Mixed Group 14 and 16 Heterocycles
A R T I C L E S
of the chemistry of these novel heterocycles will be presented
elsewhere.
5,5-Bis(trimethylsilyl)-1,3,5-dithiasilinane (34b) ([6]S
,2-Bis(bromomethyl)-1,1,1,3,3,3-hexamethyltrisilane (23b, 0.36 g, 1.0
mmol) and CS (0.12 g, 1.5 mmol) in THF (10 mL) was added at room
temperature to a slurry of NaBH (0.12 g, 3.0 mmol) in EtOH-THF
1:5, 12 mL), and the solution was stirred for 2 h. The solution was
concentrated and extracted (CH Cl ; 20 mL), the extracts were
concentrated, and the residue was chromatographed (silica gel,
CH Cl ), giving 34b as colorless crystals (0.16 g, 57%), mp 82-83
2 2
Si(TMS) ).
2
2
Experimental Section37
4
(
3
2 2
,3,7,7-Tetramethyl-1,5-dithia-3,7-disilocane (25a) ([8]S Si ). A
2
2
solution of bis(acetylthiomethyl)dimethylsilane (24a, 0.47 g, 2.0 mmol;
from reaction of bis(iodomethyl)dimethylsilane (23a) stirred overnight
in THF with excess KSAc) and 23a (0.68 g, 2.0 mmol) in EtOH (20
mL) was added dropwise during 1.5 h to a solution of KOH (0.28 g,
2
1
2
13
°
3
C; H NMR δ 3.74 (s, 2H), 2.09 (s, 4H), 0.18 (s, 18H); C NMR δ
-
1
2
5.9 (SCH S), 9.9 (SCH
2
Si), -0.5 (CH
3
); IR (thin film, cm ) 2948
5
.0 mmol) in EtOH (100 mL) with stirring under Ar at room
temperature. The solution was stirred for an additional 10 min, poured
into H O (20 mL), and extracted (CH Cl
; 2 × 20 mL). The extracts
were washed (H SO ), concentrated, and
O; 4 × 20 mL), dried (Na
the residue chromatographed (Al ; 1:6 CH Cl :C 14) giving 25a as
colorless crystals (0.16 g, 34%), mp 50-51 °C; H NMR δ 1.85 (s,
(
s), 2890 (m), 1244 (s), 837 (s); HRMS Calcd for C
Found: 280.0609. X-ray crystal structure determined.
,3,4,4,8,8,9,9-Octamethyl-1,6-diselena-3,4,8,9-tetrasilecane (42)
[10]Se (Si ). 4,4,5,5-Tetramethyl-1,2-diselena-4,5-disililane (41, 0.35
g, 1.2 mmol; from 1,2-bis(bromomethyl)tetramethyldisilane (38) and
Na Se in EtOH) and 38 (0.35 g, 1.2 mmol) in EtOH-THF (1:1, 10
mL) was added dropwise during 1.5 h to a suspension of NaBH (0.34
9
H
24
S
2
Si : 280.0627
3
2
2
2
3
2
2
4
(
2
2 2
)
O
2 3
2
2
6
H
1
2
2
1
3
8
H), 0.18 (s, 12H); C NMR δ 17.4 (CH
2
3
), -2.7 (CH ); IR (thin film,
4
-1
cm ): 2955 and 2893 (m, C-H), 2360 (w), 1715 (m), 1252 (m), 1053
m), 841 (s), 793 (m), 531 (m); LR-EIMS m/z 236 (M , 100), 221
M -Me, 19), 190 (19), 175 (55), 149 (20), 147 (20); HR-MS Calcd
g, 9.0 mmol) in EtOH-THF (1:19, 100 mL) with stirring under Ar at
room temperature. The solution was concentrated, and the residue was
+
(
(
+
2 2 2 6
chromatographed (SiO ; 1:3 CH Cl :C H14), giving 42 as colorless
for C
determined.
,3,7,7-Tetramethyl-1,5-diselena-3,7-disilocane (27a) ([8]Se
,4-Dimethyl-1,2-diselena-4-silolane (26a, 0.30 g, 1.2 mmol; from
Na Se and 23a in EtOH at 0 °C) and 23a (0.41 g, 1.2 mmol) in EtOH-
THF (1:1, 10 mL) was added dropwise during 1.5 h to a suspension of
NaBH (0.30 g, 7.9 mmol) in EtOH-THF (1:19, 100 mL) with stirring
under Ar at room temperature. The solution was stirred for 10 min,
concentrated in vacuo, poured into H O (20 mL) and extracted
CH Cl O; 4 × 20 mL),
; 2 × 20 mL). The extracts were washed (H
dried (Na SO ), and concentrated in vacuo, and the residue was
chromatographed (silica gel; 1:7 CH Cl 14), giving 27a as
colorless crystals (0.29 g, 73%), mp 30-31 °C; H NMR δ 1.75 (s,
8 20 2 2
H S Si : 236.0545. Found: 236.0548. X-ray crystal structure
1
crystals (0.21 g, 41%), mp 103-104 °C; H NMR δ 2.07 (s, 8H), 0.11
-1
(
s, 24H); 13C NMR δ 12.0 (CH
2
), -2.4 (CH
3
); IR (KBr, cm ): 2953
3
2 2
Si ).
(
s), 2891 (s), 1246 (s), 1022 (m); HR-MS Calcd for C12
H32Se
2
Si
4
:
4
4
1
47.9913. Found: 447.9906. An X-ray crystal structure was determined.
2
2
30
1
,3-Thiaselenetane S-Oxide (48). Bis(chloromethyl) sulfoxide (47,
.47 g, 10 mmol) in THF (10 mL) was added dropwise to an ice cooled
Se (10 mmol) suspension in THF (25 mL) at 0 °C. The mixture
4
Na
2
was warmed to room temperature, stirred for 2 h, filtered through Celite,
and concentrated. The brown residue was chromatographed (silica gel;
2
(
2
2
2
f
EtOAc, R 0.4), giving 48 (0.95 g, 61%) as colorless crystals, mp
2
4
1
8
4
6-88 °C after recrystallization (EtOAc; 0 °C); H NMR (CDCl
.22 (dd, J ) 5.3, 2.4 Hz, 2 H), 3.95 (dd, J ) 5.5, 2.4 Hz, 2 H); (C
3
) δ
D )
6
2
2 6
: C H
6
1
δ 3.36 (dd, J ) 5.0, 2.4 Hz, 2 H), 2.70 (dd, J ) 5.5, 2.4 Hz, 2 H);
DMSO-d ) δ 4.58 (dd, J ) 5.0, 2.4 Hz, 2 H), 4.06 (dd, J ) 5.5, 2.4
1
3
8
(
H), 0.19 (s, 12H); C NMR δ 6.5 (CH
2
3
), -1.7 (CH ); MS m/z 332
(
6
13
M , Se, 75), 245 (48), 45 (100); IR (KBr, cm-1): 2955 and 2896
+ 80
77
Hz, 2 H); C NMR (CDCl
3
) δ 41.8; Se-NMR (CDCl
GC-MS m/z 156 (M , Se, 38), 126 (20), 108 (3), 94 (100), 80 (6), 63
8); IR (KBr) 1114, 1061, 1008 cm-1 (all s); UV (CH
Cl
nm (518), 286 nm (476). Anal. Calcd for C SSeO: C, 15.49; H,
.60; S, 20.68. Found: C, 15.72; H, 2.44; S 20.84. An X-ray crystal
structure was determined.
,4-Dimethyl-1-selena-3-cyclohexene (50).32a Compound 48 (0.35
g, 2.3 mmol) in CH Cl (5 mL) and 2,3-dimethyl-1,3-butadiene (0.6 g,
.9 mmol) in a 10 mL Pyrex flask was irradiated for 3 h using a medium
3
) δ -14.9;
(
m, C-H), 2355 (w), 1361 (m), 1249 (s), 1102 (m), 1026 (m), 832 (s);
+ 80
80
80
8 2
HR-MS Calcd for C H20 Se SeSi : 331.9428. Found: 331.9435. X-ray
(
2
2
) λmax 266
crystal structure determined.
2 2
,3,7,7-Tetramethyl-1,5-ditellura-3,7-disilocane (29a) ([8]Te Si ).
2 4
H
3
2
A mixture of Te powder (1.28 g, 10 mmol) and KCN (0.67 g, 10 mmol)
in dry DMSO (20 mL) was heated to 100 °C under Ar for 1 h. The
mixture was cooled to room temperature, and 23a (1.7 g, 5 mmol) in
DMSO (5 mL) was added dropwise. After stirring for 2 h, a solution
3
2
2
6
of 23a (1.7 g, 5 mmol) in EtOH (10 mL) was added to the solution of
pressure 450 W mercury lamp (Hanovia). By GC-MS analysis, 3,4-
dimethyl-1-selena-3-cyclohexene (50) and 3,4-dimethyl-1-thia-3-cy-
clohexene 1-oxide (51) were formed in a 21:1 ratio. The mixture was
concentrated and chromatographed (silica gel, hexane), affording 50
1
bis-tellurocyanide 28a (88% yield by NMR; H NMR, DMSO-d
6
, δ
1
3
1
.87 (s, 4H), 0.31 (s, 6H); C, DMSO-d
was added dropwise by syringe during 1-1.5 h to a suspension of
NaBH (1.16 g, 30 mmol) in EtOH (60 mL) at 0 °C. The solution was
stirred for 10 min, poured into H O (50 mL), and extracted (CH Cl
× 30 mL). The extracts were washed (H O, 5 × 30 mL), dried
Na SO ), and concentrated, and the residue was chromatographed
basic Al ; hexane), giving 29a as a pale-yellow oil (0.5 g, 23%).
6
δ -1.0, -7.2). The mixture
4
1
as a light-yellow oil (0.32 g, 80%); H NMR δ 3.02 (s, 2H), 2.70 (t, J
2
2
2
;
13
)
6 Hz, 2H), 2.33 (m, 2H), 1.76 (s, 3H), 1.70 (s, 3H); C NMR
2
2
(
CDCl
3
80
) δ 129.3, 125.0, 33.0, 20.9, 20.4, 19.9, 18.4; GC-MS m/z 176
(
(
2
4
+
(M , Se, 100), 161 (10).
2
O
3
Acknowledgment. Financial support from the National Sci-
Recrystallization of the product (hexane) gave pale-yellow crystals;
1
ence Foundation (CHE-9906566, CHE-0342660, CHE-0450505,
E.B.; CHE-01300985, E.V.D.; CHE-0201555, CHE-0455575,
R.S.G.; CHE-9601809, U. Arizona HR-MS facility) and the
Petroleum Research Fund, administered by the American
Chemical Society (E.B.) is gratefully acknowledged. We thank
Professors K. Baines and B. Zwanenburg for helpful sugges-
tions.
mp 56.5-57.5 °C; H NMR δ 1.67 (s, 8H, CH
2
), 0.18 (s, 12H, Me);
); Te-NMR δ 75.2 (relative to
Te); MS m/z 428 (M , Te, 100), 342 (41), 216 (61); IR (KBr)
13
125
C NMR δ 0.4 (CH
3
), -17.0 (CH
2
+
130
Me
2
-
1
2
8 2 2
950, 2894, 1240, 827, 769, 705 cm . HRMS Calcd for C H20Si Te :
427.9202. Found 427.9196. An X-ray crystal structure was determined.
Radical Cation of 29a Quenched with Ethanol. To 29a (9 mg,
3 6
0.02 mmol) in CDCl (0.5 mL) was added NOPF (3.8 mg, 0.02 mmol)
in CD
3
CN (0.5 mL) dropwise at -55 °C. The mixture, which instantly
Supporting Information Available: Complete experimental
procedures and data on new compounds; full X-ray crystal-
lographic data on structures determined. This material is
available free of charge via the Internet at http://pubs.acs.org.
turned red, was stirred for 20 min. Then EtOH (2.8 mg, 0.06 mmol)
was added at -55 °C. GC-MS showed 3.3:1 5,5-dimethyl-1,3,5-
ditellurasilinane (37) to 4,4-dimethyl-1,2-ditellurasilolane (36).
(
37) Representative syntheses are given; full details appear in the Supporting
Information.
JA065037J
J. AM. CHEM. SOC.
9
VOL. 128, NO. 46, 2006 14961