G. Mloston, M. Celeda, H. W. Roesky, E. Parisini, J.-T. Ahlemann
NS : calcd.
FULL PAPER
OCH
H). Ϫ 13C NMR: δ ϭ 29.8 (t), 36.5 (d), 44.3 (d) and 57.6 (s) (all
Ad), 55.2 and 55.3 (2 OCH ), 113.0, 113.1, 129.4, 129.5 (CH of Ar
ring), 132.7, 135.6 (C , Ar), 159.0, 160.6 (C ϪOCH ), 162.3 (Cϭ
N). Ϫ MS; m/z (%): 375 (49) [M ], 242 (48), 135 (100) [Ad ]. Ϫ
HRMS for C25 : calcd. 375.2198; found 375.2175.
3
), 6.75/7.43 (AB system, 4 H), and 6.83/7.05 (AB system, 4 (100) [Adϩ•], 107 (6), 93 (10), 79 (12). Ϫ C23
H
29
F
6
2
497.1646; found 497.1646 (MS).
3
X-ray Data of Dithiazolidine 9[20]: C23
29 6 2 r
H F NS , M ϭ 497.59,
q
q
3
monoclinic, space group P2
1
/c (No.14). Unit cell dimensions: a ϭ
ϩ
ϩ
˚
6
2
.853(1), b ϭ 12.568(3), c ϭ 24.908(5) A, β ϭ 95.90(3)°, V ϭ
133.9(7) A , Z ϭ 4; Dcalcd. ϭ 1.549 mg/ml; F(000) ϭ 1040; T ϭ
H
29NO
2
˚
3
Ϫ1
Reaction of 1 with Adamantanethione (4f): An orange-colored
solution of 329 mg (2 mmol) of 4f and 588 mg (1.8 mmol) of 1 in
193(2) K; µ(Mo-K ) ϭ 0.314 mm . Data collection: Stoe-Siemens
α
AED four-circle diffractometer, colorless crystal (size 0.40 ϫ 0.25
CDCl
h. After this time, the solution had turned yellow and the H-
NMR spectrum of the reaction mixture no longer indicated the
3
(1.5 ml) was sealed in a glass tube and heated at 100°C for ϫ 0.20 mm) mounted on a glass fibre, cell constants from 15 cen-
1
2
tered reflections. Mo-K radiation, graphite monochromator, λ ϭ
α
0.71073 A˚ , ω-2θ scan with profile fitting. Intensity of three stand-
presence of 1. After cooling in an acetone/dry ice bath, the tube ard reflections checked every 90 min, 2θ range 6Ϫ45°, 4025 reflec-
was opened and the reaction mixture was diluted with ethanol (2
ml). The clear solution thus obtained was stored for about 12 h in 1834 with I > 2σ(I). Structure solution by SHELXS-90
a refrigerator, after which a portion of colorless needles (242 mg)
tions measured, 2797 unique and observed (Rint ϭ 0.1073), and
[20]
and re-
finement by SHELXL-93[ , non-hydrogen atoms refined aniso-
21]
with m.p. 185Ϫ189°C was filtered off. The mother liquor was con- tropically, hydrogen atoms included in calculated positions and re-
2
centrated and chromatographed on a silica gel column. Pentane fined using a riding model. Full-matrix refinement against F . Final
with increasing amounts of dichloromethane was used as the elu-
R1 ϭ 0.0537 and wR2 ϭ 0.0977 for 1834 reflections with I > 2σ(I).
ent. First, the interception product 8 was isolated as colorless crys-
R1 ϭ 0.1084 and wR2 ϭ 0.1194 for all data. Weights: SHELXL-
tals using pentane as the eluent; the next fraction contained 1,4,2- 93. Maximum and minimum peak and hole in the Fourier synthesis
0.338 and Ϫ0.284 eA˚
Ϫ3.
dithiazolidine 9 (pentane/dichloromethane, 9:1), and finally di-
spiro-trithiolane 10 was isolated upon elution with pentane/di-
chloromethane (8:2).
Dispiro[adamantane-2,5Ј-(1,2,4)-trithiolane-3Ј,2ЈЈ-adamantane]
10): Yield 71 mg (20%), m.p. 189Ϫ191°C (ref.[
: m.p.
15]
(
1
2
-(1-Adamantyl)-3,3,5,5-tetrakis(trifluoromethyl)-1,4,2-dithia-
93Ϫ195°C). The IR spectrum of this product matched that of the
previously obtained sample of 10.
zolidine (8): Yield 71 mg (8%), m.p. 65Ϫ66°C (from methanol). Ϫ
Ϫ1
IR (KBr): ν˜ ϭ 2860 cm , 1240 (br., s) and 1180 (vs) (CF
), 1090
3
1
(
s), 955, 705. Ϫ H NMR: δ ϭ 1.55Ϫ1.75 (br.) and 2.05Ϫ2.20 (br.
13
m, 15 H, Ad). Ϫ C NMR: δ ϭ 30.8, 35.6 (2 t), 42.2 (d) and 68.7
Ƞ
Dedicated to Professor Günter Siegemund on the occasion of
his 60th birthday.
2
2
(
s) (all Ad), 64.6 (sept, JCϪF ϭ 30.1 Hz, C-5), 89.0 (sept, JCϪF ϭ
1
[1]
3
J
0.0 Hz, C-3), 122.7 (q, JCϪF ϭ 291.1 Hz, 2 CF
3
) and 123.0 (q,
). Ϫ 19F NMR: δ ϭ Ϫ63.44 (br. s) and
3
R. Maier, J. Morgenstern, J. Fabian, Angew. Chem. 1964, 76,
157Ϫ167; Angew. Chem. Int. Ed. Engl. 1964, 3, 277Ϫ278; J.
Voss, Methoden Org. Chem. Houben-Weyl (Ed.: D. Klamann),
G. Thieme Verlag, Stuttgart, 1985, vol. E 11/1, p. 195Ϫ231.
[2] [2a]
1
CϪF ϭ 285.5 Hz, 2 CF
Ϫ67.07 (s). Ϫ MS; m/z (%): 378 (36) [M Ϫ Ad], 135 (100) [Ad ].
Ϫ HRMS: C16 : calcd. 513.0454; found 513.0376.
ϩ
ϩ
H
15
F
12NS
2
L. Fisera, R. Huisgen, I. Kalwinsch, E. Langhals, X. Li, G.
Mloston, K. Polborn, J. Rapp, W. Sickling, R. Sustmann, Pure
X-ray Data of Dithiazolidine 8[20]: C16
15 2 r
H F12NS , M ϭ 513.41,
[2b]
Appl. Chem. 1996, 68, 789Ϫ798. Ϫ
A. Caperucci, M. C.
¯
triclinic, space group P1 (No.2). Unit cell dimensions: a ϭ 6.988(1),
Ferrara, A. DeglЈInnocenti, B. F. Bonini, G. Mazzanti, P . Za-
˚
[2c]
b ϭ 9.732(2), c ϭ 28.990(6) A, α ϭ 91.10(3), β ϭ 92.14(3), γ ϭ
nini, A. Ricci, Synlett 1992, 880Ϫ882. Ϫ
G. Mloston, H.
˚
3
Heimgartner, Helv. Chim. Acta 1996, 79, 1785Ϫ1792.
1
1
07.33(3)°, V ϭ 1880(1) A , Z ϭ 4; Dcalcd. ϭ 1.814 mg/ml; F(000) ϭ
[3]
) ϭ 0.403 mmϪ1. Data collection:
R. Huisgen, E. Langhals, Tetrahedron Lett. 1989, 30,
032; T ϭ 193(2) K; µ(Mo-K
α
5
369Ϫ5372.
Stoe-Siemens AED four-circle diffractometer, colorless crystal (size
.60 ϫ 0.40 ϫ 0.30 mm) mounted on a glass fibre, cell constants
[4]
J. Sauer, J. Schatz, Tetrahedron Lett. 1994, 35, 4767Ϫ4770.
R. Huisgen, C. Fulka, I. Kalwinsch, X. Li, G. Mloston, J. R.
Moran, A. Pröbstl, Bull. Soc. Chem. Belg. 1984, 93, 511Ϫ532.
R. Huisgen, L. Fisera, H. Giera, R. Sustmann, J. Am. Chem.
Soc. 1995, 117, 9671Ϫ9678.
[
[
5]
6]
0
from 18 centered reflections. Mo-K
chromator, λ ϭ 0.71073 A, ω-2θ scan with profile fitting. Intensity
of three standard reflections checked every 90 min, 2θ range 7Ϫ45°,
α
radiation, graphite mono-
˚
[7] [7a]
G. Mloston, H. Heimgartner, Helv. Chim. Acta 1995, 78,
[
7b]
6
0
9
381 reflections measured, 4914 unique and observed (Rint
ϭ
1298Ϫ1310. Ϫ
Heimgartner, Helv. Chim. Acta 1993, 76, 2147Ϫ2154.
8] [8a]
G. Mloston, J. Romanski, A. Linden, H.
.0605), and 3587 with I > 2σ(I). Structure solution by SHELXS-
[
[
20]
[21]
G. Mloston, Z. Skrzypek, Bull. Soc. Chim. Belg. 1990, 99,
0
and refinement by SHELXL-93 , non-hydrogen atoms re-
[8b]
1
67Ϫ170. Ϫ
G. Mloston, A. Linden, H. Heimgartner, Pol.
fined anisotropically, hydrogen atoms included in calculated posi-
tions and refined using a riding model. Full-matrix refinement
J. Chem. 1997, 71, 32Ϫ39.
[9]
A. Schönberg, W. Urban, J. Chem. Soc. 1935, 530Ϫ531.
A. May, H. W. Roesky, D. Stalke, F. Pauer, G. M. Sheldrick,
Chem. Ber. 1990, 123, 1475Ϫ1478.
[
[
10]
2
against F . Final R1 ϭ 0.0663 and wR2 ϭ 0.1492 for 3587 reflec-
tions with I > 2σ(I). R1 ϭ 0.0996 and wR2 ϭ 0.1707 for all data.
11]
H. W. Roesky, A. May, M. Noltemeyer, J. Fluorine Chem. 1993,
Weights: SHELXL-93. Maximum and minimum peak and hole in
6
2, 77Ϫ99.
˚
Ϫ3
[12] [12a]
[12b]
the Fourier synthesis 0.447 and Ϫ0.424 eA
.
S. Motoki, T. Saito, Sulfur Rep. 1984, 4, 33Ϫ58. Ϫ
L.
N. Markovsky, V. M. Timoshenko, Yu. G. Shermolowich, Zh.
Org. Khim. 1995, 31, 161Ϫ178 (Chem. Abstr. 1996, 124,
116274a); see also: J. Fabian, G. Mloston, Pol. J. Chem., sub-
mitted.
13]
2
-(1-Adamantyl)-3,3-bis(trifluoromethyl)spiro[(1,4,2)-dithia-
zolidine-5,2Ј-adamantane] (9): Overall yield after filtration and
chromatography 478 mg (53%), m.p. 184Ϫ186°C (from methanol/
dichloromethane). Ϫ IR (KBr): ν˜ ϭ 2860 cm , 1450 (s), 1240 (s),
[
Ϫ1
T. Saito, I. Oikawa, S. Motoki, Bull. Chem. Soc. Jpn. 1980,
53, 1023Ϫ1027.
1
and 1180 (vs) (all CF
3
), 1100, 1060, 920, 715. Ϫ H NMR: δ ϭ
[14]
R. Huisgen, G. Mloston, Tetrahedron Lett. 1985, 26,
1
3
6
2
.58Ϫ2.12 (m) and 2.36 (br.) (all Ad). Ϫ 13C NMR: δ ϭ 26.4, 26.8,
1049Ϫ1052.
[15]
G. Mloston, H. Heimgartner, J. Romanski, Pol. J. Chem. 1996,
70, 437Ϫ445.
5.8, 36.0, 36.5, 36.6, 37.3 and 42.2 [all Ad (ϫ2)], 64.0 (s, C-5),
9.6 (s, Ad), 87.5 (sept, JCϪF ϭ 28.1 Hz, C-3), 123.8 (q, JCϪF
90.0 Hz, 2 CF
2
1
ϭ
[16] [16a]
[16b]
R. Huisgen, J. Rapp, Tetrahedron 1997, 53, 939Ϫ960. Ϫ
W. M. McGregor, D. C. Sherrington, Chem. Soc. Rev.
19
3
). Ϫ F NMR: δ ϭ Ϫ63.95 (s, 2 CF
3
). Ϫ MS; m/
ϩ
ϩ
ϩ•
z (%): 497 (2) [M ], 364 (< 1) [M Ϫ Ad], 166 (6) [AdϭS ], 135
1993, 199Ϫ204.
464
Eur. J. Org. Chem. 1998, 459Ϫ465