5722
T. Rosenau et al. / Tetrahedron 60 (2004) 5719–5723
plates (5£10 cm, 0.25 mm) with fluorescence detection
under UV light at 254 nm. Melting points, determined on a
Kofler-type micro hot stage with a Reichert-Biovar
microscope, are uncorrected.
stirring to 100 8C for 1 h. A yellow solid precipitated, which
was collected by filtration after additional stirring for 3 h at
rt. The solid was thoroughly washed with ethyl acetate and
dried in vacuo to provide 3 (1.87 g, 72%), mp (H O)
2
.300 8C. Crystals for X-ray diffraction were obtained by
slow evaporation of a concentrated aqueous solution,. H
1
X-ray data collection was performed with a Bruker AXS
Smart APEX CCD diffractometer and graphite mono-
chromatized Mo Ka radiation; corrections for absorption
with the program SADABS, structure solution with
1
3
NMR (D O): d 3.08 (s, 12H, Me). C NMR (D O): d 25.4
2
2
(Me), 94.4 (C–S), 177.0 (C–O). Anal. Calcd for
C H O S (260.33): C 46.14, H 4.65, S 24.63. Found: C
45.82, H 4.41. Recrystallization from glacial acetic acid
1
0 12 4 2
2
direct methods, structure refinement on F (Bruker AXS,
2
6
001: programs SMART, version 5.626; SAINT, version
.36A; SADABS version 2.05; XPREP, version 6.12;
provided the bis(acetic acid) adduct as yellow needles, mp
1
182–184 8C. H NMR (D O): d 2.22 (s, 6H, Me in Ac), 3.20
2
1
3
SHELXTL, version 6.10. Bruker AXS Inc., Madison, WI,
USA).
(s, 12H, Me). C NMR (D O): d 21.4 (Me in Ac), 25.8
2
(Me), 94.8 (C–S), 177.2 (C–O), 177.5 (C–O in Ac). Anal.
Calcd for C H O S (380.44): C 44.20, H 5.30, S 16.86.
Found: C 44.08, H 5.40. Recrystallization from formic acid
1
4 20 8 2
CCDC-232906 and 232907 contain the supplementary
by contacting The Cambridge Crystallographic Data Centre,
provided the bis(formic acid) adduct as yellow needles, mp
1
188–191 8C. H NMR (D O): d 3.22 (s, 12H, Me), 8.25 (s,
2
1
3
2H, HCO). C NMR (D O): d 25.6 (Me), 94.9 (C–S), 177.4
2
(C–O), 179.3 (HCO). Anal. Calcd for C H O S
8 2
1
2
16
1
3
2, Union Road, Cambridge CB2 1EZ, UK; fax: þ44-1223-
(352.38): C 40.90, H 4.58, S 18.20. Found: C 41.19, H
4.82.
36033.
Crystal data for bis(sulfonium ylide) 3. C H O S ,
0 12 4 2
Sulfonium ylide 4. Using 2-hydroxynaphthoquinone (2)
(1.74 g, 10 mmol) instead of 1, compound 4 was obtained
according to the above procedure (1.97 g, 84%), mp 263–
265 8C. Crystals for X-ray diffraction were obtained by slow
cooling of a concentrated solution in water/methanol
1
M¼260.32, monoclinic, space group P2 /c, a¼6.0629(4),
1
˚
b¼7.7367(5), c¼11.9325(7) A, b¼91.087(1)8, V¼
˚
3
3
5
59.62(6) A , Z¼2, D
¼1.545 g/cm , T¼300(2) K,
calcd
2
1
m¼0.470 mm , F(000)¼272, yellow prism (0.70£
1
0
.35£0.35 mm), total/unique reflections 4181/1605,
(v/v¼2:1). H NMR (DCOOD): d 3.30 (s, 6H, Me), 7.82
Ar
Ar
Ar
13
R ¼0.019. Final refinement: data/restraints/parameters
int
(t, 1H, H), 7.92 (t, 1H, H), 8.11 (t, 2H, H). C NMR
(DCOOD): d 25.7 (Me), 98.5 (C–S), 127.5 (CH), 128.3
1
605/0/78, GOF¼1.08, R ¼0.027, wR ¼0.073 (all data).
1
2
(CH), 131.3, 134.1, 134.3 (CH), 136.5 (CH), 172.2, 181.6,
182.4. Anal. Calcd for C H O S (234.28): C 61.52, H
4.30, S 13.69. Found: C 61.09, H 4.20.
Crystal data for sulfonium ylide 4. C H O S, M¼234.26,
1
2
10
3
12 10 3
orthorhombic, space group Pnma, a¼9.5360(12),
˚
˚
3
b¼9.5360(12), c¼15.924(2) A, V¼1072.4(2) A , Z¼4,
3
21
D
¼1. 451 g/cm , T¼297(2) K, m¼0.289 mm
,
Mannich bisbetaine 6. Bisylide 3 (0.52 g, 2 mmol) was
suspended in DMF (50 mL) and heated to 70 8C. A solution
of NMMO monohydrate (5, 0.57 g, 4.2 mmol) in DMF
(10 mL) was added dropwise during 1 min. After complete
addition, the red mixture became clear almost immediately,
and a few minutes later a brick-red solid started to
precipitate. The mixture was stirred for additional two
hours and cooled to rt. The precipitate was isolated by
filtration, washed thoroughly with ethyl acetate and dried in
calcd
F(000)¼488, yellow prism (0.58£0.16£0.14 mm), total/
unique reflections 7764/1611, R ¼0.025. Final refinement:
int
data/restraints/parameters
1611/0/95,
R ¼0.058, wR ¼0.143 (all data).
GOF¼1.05,
1
2
The solid state NMR measurements were recorded on a
Bruker DMX Avance 400 spectrometer, using a double
1
3
channel 4 mm CPMAS. The C CPMAS spectra were
acquired at a radio frequency of 100.62. MHz. The spinning
frequency was 12500 Hz and was stabilized to ^2 Hz. 222
scans have been acquired using a repetition time of 6 s, a
CP-time of 5 ms (50% ramp on proton channel) and TPPM
1
vacuo to give 6a (0.49 g, 72%), mp 265 8C (decomp.). H
NMR (D O): d 3.20 (t, 8H, N–CH –CH ), 3.87 (m, 8H, O–
2
2
2
1
3
CH ), 3.95 (s, 4H, N–CH –C). C NMR (D O): d 51.8
2
2
2
(N–CH –CH ), 52.2 (N–CH –C), 64.5 (O–CH ), 103.6
2
2
2
2
8
decoupling with a phase shift of 108 during the acquisition
time.
(C), 180.1 (C–O). Anal. Calcd for the monohydrate
C H N O (356.38): C 53.93, H 6.79, N 7.86. Found: C
1
6 24 2 7
54.50, H 6.25, N 7.42.
Spectra in solution were recorded with a Bruker Avance
1
DPX instrument operating at 300.13 MHz for H and
3
Mannich betaine 7. Employing naphtho-ylide 4 (0.47 g,
2 mmol) instead of 3, compound 7 was obtained according
1
7
5.47 MHz for C using tetramethylsilane as internal
1
standard. Homo- and heteronuclear 2D NMR spectroscopy
was performed with Bruker standard software. Chemical
to the above procedure in 87% yield, mp 192–196 8C. H
NMR (D O): d 3.16 (t, 4H, N–CH –CH ), 3.80 (t, 4H,
2
2
2
1
3
Ar
shifts are given in ppm, coupling constants in Hz. C peaks
were assigned by means of APT, HMQC and HMBC
spectra.
O–CH ), 3.92 (s, 2H, N–CH –C), 7.81 (t, 1H, H), 7.90
2 2
Ar
Ar
13
(t, 1H, H), 8.10 (t, 2H, H). C NMR (D O): d 51.4
2
(N–CH –CH ), 52.4 (N–CH –C), 64.3 (O–CH ), 101.9,
2
2
2
2
1
27.0 (CH), 128.8 (CH), 131.1, 134.5 (CH), 134.6, 136.7
(CH), 177.8, 182.0, 183.1. Anal. Calcd for C H NO
4
Bis(sulfonium ylide) 3. 2,5-Dihydroxybenzoquinone
1
5
15
(1.40 g, 10 mmol) was suspended in a mixture of acetic
anhydride (20 mL) and DMSO (5 mL) and heated under
(273.29): C 65.93, H 5.53, N 5.13. Found: C 66.08, H 5.71,
N 4.97.