N, 3.13. Found: C, 56.34; H, 4.82; N, 3.00. 4d : mp
-1
-1
H
16Cl
1
N
1
S
1
:
22 1 1 1
H I N S :
1
(
211-212 °C H NMR(400 MHz, CDCl
3.51 (sept, J ) 6.4 Hz, 1H), 7.84-7.95 (m, 9H), 8.04-8.06 (m, 6H);
NMR (100 MHz, CDCl ) δ 25.6, 48.9, 129.0, 130.9, 131.4, 136.4; IR
(KBr) 1168 cm- (SN). Anal. Calcd for C21
: C, 56.38; H, 4.96;
N, 3.13. Found: C, 56.35; H, 4.95; N, 3.02.
3
) δ 1.21 (d, J ) 6.4 Hz, 6H),
13
C
4
7, 157.
3
1
(15) Furukawa, N.; Yoshimura, T.; Omata, T.; Oae, S. Chem. Ind.
22 1 1 1
H I N S
1
972, A2, 1972.