986 J. Am. Chem. Soc., Vol. 119, No. 5, 1997
Sander et al.
(Messer-Griesheim, 99.9999%), mixtures of argon and oxygen (Messer
Griesheim, 99.998%), or mixtures of argon and sulfur dioxide (99.97%)
on top of a CsI (IR) or sapphire (UV-vis) window with a rate of
approximately 0.15 mmol/min. In order to obtain optically clear
matrices, the cold window was retained at 30 K (Ar), 25-30 K (Ar/
O2), or 17 K (Ar/SO2) during deposition and afterward cooled to 8-10
K. Ozone was generated with an Ozonizer (Demag), trapped at 77 K
and purified according to ref 33.
Infrared spectra were recorded by using a Bruker IFS66 FTIR
spectrometer with a standard resolution of 1 cm-1 in the range of 400-
4000 cm-1. Irradiations were carried out with use of Osram HBO 500
W/2 mercury high-pressure arc lamps in Oriel housings equipped with
quartz optics. IR irradiation from the lamps was absorbed by a 10 cm
path of water. Schott cut off filters were used (50% transmission at
the wavelength specified) in combination with dichroic mirrors.
The IR spectroscopic data of 5 and 6 are described in Tables 1 and
2.
Phenyl(phenylsulfonyl)carbene (11). Irradiation (λ > 475 nm, Ar,
10 K) of the matrix-isolated sulfonyldiazomethane 10 produced carbene
11 as the main product. IR (Ar, 10 K): 1587 (17), 1559 (5), 1325
(46), 1289 (10), 1154 (41), 1087 (37), 914 (37), 877 (3), 773 (3), 748
(27), 732 (44), 671 (32), 609 (5), 569 (100), 544 (54) cm-1 (rel
intensity). UV (Ar, 10 K): 250, 274 nm.
Phenyl Phenylsulfonyl Ketone O-Oxide (12). Annealing carbene
11 in an 0.5% O2-doped argon matrix at 41 K produced carbonyl oxide
12 as the main product. IR (Ar, 10 K): 1596 (43, 1.0), 1379 (43,
1.0), 1362 (57, 1.0), 1170 (89, 1.0), 1090 (36, 1.0), 1018 (29, 0.970),
999 (36, 0.965), 974 (43, 1.0), 951 (32, 0.928), 931 (18, 0.930), 909
(50, 1.0), 767 (46, 1.0), 728 (29, 1.0), 684 (71, 1.0), 627 (29, 0.976),
597 (100, 1.0), 587 (68, 1.0) cm-1 (rel intensity, ratio of 18O/16O isotopic
frequencies νi/ν).
Phenyl Phenylsulfonyl Ketone (13). Irradiation (λ > 590 nm, Ar,
10 K) of matrix-isolated carbonyl oxide 12 produced ketone 13 and
phenyl(phenylsulfonyl)dioxirane (14) as the main products. IR (Ar,
10 K): 1719 (38, 0.980), 1600 (15, 1.0), 1329 (31, 1.0), 1220 (69,
1.0), 1155 (100, 1.0), 1034 (15, 0.945), 898 (8, 1.0), 777 (46, 1.0),
724 (54, 1.0), 569 (46, 1.0) cm-1 (rel intensity, ratio of 18O/16O isotopic
frequencies νi/ν).
benzaldehyde (31 mmol, 3.3 g), and benzyltriethylammonium chloride
(160 mg) in acetonitrile (8 mL) cooled in ice. After 1.5 h of stirring
at 0 °C, the solid material was collected by filtration and washed with
water until the filtrate was neutral. The product was dissolved in
dichloromethane and dried over anhydrous sodium sulfate. The solvent
was removed under reduced pressure to give 4.6 g (67%) of oxirane
18, mp 102-103 °C (lit.31 102-104 °C). 1H NMR (80 MHz, CDCl3):
δ ) 4.18 (d, 1H), 4.55 (d, 1H), 7.15-8.05 (m, 10H, aromatic) ppm.
MS: m/z (%) ) 260 (1.3) [M+], 141 (3.5) [M+ - C6H5CH(O)CH ],
119 (72) [M+ - C6H5SO2], 91 (100) [C6H5CH2+], 77 (36) [C6H5+].
2-Phenyl-2-(phenylsulfonyl)acetaldehyde (19). A modification of
a procedure by Zwanenburg et al.30 was used to prepare aldehyde 19.
A solution of boron trifluoride-etherate (7.5 mmol, 1 g) in dichlo-
romethane (7 ml) was added slowly to a solution of oxirane 18 (7 mmol,
1.8 g) in dichloromethane (52 mL) cooled in ice. After 10 min of
stirring at 0 °C, water was added very carefully. The organic layer
was separated and pentane was added to remove the main part of the
contamination. The solution was filtered and evaporated under reduced
pressure. The residue was chromatographed on silica in pentane/ether
1:1 to give 0.5 g (26%) of 19. 1H NMR (80 MHz, CDCl3): δ ) 4.9
(d, J ) 2.5 Hz, 1H, C6H5C(CHO)HSO2-), 7.15-7.7 (m, 10H, aromatic),
10.0 (d, J ) 2.5 Hz, 1H, C6H5C(CHO)HSO2-) ppm.
Phenyl(phenylsulfonyl)diazomethane (10). For the synthesis of
10 a modified method by van Leusen et al.32 was used. To the stirred
solution of 0.5 mg (1.8 mmol) of aldehyde 19 in 28 mL of
dichloromethane were added 2.1 g (9.4 mmol) of p-carboxybenzene-
sulfonyl acid and 14 ml of 2 M aqueous ammonia. After 20 h of stirring
at room temperature in the dark, the organic layer was slowly filtered
over alumina (Merck, activity II-III) and concentrated. The resulting
red oil was purified by chromatography on alumina with CCl4 as eluent.
The resulting red oil was crystallized from hexane to give 0.098 g (21%)
of 10, mp 45-46 °C (dec.). 1H NMR (400 MHz, CDCl3): δ ) 7.15-
7.62 (m, 8H, aromatic), 7.88 (d, 3J ) 8.3 Hz, 2H, aromatic) ppm. 13C
NMR (100 MHz, CDCl3): δ ) 123.33, 124.61, 126.66, 127.19, 129.34,
133.48, 142.39 ppm. IR (KBr): ν ) 2081 (s), 1594 (m), 1493 (m),
1329 (s), 1149 (s), 754 (m) cm -1. UV (CH3CN): λmax (log ꢀ) ) 196
(4.42), 261 (4.03), 444 (2.06) nm. MS: m/z (%) ) 258 (9) [M+], 141
(7) [M+ - C(C6H5)N2], 77 (100) [C6H5+], 28 (27) [N2+]. Anal. Calcd
for C13H10N2O2S: C, 60.46; H, 3.90; N, 10.84; S, 12.41. Found: C,
60.52; H, 3.86; N, 10.76; S, 12.43.
Phenyl(phenylsulfonyl)dioxirane (14). IR (Ar, 10 K): 1582 (9,
1.0), 1352 (27, 1.0), 1159 (55, 1.0), 1091 (9, 1.0), 917 (5, 1.0), 755
(27, 1.0), 726 (36, 1.0), 687 (45, 1.0), 608 (55, 1.0), 582 (100, 1.0)
cm-1 (rel intensity, ratio of 18O/16O isotopic frequencies νi/ν).
O,S-Diphenyl Thiocarbonate S,S-Dioxide (15). Irradiation (λ >
420 nm, Ar, 10 K) of matrix-isolated dioxirane 14 produced 15 as the
main product. IR (Ar, 10 K): 1775 (67, 0.982), 1411 (44, 1.0), 1329
(11, 1.0), 1238, (56, 1.0), 1223 (11, 0.995), 1205 (100, 1.0), 1167 (89,
1.0), 1111 (44, 1.0), 992 (56, 1.0), 827 (22, 0.947), 763 (78, 0.982),
653 (33, 1.0), 592 (78, 1.0) cm-1 (rel intensity, ratio of 18O/16O isotopic
frequencies νi/ν).
Acknowledgment. This work was financially supported by
the Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie. A.K. gratefully acknowledges a graduate
fellowship by the Land Niedersachsen. We also thank Prof.
B. Zwanenburg and Dr. H. J. F. Philipse for their hospitality
and helpful advice in the synthesis of diphenylsulfine.
Matrix Spectroscopy. Matrix-isolation experiments were performed
by standard techniques with an APD CSW-202 Displex closed-cycle
helium cryostat. Matrices were produced by deposition of argon
(31) Zwanenburg; Binne; Wiel, Ter and J Tetrahedron Lett. 1970, 12,
JA962949K
935-936.
(32) Van Leusen, A. M.; Reith, B. A.; Van Leusen, D. Tetrahedron 1975,
31, 597-600.
(33) Tra¨ubel, M. Ph.D. Dissertation, Technische Universita¨t Braunsch-
weig, 1994.