Sultam and sultim structures, part 2. Functionalized novel cyclic sulfin- and sulfonamides: A comparison of hydrogen bonding formation in sulfoxides and sulfones

Article abstract of DOI:10.1515/znb-2002-0404

The stable hydroperoxides rac-cis-2a,d and 4a,c were synthesized by oxidation of the salts 1. The 3-hydroxy sultims rac-cis-3a,b and sultams 5a,e were obtained by reduction of the corresponding hydroperoxides 2 and 4. Crystal structure analyses were perfo

Full text of DOI:10.1515/znb-2002-0404

Sultam and Sultim Structures, Part 2 [1].
Functionalized Novel Cyclic Sulfin- and Sulfonamides: A Comparison
*
of Hydrogen Bonding Formation in Sulfoxides and Sulfones
a
a
a
a
B a¨ rbel Schulze , Kathleen Taubert , Feyissa Gadissa Gelalcha , Christine Hartung ,
b
and Joachim Sieler
a
Institut f u¨ r Organische Chemie, Universit a¨ t Leipzig, Johannisallee 29, D-04103 Leipzig
Institut f u¨ r Anorganische Chemie, Universit a¨ t Leipzig, Johannisallee 29, D-04103 Leipzig
b
Reprint requests to Prof. Dr. B. Schulze. E-mail: bschulze@organik.chemie.uni-leipzig.de
Z. Naturforsch. 57 b, 383–392 (2002); received February 26, 2002
Sultams, Sultims, Intermolecular Hydrogen Bonds
The stable hydroperoxides rac-cis-2a,d and 4a,c were synthesized by oxidation of the salts 1.
The 3-hydroxy sultims rac-cis-3a,b and sultams 5a,e were obtained by reduction of the corre-
sponding hydroperoxides2 and 4. Crystal structure analyses were performed for compounds 3b,
4
a, 5a, 5e and revealed a variety of intermolecular contacts leading to cyclodimers, tetramers
and polymers. In carboxylic esters 4a and 5a, cyclodimers with a 20- or 22-membered ring are
formed via ‘head-to-tail’ CO H-O hydrogen bonds and / -interactions, without participation
of the SO group. The 1,1-dioxide 4c, which has no carbonyl substituent, forms a tetrameric
2
unit by combining two symmetry independent molecules through strong OO-H O-S-O and
short nonclassical O-S-O H-C hydrogen bonds. The sultam 1,1-dioxide 5e, bearing a highly
substituted 2-phenyl ring, exhibits in the solid state strong intermolecular O-S-O H-O hy-
drogen bonds and forms the first polymer chain in this cyclic sulfonamide series. In sultims
2
a, 3a and 3b, but not in 2d, strong intermolecular S-O H-O hydrogen bonds are observed
and polymer chains originate from the c-glide plane (space group P2 /c)in 2a and from two
1
symmetry independent molecules in 3a. In the 1-oxide 2d a ‘head-to-head’ dimer was found
with two strong SO H-OO hydrogen bonds in a 14- or 16-membered ring. Short nonclassical
C-H O-C interactions connect the dimers to form polymeric chains.
Introduction
metathesis (RCM)reactions of vinylsulfonamide
templates catalyzed by the Grubbs ruthenium alkyli-
dene complex [10].
Recently, we have investigated the oxidation of
isothiazolium salts 1 and have found a new type of
cyclic sulfin- and sulfonamides with hydroxy and
hydroperoxy functions [11 - 13].
In this paper, we report on the synthesis and X-ray
diffraction analysis of compounds with sulfonyl and
sulfoxide groups which are interesting hydrogen-
bonding acceptors. This study should further our
understanding of noncovalent interactions between
the molecules and provide more detailed knowledge
concerning the three-dimensional structure of these
highly oxyfunctionalized S,N-heterocycles 2 - 5.
Cyclic sulfonamides (sultams)have attracted
considerable synthetic interest as chiral auxiliaries
in asymmetric synthesis since Oppolzer’s discovery
of campher sultam [2]. Toluene-2, -sultam and the
corresponding oxaziridines have also been applied
as chiral auxiliaries and for asymmetric oxidations
[
3 - 5]. 1,2-Benzisothiazole 1,1-dioxides are also a
class of compounds with a wide spectrum of biolog-
ical activities [6, 7]. The first non-benzoannelated
4
-amino-2,3-dihydroisothiazole 1,1-dioxides, lack-
ing a 3-oxo group, with anti-HIV-1 activity has re-
cently been described [8]. 5-Aryl-4-hydroxy-2,3-
dihydroisothiazole 1,1-dioxides can be used as her-
bicides, fungicides and pesticides [9]. New cyclic
vinylsultams have been synthesized by ring-closing
Results and Discussion
Presented in part at the 5th Conference on Iminium
S-Oxides rac-cis-2a [13] and rac-cis-2d are syn-
Salts (ImSaT-5), Stimpfach-Rechenberg (Germany), thesized conveniently by oxidation with H O in
2
2
September 11 - 13, 2001.
glacial acetic acid (r. t., 3 h)of isothiazolium salts
0
932–0776/02/0400–0383 $ 06.00 c 2002 Verlag der Zeitschrift f u¨ r Naturforschung, T u¨ bingen www.znaturforsch.com
K
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3
84
Table 1. Crystal data and structure refinement for 3b, 4a, 5a and 5e.
4a
B. Schulze et al. · Sultam and Sultim Structures, Part 2
3b
5a
5e
Empirical formula
Formula weight
Temperature [K]
Crystal system
Space group
C
15
H
17NO
4
S
C
13
H
15NO
6
S
C
13
H
15NO
5
S
17 2 4
C H21Cl NO S
307.36
223(2)223(2)215(2)218(2)
monoclinic monoclinic
P2 /c P2 /c
15.58620(10)11.6602(9) 8.2663(9)
313.32
297.32
406.31
monoclinic
P2 /c
9.5348(14)
monoclinic
P2 /c
1
1
1
1
˚
a [A]
˚
b [A]
8.00940(10)6.7397(5) 21.668(2) 13.1309(19)
12.2654(2)18.4321(15 8) .0014(9) 15.736(2)
˚
c [A]
[
]
111.13
91.720(2)105.637(2 1) 07.222(3)
3
˚
Volume [A ]
1428.17(3)1447.86(19 1) 380.2(3) 1881.9(5)
4
4
4
4
3
Density [Mg/m ]
1.429
1.437
1.431
0.253
1.434
0.477
1
Absorption coeff.[mm
Crystal size [mm]
]
0.242
0.250
0.25 0.20 0.20
1.40 - 27.53
0.30 0.20 0.20
2.21 - 28.75
0.20 0.20 0.15
1.88 - 28.92
0.20 0.20 0.10
2.06 - 28.98
Range for data collect. [ ]
Index ranges
–18
h
k
l
20,
9,
15
–15
–9
–24
9148
3474
[Rint = 0.0272]
SADABS
h
15,
9,
17
–11
h
k
l
10,
28,
4
–12
h
k
l
12,
17,
14
–10
–15
k
–28
–17
l
–10
–20
Reflections collected
Independent reflections
12543
3027
8980
3309
11885
4604
[Rint = 0.0479]
SADABS
[
R
int = 0.0782]
[Rint = 0.0760]
SADABS
Absorption correction
Max. / min. transmission
Data / parameters
Goodness-of-Fit on F
Final R indices [I > 2 (I)]
SADABS
0.9532 / 0.9419
3027 / 240
0.990
0.9517 / 0.9287
3474 / 250
1.048
0.9630 /0.9511
3309 / 241
1.002
0.9538 / 0.9106
4604 / 278
1.031
2
R
1
= 0.0542,
wR = 0.1305
= 0.0747,
wR = 0.1467
0.785 / –0.730
R
1
= 0.0399,
wR = 0.1053
= 0.0627,
wR = 0.1147
0.297 / –0.332
R
1
= 0.0700,
wR = 0.1710
= 0.1011,
wR = 0.1933
0.591 / –0.081
R
1
= 0.0599,
wR = 0.1675
= 0.1218,
wR = 0.2038
0.478 / –0.475
2
2
2
2
R Indices (all data)
R
1
R
1
R
1
R
1
2
2
2
2
3
˚
Lgst diff peak/hole [e A
]
1
containing an electron-withdrawing substituent at
the 2-aryl ring [12]. The same oxidation of the salts sulfones 4a and 5a are presented in Fig. 1. These
gave stable hydroperoxides 4a [13] and 4c [11] compounds form, surprisingly, compact new dimers
after 24 h without isolation of the 1-oxides 2. The in the solid state through C=O H-O interactions re-
-hydroxy sultims 3a [13], 3b and sultams 5a [13] lated by a center of symmetry inversion (Fig. 2). The
The structures of methoxycarbonyl-substituted
1
3
were formed by oxidation of DMSO with the cor- dimers are held together by strong intermolecular
responding hydroperoxides rac-cis-2 or 4. The 3- hydrogen bonds (C=O H-OO in 4a and C=O H-
hydroxy sultam 5e was synthesized by reduction of O in 5a). The bond parameters of these hydrogen
the hydroperoxide 4e with methylphenylsulfide.
bonds are very similar (Table 3). The torsion angle
between the isothiazole ring and the 2-aryl sub-
stituent is 163.4 (4a)and 166.2 (5a), respectively.
The analytical results and some physical proper-
ties of the novel 1-oxide 3b and 1,1-dioxide 5e are
described in the experimental part. The solid-state
structures of sulfoxide 3b and the sulfone amide
structures 4a, 5a and 5e were revealed by X-ray
crystallography. Crystallographic data are given in
Table 1, selected bond distance and angles in Ta-
ble 2. In the following we compare the solid state
structures of these compounds with those of 2a [13],
The two SO groups do not participate in a hydrogen
2
bond. They point in opposite directions in this new
‘head-to-tail’ dimers. However, other forces such
as the / interaction of the phenyl ring can also
provide stability, especially in 5a. The two aromatic
˚
planes in there dimers are separated by 3.54 A (4a)
˚
and 3.51 A (5a), respectively. The hydrogen bonds
held together a 20- or 22-membered ring, depend-
3
a [13], 2d [12] and 4c [11].
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B. Schulze et al. · Sultam and Sultim Structures, Part 2
385
˚
Table 2. Selected bond lengths [A] and angles [ ] for
b, 4a, 5a and5e with estimated standard deviations in
parentheses.
3
˚
Bond lengths [A]
Angles [ ]
3
b S(1)-O(1) 1.4858(19) O(1)-S(1)-N(1) 110.83(11)
S(1)-N(1) 1.686(2) O(1)-S(1)-C(3) 104.60(12)
S(1)-C(3) 1.775(3) N(1)-S(1)-C(3)
89.55(11)
O(2)-C(1) 1.407(3) C(1)-N(1)-S(1) 116.84(16)
N(1)-C(1) 1.476(3) O(2)-C(1)-C(2) 112.19(19)
C(1)-C(2) 1.494(3) N(1)-C(1)-C(2) 110.7(2)
C(2)-C(3) 1.320(4) C(3)-C(2)-C(1) 104.20(19)
C(2)-C(3)-S(1) 115.6(2)
4
a S(1)-O(4) 1.4280(14) O(4)-S(1)-O(3) 115.81(8)
S(1)-O(3) 1.4307(13) O(4)-S(1)-N(1) 110.49(8)
S(1)-N(1) 1.6623(14) O(3)-S(1)-N(1) 110.71(8)
S(1)-C(4) 1.7388(17) O(4)-S(1)-C(4) 112.21(8)
O(1)-C(1) 1.417(2) O(3)-S(1)-C(4) 111.28(8)
O(1)-O(2) 1.4615(19) N(1)-S(1)-C(4)
94.32(8)
O(2)-H(14) 0.92(3) C(1)-O(1)-O(2) 107.90(12)
N(1)-C(1) 1.452(2) O(1)-O(2)-H(14) 102.4(16)
C(1)-C(2) 1.508(2) C(1)-N(1)-S(1) 112.70(11)
C(2)-C(3) 1.488(3) O(1)-C(1)-N(1) 112.51(14)
O(1)-C(1)-C(2) 113.18(14)
5
a S(1)-O(1) 1.434(2) O(1)-S(1)-O(2) 115.30(13)
S(1-O(2) 1.4373(19) O(1)-S(1)-N(1) 110.38(12)
S(1)-N(1) 1.656(2) O(2)-S(1)-N(1) 112.19(13)
S(1)-C(3) 1.751(3) O(1)-S(1)-C(3) 111.81(13)
O(3)-C(1) 1.393(4) O(2)-S(1)-C(3) 110.85(13)
Scheme 1.
O(3)-H(30) 0.784(4) N(1)-S(1)-C(3)
94.46(13)
ing on whether two OH-(5a)or OOH-functions ( 4a)
are involved in the cyclic hydrogen-bond motif.
Interestingly, the 1-oxides 2a and 3a, with the
same substituent pattern as 4a/5a, do not show
N(1)-C(1) 1.479(3) C(1)-O(3)-H(30) 114(3)
C(1)-C(2) 1.502(4) N(1)-C(1)-C(2) 106.2(2)
C(2)-C(3) 1.340(4) C(1)-N(1)-S(1) 113.23(18)
O(3)-C(1)-N(1) 112.2(2)
5
e S(1)-O(1) 1.425(3) O(1)-S(1)-O(2) 114.8(2)
S(1)-O(2) 1.447(3) O(1)-S(1)-N(1) 112.90(19)
S(1)-N(1) 1.622(3) O(2)-S(1)-N(1) 110.25(18)
S(1)-C(3) 1.738(4) O(1)-S(1)-C(3) 112.0(2)
dimerization with participation of the p-CO Me
2
group [13]. They form polymer chains through
˚
strong intermolecular S-O H-O bridges (2.682 A
˚
in 2a and 2.763 A in 3a), similar to 3b (Table 3)[14].
O(3)-C(1) 1.369(5) N(1)-S(1)-C(3)
93.66(16)
N(1)-C(1) 1.496(4) C(1)-N(1)-S(1) 115.8 (2)
C(1)-C(2) 1.538(5) C(3)-C(2)-C(1) 116.3(3)
C(2)-C(3) 1.319(5) O(3)-C(1)-N(1) 110.7(3)
O(3)-C(1)-C(2) 110.0(3)
In 2a the polymer chains are formed by the c-
glide plane (space group P2 /c, Fig. 4)and in 3a two
1
symmetry independent molecules are connected by
an intermolecular O-H O-S hydrogen bond. The
polymer chains are formed by translation in direc-
tion of the b-axis (Fig. 5).
The bicyclic 1-oxide 3b (Fig. 3)shows the same
Most organic molecules that form dimers through intermolecular association through S-O H-O inter-
˚
hydrogen bonding give rise to a cyclic array of actions (2.723 A)between the sulfoxide O-atom and
eight atoms. Hydrogen-bonded dimers containing the H-atom of the HO-group of a second molecule,
a cyclic array of more than eight atoms are seldom resulting in the formation of polymer chains by the
encountered. A 12/14-membered hydrogen-bonded symmetry operation of the c-glide plane in the space
dimeric structure of 2-alkyl-3-hydroxybenzisothi- group P21/c, in which CH/ interactions involving
azole 1,1-dioxides has been reported recently [15]. the N-aryl ring can play an important role (Fig. 6).
In this case a molecular 'head-to-head' association The 2-aryl group is 8.4 out of plane of the isothia-
˚
through S-O H-O interaction (2.806 A)was found. zole ring.
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Fig. 1. Molecular structure
of 4a (top)and 5a (bottom)
with labelling and displace-
ment ellipsoids at the 50%
probility level.
Fig. 2. The centrosymmetric dimers of
4
a (left)and 5a (right)with O-H O=C
hydrogen bonds.
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B. Schulze et al. · Sultam and Sultim Structures, Part 2
387
Fig. 3. Molecular structure
of 3b (top)and 5e (bottom)
with labelling and displace-
ment ellipsoids at the 50%
probility level.
Fig. 4. Polymer arrangement of the
molecules of 2a by strong hydrogen
bonds OO-H OS. Symmetry code
1
1
1
a: x, /
2
– y, /
2
+ z; b: x, /
2
– y,
1
1
/
2
+ z.
The 1-oxide 2d, with two o-chloro substitutents membered ring, stabilized through two intermolec-
˚
at the N-aryl ring, is also arranged as a polymer, ular S-O H-O-O hydrogen bonds (2.833 A)be-
namely as a ‘head-to-head’ dimer with a 14- or 16- tween the sulfoxide O-atom and the HOO group of a
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388
B. Schulze et al. · Sultam and Sultim Structures, Part 2
Fig. 5. Polymer structure of 3a by strong hydrogen bonds between the two symmetry independent molecules a and b
along the crystallgraphic y-axis.
Fig. 6. Polymer structure of 3b
by strong S=O HO bonds. The
molecule b is formed by the c-glide
plane.
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B. Schulze et al. · Sultam and Sultim Structures, Part 2
389
a
b
Table 3. Geometric data for the hydrogen
bonds O-H O, in the solid state of 1-
oxides 2a, 2d, 3a, 3b and 1,1-dioxides
˚ ˚ ˚
D-H [A] H A [A] D A [A] D-H A [ ]
D-H A
c
2
a O(2)-H(30) O(3b) 0.91(3)1.80(3) 2.682
162(3)
4
a, 4g and 5a, 5e.
2
d O(2)-H(20) O(3)0.81(3 )2 .12(3 )2 .833(4) 147(2)
C(7)-H(17) O(1)0.97(3 2) .53(2 3) .379(2) 146(2)
a
Data calculated by using the program
3
a O(2)-H(20) O(5)0.82(4 )1 .96(4 )2 .741(3) 160(4)
b
SHELXL [16]; D: donor atom; A: ac-
O(6)-H(60) O(1)0.73(3 )2 .06(3 )2 .763(3) 163(3)
c
1
1
2 2
ceptor atom; b: x, / – y, / + z.
3
b O(2)-H(20) O(1)0.87(4 )1 .89(4 )2 .722(2) 158(4)
4
a O(2)-H(14) O(6)0.92(3 )1 .83(3 )2 .746(2) 174(2)
4
c O(2)-H(6) O(7)0.81( 32 ). 07( 42 ). 779(3 )1 45(4)
O(6)-H(20) O(8)0.82(3 )2 .01(3 )2 .779(3) 157(3)
C(3)-H(2) O(7)0.93( 23 .) 59(3 .) 237(2 )1 27(3)
C(20)-H(19) O(3)0.98(3) 2.46(4) 3.136(2) 126(2)
a O(3)-H(30) O(4)0.78(4 )2 .01(4 )2 .752(3) 158(4)
e O(3)-H(30) O(2)0.75(4 )1 .94(5 )2 .690(4) 172(5)
5
5
Fig. 7. Polymer structure of 2d with a centrosymmetric dimer arrangement mainted by strong hydrogen bonds
S(1a)-O(3a) H(2c)-O(2c)-O(1c)-C(7c)and S(1c)-O(3c) H(2a)-O(2a)-O(1a)-C(7a)as well as weak hydrogen bonds
C(7b)-H(7b) O(1c)-C(7c) and C(7c)-H(7c) O(1b)-C(7b).
second molecule. These dimers are connected by (Fig. 8). The polymer chains with the intermolecu-
short C(7)-H O(1)nonclassical hydrogen bonds
lar O-H O-hydrogen bonds are formed by a 21-
through centers of symmetry along the c-axis (Ta- scew axis in the space group P2 /c. The 2-aryl
1
ble 3 and Fig. 7). The torsion angle between the ring is almost perpendicular to the isothiazole ring
˚
isothiazole ring and the 2-aryl substituent is 93.2 . plane (84.2 ). The interatomic distance of 2.690 A
Therefore, the CH/ interaction can not stabilize determined for O-S-O H-O allows the formation
the polymer structure and the dimerization is more of strong intermolecular hydrogen bonds between
favorable.
For a comparative study, we prepared a further
,1-dioxide 5e in which the 2-aryl ring is highly
substituted, also with two chloro substituents and
coplanar heterocyclic systems. This is a new feature
of intermolecular interaction of such structures and
the first polymer motif of cyclic sulfonamides 5.
1
The 1,1-dioxide 4c crystallizes in the space group
an O-isopropyl group (Fig. 3). The crystallographic P1 with two symmetry independent molecules
data reveal the existence of only intermolecular hy- (Fig. 9). One of them independent forms dimers
drogen bonds, involving the 3-OH group and the with a center of symmetry and a strong intermolec-
oxygen of the sulfone group of a second molecule ular O-O-H O-S-O hydrogen bond. The other in-
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390
B. Schulze et al. · Sultam and Sultim Structures, Part 2
Fig. 8. Polymer structure of 5e by strong O-H O-S-O hydrogen bonds, generated by the 2
crystallographic y-axis.
1
-screw axis along the
Fig. 9. Tetrameric arrangement of 4c with strong hydrogenbonds S(2a)-O(8a) H(6b)-O(6b)and S(2b)-O(8b) H(6b)-
O(6b), which are generated by a centre of symmetry and a weak hydrogen bond S(1a)-O(3a) H-C. The molecules
with the atoms S(1a)and S(1b)are symmetry independent.
dependent molecule is connected to this dimeric unit
In conclusion, the discussed compounds were
by strong OO-H O-S'-O hydrogen bonds and weak found to exist as dimer, tetramer and polymer struc-
hydrogen bonds C-H O-S'-O to form a tetrameric tures through intermolecular hydrogen bonds with
unit.
the participation of S-O, SO and CO groups. If
2
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B. Schulze et al. · Sultam and Sultim Structures, Part 2
391
there is a possibility of strong hydrogen bonding residue by crystallization from ethanol provided rac-cis-
between C=O H-OO groups, as in the case of 4a 3b. Yield: 67%. M. p. 140 - 143 C. – IR (KBr): = 1042
1
(
SO), 1275, 1606, 1712 cm (C=O). – UV (ethanol):
and 5a, the weak O-acceptor of the SO function
2
1
(
lg ): 274.5 (3.53) nm. – H NMR (acetone-d
1.80 (m, 4H, 2 CH ), 2.40 (m, 4H, 2 CH ), 3.85
), 5.91 (m, 2H, 3-H and 3-OH), 7.99, 7.43
6
):
group does not participate. Therefore, the corre-
sponding 1,1-dioxides 4a and 5a show in the solid
state a self complementary hydrogen-bonding do-
nor-acceptor system that dimerizes through ‘head-
to-tail’ CO H-O hydrogen bonds and is stabi-
max
=
2
2
(
(
2
1
s, 3H, OCH
AB = 9.0 Hz, o/m-H). – C NMR (aceton-d
2.6, 23.4, 24.8 (C-4,5,6,7); 52.7 (OCH ), 89.7 (C-3),
16.9 (2 arom. CH), 124.7 (arom. C), 132.4 (2 arom.
3
1
3
J
6
): = 22.2,
3
lized by
-interactions. Compounds 2a and 3a,b
CH), 140.8 (arom. C), 145.2(C-7a), 148.0 (C-3a), 167.5
with sulfoxide functions, form exclusively polymer
structures through intermolecular S-O H-OO (2a)
or S-O H-O (3a,b)hydrogen bonds. In 5e, a 1,1-
dioxide without a CO-function, a different type of
strong intermolecular OSO H-O hydrogen bond is
found. This is the first solid polymer structure of a
+
+
(
C=O). – MS: m/z = 307 (M , 10), 259 ([M-SO] , 100). –
S (307.39): calcd. C 58.61, H 5.59, N 4.56, O
0.80, S 10.43; found C 58.30, H 5.58, N 4.52, O 20.82,
S 10.60.
15
C H17NO
4
2
2
5
1
-(2,5-Dichloro-4-isopropyloxyphenyl)-3-hydroxy-
,6,7,8-tetrahydro-4H-cyclohepta[d]isothiazole
,1-dioxide (5e)
1,1-dioxide.
Surprisingly, a ‘head-to-head’ dimer with two
strong SO H-OO hydrogen bonds was found in the
-oxide 2d. This is the first example of hydrogen-
2 2
H O (0.7 ml, 30%)was added to a stirred suspen-
1
sion of 1e (0.26 mmol)in AcOH (0.7 ml)at r. t. Af-
ter 8 h a colourless precipitate 4e crystallized. The 1,1-
dioxide 4e was reduced to 5e with one equivalent of
methylphenylsulfide in dichloromethane. Purification of
e was achieved by column chromatography on silca gel
using ethyl acetate / n-hexane 4:5 (v/v)as eluent. Yield:
bonding interactions between a sulfoxide group re-
sulting in the formation of a 14/16-membered ring.
The polymer chain of this 2d dimer is stabilized ad-
ditionally through short nonclassical C-H O-C hy-
drogen bonds. The tetramer structure in 4c is formed
by combination of strong OO-H O-S-O and short
O-S-O H-C hydrogen bonds.
5
9
1
(
6
4%. M. p. 204 - 207 C. – IR (KBr): = 1280s (SO
2
),
).). – UV (ethanol): max (lg : 284.0
): = 1,40 (d, J = 6.0 Hz,
), 1.70 - 1.90 (6H, 3CH ), 2.50 - 2.70 (m, 4H,
), 3.21 (d, J = 10.6 Hz, 1H, 3-OH), 4.57 (m, 1H,
), 5.42 (d, J = 10.6 Hz, 1H, 3-H), 7.05 (s, 1H,
1
155s cm (SO
1.97)nm. – H NMR (CDCl
3
2
1
Experimental
H, 2 CH
CH
3
2
2
2
General. M. p.: Boetius micro-melting-point appara-
CH(CH
arom. H), 7.54 (s, 1H, arom. H). – C NMR (CDCl
= 22.0 (CH ), 23.7, 26.4, 26.8, 28.8, 30.3 (C-4,5,6,7,8),
3 2
)
tus; corrected. IR spectra: Genisis FTIR Unicam Analyt-
1
3
1
3
):
ical System (ATI Mattson); KBr pellets; values in cm
.
1
3
H-NMR: Varian Gemini-200 and Varian Unity-400; in
1
3
73.0 (O-CH, 84.3 (C-3), 116.0 (arom.), 122.9, 123.1 (2
ppm rel. to TMS as internal standard, J in Hz. C-NMR
spectra: 50 or 100 MHz, recorded on the above spectrom-
eters. MS: Quadrupol-MS VG 12-250; 70 eV. Elemental
analysis: Heraeus CHNO Rapid Analyzer.
arom.), 134.7 (arom.), 134.8 (arom.), 137.3 (C-8a), 145.5
+
(
C
1
C-3a), 155.1 (C-O-iPr). – EI-MS: m/z = 406 (M ) . –
17
H
21Cl
2
NO
4
S (406.32): calcd. C 50.25, H 5.21, Cl
7.45, N 3.45, O 15.75, S 7.89; found C 50.43, H 5.28,
Cl 17.31, N 3.51, O 15.62, S 7.93.
Syntheses. The salts 1b,d were prepared according to
[
12]; 1a according to [13]; 1c to [11]. The 1-oxides 2a,3a
Single crystal X-ray diffractometry: Crystal of 3b, 4a,
a and 5e were obtained from acetone. The intensities
and the 1,1-dioxides 4a,5a are described in [13] the hy-
droperoxides 2b,d and 4c in [11, 12].
5
were measured on a Siemens SMART CCD diffrac-
tometer. Relevant crystallographic data are listed in Ta-
ble 1. The structures were solved by direct methods
with SHELXS-97 [16]. The refinement was done with
SHELXL-97 [16]. Details of the structure analyses have
been deposited with the Cambridge Crystallographic Data
cis-2,3,4,5,6,7-Hexahydro-3-hydroxy-2(4-methoxycarb-
onylphenyl)-1,2-benzisothiazole 1-oxide (rac-cis-3b)
H
2
O
2
(0.7 ml, 30%)was added to a stirred suspension
of 1b (0.26 mmol)in AcOH (0.7 ml)at r. t. After 2 - 3 h,
the starting material was dissolved and a colorless precip- Centre, CCDC-179236 for 3b, -179238 for 4a, -179237
itate (rac-cis-3b)was immediately filtered off to prevent
oxidation to 4b. The crude product was washed with H
for 5a and -179235 for 5e. Copies of the data can be ob-
O, tained, free of charge, from CCDC, 12 Union Road, Cam-
2
recrystallized from isopropanol and dissolved in DMSO. bridge, CB2 1EZ UK (fax: +44-1233-336033; e-mail: de-
After 24 h the solution was lyophilized. Purification of posit@ccdc.cam.ac.uk; internet: //www.ccdc.cam.ac.uk).
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392
B. Schulze et al. · Sultam and Sultim Structures, Part 2
Acknowledgements
The work was supported by Deutsche Forschungsge-
meinschaft and by Fonds der Chemischen Industrie.
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