Synthesis of stable arsonium and sulfur ylides from perfluoroalkanesulfonyl diazocarbonyl compounds and their X-ray diffraction analysis

Article abstract of DOI:10.1016/j.jfluchem.2008.01.007

A series of stable fluorine-containing arsonium ylides and sulfur ylides were simply synthesized from perfluoroalkanesulfonyl diazocarbonyl compounds in the presence of rhodium catalyst. The ylide products are fairly stable due to the strong electron-withdrawing properties of perfluoroalkanesulfonyl group and carbonyl group. They are fully confirmed by spectral methods and the structures of 3ba and 3cd are also established by X-ray single crystal diffraction analysis. Several interesting features about the ylide structures and some weak fluorine interaction between them are described here.

Full text of DOI:10.1016/j.jfluchem.2008.01.007

Available online at www.sciencedirect.com
Journal of Fluorine Chemistry 129 (2008) 343–348
www.elsevier.com/locate/fluor
Synthesis of stable arsonium and sulfur ylides from
perfluoroalkanesulfonyl diazocarbonyl compounds
and their X-ray diffraction analysis
Wan Pang a,b, Shifa Zhu b, Chunhui Xing b, Nianhua Luo b,
b,
Huanfeng Jiang a, , Shizheng Zhu
*
*
a College of Chemistry, South China University of Technology, Guangzhou 510640, China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Lu, Shanghai 200032, China
Received 11 November 2007; received in revised form 5 January 2008; accepted 7 January 2008
Available online 5 February 2008
Abstract
A series of stable fluorine-containing arsonium ylides and sulfur ylides were simply synthesized from perfluoroalkanesulfonyl diazocarbonyl
compounds in the presence of rhodium catalyst. The ylide products are fairly stable due to the strong electron-withdrawing properties of
perfluoroalkanesulfonyl group and carbonyl group. They are fully confirmed by spectral methods and the structures of 3ba and 3cd are also
established by X-ray single crystal diffraction analysis. Several interesting features about the ylide structures and some weak fluorine interaction
between them are described here.
# 2008 Elsevier B.V. All rights reserved.
Keywords: Perfluoroalkanesulfonyl; Ylides; Diazocarbonyl compound; X-ray diffraction analysis; Weak fluorine interaction
1. Introduction
the ylide carbon and their structures do not facilitate subsequent
rapid reactions.
It is known that both direct and indirect routes for the
formation of ylide from diazocarbonyl compounds have been
well developed [1]. Thermal, photochemical and catalytic
methods have been used, but catalytic methodologies offer the
greatest advantages. Metal carbenes derived from a-diazo-
carbonyl compounds are highly electrophilic. They readily
react with an available Lewis base to effect ylide formation
[2].
Per(poly)fluoroalkanesulfonyl group, RfSO2, is one of the
strongest electron-withdrawing groups which can active a-C–H
bonds and adjacent olefins or function as nucleofugic leaving
group having an electron pair to form sulfinate anions depending
upon their environment [4]. Due to their various reactivities,
per(poly)fluoroalkanesulfonyl groups are of special interest in
organic chemistry, especially in organofluorine chemistry.
In the last decade, weak fluorine interaction, aryl-perfluoro-
ary-, C–FÁ Á ÁH, FÁ Á ÁF, FÁ Á ÁO and FÁ Á ÁpF interactions, gained an
increasing interest. They are interactions between electron–
neutral atoms or structures, which are not sensitive to the solvent,
pH value. They are ubiquitous in the fluorine-containing
molecules. Herein, how to make use of these ubiquitous weak
interactions remained a great challenge to chemists [5].
In this paper, we describe a simple synthesis of stable
perfluoroalkanesulfonyl-containing ylides from perfluoroalk-
anesulfonyl diazocarbonyl compounds by catalytic methods.
Furthermore, some interesting structural features and weak
fluorine interactions of the stable ylide 3ba and 3cd are also
reported here.
The most common reactions of catalytically generated ylide
are [2,3]-sigmatropic rearrangement of allyl-substituted ylide
intermediates; [1,2] insertion or Stevens rearrangement; b-
hydride elimination; dipolar cycloaddition. These processes,
which can proceed intermolecularly or intramolecularly, have
showngreatversatilityinthesynthesisofnaturalproducts[3]. On
the other hand, these ylide carbenes also can be isolated as stable
reaction products if two electron-withdrawing groups stabilize
* Corresponding authors. Tel.: +86 21 54925184; fax: +86 21 64166128.
E-mail address: zhusz@mail.sioc.ac.cn (S. Zhu).
0022-1139/$ – see front matter # 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2008.01.007

344
W. Pang et al. / Journal of Fluorine Chemistry 129 (2008) 343–348
the negative charge. The structures of products 3 were
determined by IR and NMR (1H, 19F) spectroscopy, mass
spectrometry and elemental analysis. Infrared spectroscopy
demonstrated significant lowering of the carbonyl frequency,
consistent with the presence of an electron-rich center (ylidic
carbon) in the a-position [7].
Scheme 1.
The ylides 3 were soluble in chloroform, dichloromethane
and ethyl acetate, but not in the less polar solvent hexane. Solid
state structure of 3ba, obtained by recrystallization from
hexane-ethyl acetate at room temperature, illustrates an ylide
structure (Fig. 1). Analysis of the Fig. 1 showed several
interesting features: the four atoms As1, C1, C2, O1 are
˚
coplanar with the distance deviation of 0.172 A from the plane
Scheme 2.
of As1, C1 and C2 and with the sums of the C1-centered bond
angles 8C1 = 358.88, indicating an sp2 hybridization of the
P
˚
ylide carbanion C1. The distance of As1–C1 (1.888 (6) A) is
˚
considerably shorter than those of As1–C9 (1.915 (6) A), As1–
2. Results and discussion
˚
˚
Diazocarbonyl compound 1 can be conveniently prepared by
the diazo group transfer reactions with polyfluoroalkanesulfo-
nyl azide as diazo transfer reagent (Scheme 1) [6].
C15 (1.921 (6) A), As1–C21 (1.924 (6) A). These results
suggest little double-bond character for the ylidic bond as well
as a negligibly small electrostatic attraction between the
oppositely charged As1 and C1. The As1–C1–C2 bond angle is
The stable perfluoroalkanesulfonyl-containing ylides 3 were
easily prepared as shown in Scheme 2. Treatment of
diazocarbonyl compound 1 (0.5 mmol) with triphenylarsine,
sulfide or sulfoxide 2 (0.5 mmol) in the presence of Rh2(OAc)4
(1 mol%) afforded stable ylides 3 in 27–96% overall yields.
The results are summarized in Table 1.
˚
110.2 (5)8. The distance of As1Á Á ÁO1 is 2.756 A, which is
˚
shorter than that of the sum of van der Waals radii (3.37 A).
Interestingly, analysis of the X-ray crystal structure of 3ba, we
˚
found that the bond length of the C1–C2 is 1.432 (9) A, which is
˚
longer than the standard double bond of C C (1.34 A), but
˚
shorter than the single bong of C–C (1.53 A). And the bond
˚
length of the C2–O1 is 1.241 (8) A, which is longer than the
˚
standard double bond of C O (1.22 A), but shorter than the
˚
single bong of C–O (1.43 A). In addition to the intramolecular
As indicated in Table 1, because of two strong withdrawing
groups, all of the triphenylarine, dimethylsulfide, dimethylsulf-
oxide and tetramethylene sulfoxide can afford the stable ylides.
The yields varied greatly depending on the power of electron
withdrawing of Rf and R. For instance, comparing entries 1
(R = Me) and 2 (R = Ph), it is clear that 1b gives a markedly
higher conversion to the coupled product than 1a. We
speculated that the strength of the electron-withdrawing and
conjugate effect of phenyl was stronger than methyl.
˚
short As1Á Á ÁO1 (2.756 A) contact, two nearly vertical C2–
O1Á Á ÁH* secondary bonding to one of the phenyl of an adjacent
˚
molecule was found with OÁ Á ÁH distance of 2.502 and 2.698 A,
which links individual molecules of 3ba into infinite zigzag
chains (Fig. 2). In addition, the packing structure of 3ba
is further stabilized by a nearly linear C–FÁ Á ÁH* weak
These ylides 3 are quite stable and can be stored indefinitely
at room temperature. For example, the ylide 3ba can be heated
to melting without any decomposition. Key to the success of the
synthesis of 3 seems to be the presence of two highly electron-
withdrawing perfluoroalkylsulfonyl group and carbonyl group
which stabilize the ylide carbanions through delocalization of
Table 1
Reaction results of perfluoroalkanesulfonyl diazocarbonyl compounds 1 with 2
Entry
1
Rf
R
2 (Y)
Product Yield (%)a m.p. (8C)
1
2
3
4
5
6
7
8
a
b
c
d
e
c
c
c
ClC4F8 CH3
ClC4F8 Ph
Ph3As
Ph3As
Ph3As
Ph3As
3aa
3ba
3ca
3da
3ea
3cb
3cc
3cd
28
96
65
60
32
42
27
40
205–207
196–198
156–158
197–199
151–153
67–69
CF3
CF3
CF3
CF3
CF3
CF3
CH3
Ph
OC2H5 Ph3As
CH3
CH3
CH3
CH3SCH3
Me2S(O)
144–146
148–150
a
Isolate yield based on 1.
Fig. 1. The molecular structure of compound 3ba.

W. Pang et al. / Journal of Fluorine Chemistry 129 (2008) 343–348
345
Fig. 2. Packing map of compound 3ba by OÁ Á ÁH bands.
Fig. 3. Packing map of compound 3ba by FÁ Á ÁH bands.
˚
˚
with the distance deviation of 0.050 A from the plane of S1,
intermolecular interactions. The FÁ Á ÁH* distance is 2.607 A
and the C–FÁ Á ÁH* angle is 178.898, which links individual
molecules of 3ba into infinite linear chains (Fig. 3).
Likewise, we can seen from the crystal structure of sulfur
ylide 3cd (Fig. 4), the four atoms S1, C5, C6, O2 are coplanar
C5 and C6 and with the sums of the C5–centered bond angles
8C5 = 357.18, indicating an sp2 hybridization of the ylide
P
˚
carbanion C5. The distance of S1–C5 is 1.715 (3) A, which is
˚
between the standard single bong of S–C (1.81 A) and double
˚
bond of S C (1.61 A). These results suggest little double-
bond character for the ylidic bond as well as a negligibly
small electrostatic attraction between the oppositely charged
S1 and C5. The S1–C5–C6 bond angle is 114.62 (18)8. The
˚
distance of S1Á Á ÁO2 is 2.800 A, which is shorter than that of
˚
the sum of van der Waals radii (3.32 A). Interestingly,
analysis of the X-ray crystal structure of 3cd, we found that
˚
the bond length of the C5–C6 is 1.455 (9) A, which is longer
˚
than the standard double bond of C C (1.34 A), but shorter
˚
than the single bong of C–C (1.53 A). And the bond length of
˚
the C6–O2 is 1.226 (3) A, which is longer than the standard
˚
double bond of C O (1.22 A), but shorter than the single bong
˚
of C–O (1.43 A). In addition to the intramolecular short
˚
S1Á Á ÁO2 (2.800 A) contact, two nearly parallel C6–O2Á Á ÁH*
secondary bonding to one of the five-membered of an adjacent
˚
molecule were found with the distances of 2.356 A
˚
(O2Á Á ÁH4B) and 2.698 A (O4Á Á ÁH1A), which links individual
molecules of 3cd into infinite zigzag chains (Fig. 5). Some
selected bond lengths and angles of compounds 3ba and 3cd
are summarized in Table 2.
Fig. 4. The molecular structure of compound 3cd.

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W. Pang et al. / Journal of Fluorine Chemistry 129 (2008) 343–348
Fig. 5. Packing map of compound 3cd by OÁ Á ÁH bands.
Table 2
˚
Selected bond lengths (A) and angles (8) of compound 3ba and 3cd
Compound 3ba
Compound 3cd
˚
Bond lengths (A)
˚
Bond lengths (A)
Angles (8)
Angles (8)
As1–C1: 1.888 (6)
C1–C2: 1.432 (9)
C2–O1: 1.241 (8)
O1Á Á ÁAs1: 2.756
As1–C1–S1: 121.1 (4)
S1–C1–C2: 127.4 (5)
S1–C5: 1.715 (3)
C5–C6: 1.455 (3)
C6–O2: 1.226 (3)
O2Á Á ÁS1: 2.800
S1–C5–S2: 117.09 (14)
S2–C5–C6: 125.4 (2)
C2–C1–As1: 110.2 (5)
C6–C5–S1: 114.62 (18)
P
P
8C1 = 358.78
8C5 = 357.18
The distance deviation of O1 from the plane of As1, C1 and
The distance deviation of O2 from the plane of S1, C5 and
˚
C2 = 0.172 A
˚
C6 = 0.050 A
3. Conclusion
10 min, TLC showed that the reaction was completed. The
solvent was evaporated and the residue was purified by column
chromatography on silica gel using ether-hexane as eluent to
give 1a (78%).
In conclusion, stable perfluoroalkanesulfonyl-containing
arsonium ylides and sulfur ylides have been readily prepared
through the decomposition of perfluoroalkanesulfonyl diazo-
carbonyl compounds in the presence of rhodium catalyst. The
X-ray crystal analyses of 3ba and 3cd clearly demonstrated the
presence of weak fluorine interactions. The further chemical
transformation and the weak fluorine interactions of these
perfluoroalkanesulfonyl-containing ylides are the subject of on-
going investigations in our laboratory.
4.2. 1-(4-Chloro-1,1,2,2,3,3,4,4-octafluorobutylsulfonyl)-
1-diazopropan-2-one (1a)
Pale yellow oil. 1H NMR (300 MHz, CDCl3): d 2.48 (CH3,
s). 19F NMR (282 MHz, CDCl3): d À68.4 to À68.5 (2F, m),
À112.2 to À112.3 (2F, m), À119.8 to À120.4 (4F, m).
4. Experimental
4.3. 2-(4-Chloro-1,1,2,2,3,3,4,4-octafluorobutylsulfonyl)-
2-diazo-1-phenylethanone (1b)
Melting points were measured in a SGW1 X-4 micro-
melting point apparatus and were uncorrected. 1H and 19F NMR
spectra were recorded on a Bruker AM-300 spectrometer with
Me4Si and CFCl3 (with upfield negative) as the internal and
external standards, respectively. IR spectra were obtained with
a Nicolet AV-360 spectrophotometer. Lower resolution mass
spectrums were obtained on a Finnigan GC-MS 4021
instrument. The X-ray structural analysis was performed with
a Rigaku/AFC 7R Diffractometer. Elemental analyses were
performed by this institute.
White solid; m.p. 86–88 8C. 1H NMR (300 MHz, CDCl3): d
7.49–7.71 (5H, m). 19F NMR (282 MHz, CDCl3): d À68.3 (2F,
t, J = 12.4 Hz), À110.8 (2F, t, J = 14.4 Hz), À119.8 to À120.2
(4F, m).
4.4. 1-Diazo-1-(trifluoromethylsulfonyl)propan-2-one (1c)
White solid; m.p. 40–42 8C. 1H NMR (300 MHz, CDCl3): d
2.44 (CH3, s). 19F NMR (282 MHz, CDCl3): d À78.6 (CF3, s).
4.1. General procedure for the preparation of compound 1
4.5. 2-Diazo-1-phenyl-2-(trifluoromethylsulfonyl)ethanone
(1d)
The mixture of ClC4F8SO2CH2COCH3 (2.50 g, 7 mmol),
IC2F4OC2F4SO2N3 (3.17 g, 7.1 mmol) in anhydrous CH2Cl2
(40 ml) was cooled in an ice-water bath and then Et3N (1.0 ml,
0.72 mmol) was added dropwise over 20 min. After stirring for
White solid; m.p. 37–38 8C. 1H NMR (300 MHz, CDCl3): d
7.62–7.70 (3H, m), 7.49–7.54 (2 H, m). 19F NMR (282 MHz,
CDCl3): d À77.1 (CF3, s).

W. Pang et al. / Journal of Fluorine Chemistry 129 (2008) 343–348
347
4.6. Ethyl 2-diazo-2-(trifluoromethylsulfonyl)acetate (1e)
The final cycle of fullmatrix least-square refinement was
base on F2. The final R and wR value were 0.0809 and 0.2084,
respectively. All calculations were performed using the
SHELX-97 program.
Pale yellow oil. 1H NMR (300 MHz, CDCl3): d 4.38 (2H, q,
J = 7.2 Hz), 1.36 (3H, t, J = 7.2 Hz). 19F NMR (282 MHz,
CDCl3): d À77.8 (CF3, s).
4.10. 1-(Trifluoromethanesulfonyl)-1-(triphenyl-l5-
arsanylidene)-propan-2-one (3ca)
4.7. General procedure for the synthesis of stable ylides
from the decomposition of diazocompounds
Colorless solid; m.p. 156–158 8C. IR (KBr) n: 3064, 1589,
1485, 1439, 1340, 1284, 1204, 1176, 1147, 1081, 1052, 1000,
A solution of diazocompound 1 (0.5 mmol) in toluene (2 ml)
was added dropwise over a certain period (10–30 min) to a
stirred solution of the AsPh3 2 (0.5 mmol) and Rh2(OAc)4
(2 mg, 1 mol%) in toluene (2 ml), and heated at reflux
temperature under a nitrogen atmosphere. After heating for
an additional 2–4 h, the reaction was completed (monitored by
TLC). The solvent was evaporated under reduced pressure and
the residue was purified by column chromatography on silica
gel using ethyl acetate–hexane (V/V = 1:5) to afford the
corresponding arsonium ylides. Preparation of sulfur ylides is
similar as the above procedure.
1
885, 740, 689 cmÀ1. H NMR (CDCl3) d: 7.60–7.48 (m, 15H,
Ar–H), 2.45 (s, 3H, CH3). 19F NMR (CDCl3) d: À79.8 (s, 3F).
MS m/z (%): 495 (M+ + 1, 18), 481 (18), 427 (78), 360 (39), 344
(95), 306 (12), 226 (56), 165 (30), 152 (100), 132 (6), 77 (29),
69 (15), 51 (40), 43 (91). Anal. Calcd for C22H18AsF3O3S: C;
53.45, H; 3.67%. Found: C; 53.61, H; 3.83%.
4.11. 2-(Trifluoromethanesulfonyl)-2-(triphenyl-l5-
arsanylidene)-1-phenyl-ethanone (3da)
Colorless solid; m.p. 197–199 8C. IR (KBr) n: 3060, 1582,
1535, 1441, 1352, 1204, 1178, 1163, 1118, 1081, 1018, 746,
4.8. 1-(4-Chloro-1,1,2,2,3,3,4,4-octafluoro-butane-1-
sulfonyl)-1-(triphenyl-5-arsanylidene)-propan-2-one (3aa)
1
691, 613 cmÀ1. H NMR (CDCl3) d: 7.69–7.36 (m, 20H, Ar–
H). 19F NMR (CDCl3) d: À77.9 (s, 3F). MS (ESI): 557
(M+ + 1). Anal. Calcd for C27H20AsF3O3S: C; 58.28, H; 3.62%.
Found: C; 58.29, H; 3.58%.
Colorless solid; m.p. 205–207 8C. IR (KBr) n: 3648, 1583,
1484, 1440, 1343, 1286, 1194, 1157, 1081, 955, 742, 689 cmÀ1
.
1H NMR (CDCl3) d: 7.59–7.48 (m, 15H, Ar–H), 2.46 (s, 3H,
CH3). 19F NMR (CDCl3) d: À67.8 (t, J = 13 Hz, 2F), À110.5 to
À113.1 (m, 2F), À119.3 to À120.0 (m, 4F). MS (ESI): 661
(M+). Anal. Calcd for C25H18AsClF8O3S: C; 45.44, H; 2.75%.
Found: C; 45.46, H; 2.71%.
4.12. 1-(Trifluoromethanesulfonyl)-1-(triphenyl-l5-
arsanylidene)-acetic acid ethyl ester (3ea)
Colorless solid; m.p. 151–153 8C. IR (KBr) n: 2979, 1630,
1481, 1444, 1371, 1334, 1281, 1206, 1178, 1069, 1035, 742,
1
4.9. 2-(4-Chloro-1,1,2,2,3,3,4,4-octafluoro-butane-1-
sulfonyl)-2-(triphenyl-5-arsanylidene) -1-phenyl-ethanone
(3ba)
691, 619 cmÀ1. H NMR (CDCl3) d: 7.65–7.51 (m, 15H, Ar–
H), 3.95 (q, J = 7Hz, 2H, CH2), 0.91 (t, J = 7Hz, 3H). 19F NMR
(CDCl3) d: À79.2 (s, 3F). MS (ESI): 525 (M+ + 1). Anal. Calcd
for C23H20AsF3O3S: C; 52.68, H; 3.84%. Found: C; 52.37, H;
3.75%.
Colorless solid; m.p. 196–198 8C. IR (KBr) n: 3064, 1546,
1485, 1441, 1347, 1204, 1156, 1108, 1080, 955, 774, 742,
689 cmÀ1. 1H NMR (CDCl3) d: 7.70–7.36 (m, 20H, Ar–H). 19
F
4.13. 1-(Trifluoromethanesulfonyl)-1-
(dimethylsulfuranylidene)-propan-2-one (3cb)
NMR (CDCl3) d: À67.9 (t, J = 14 Hz, 2F), À108.1 to À110.3
(m, 2F), À118.5 to À121.4 (m, 4F). MS (ESI): 723 (M+ + 1).
Anal. Calcd for C30H20AsClF8O3S: C; 49.84, H; 2.79%. Found:
C; 49.88, H; 2.86%.
Colorless solid; m.p. 67–69 8C. IR (KBr) n: 3045, 2940,
1618, 1414, 1337, 1266, 1205, 1145, 1045, 967, 915, 756, 686,
639 cmÀ1. 1H NMR (CDCl3) d: 3.06 (s, 6H), 2.38 (s, 3H, CH3).
19F NMR (CDCl3) d: À80.3 (s, 3F). MS m/z (%): 250 (M+, 16),
235 (8), 181 (42), 117 (6), 102 (51), 69 (10), 62 (17), 43 (100).
Anal. Calcd for C6H9F3O3S2: C; 28.80, H; 3.62%. Found: C;
28.84, H; 3.70%.
X-raydataof3baC30H20AsClF8O3S:Mw = 722.89,CCDCno.
˚
654257, triclinic, space group: P-1, a = 10.6294 (10) A,
˚
˚
b = 11.6971 (11) A, c = 12.4767 (12) A; a = 80.7060 (10)8,
3
˚
b = 85.4170 (10)8, g = 75.1610 (10)8; V = 1478.6 (2) A ,
Z = 2, Dc = 1.624 g/cm3, F(0 0 0) = 724. Radiation, Mo Ka
˚
(l = 0.71073 A). Crystal dimension, 0.30 mm  0.20 mm Â
0.20 mm.
Intensity data were collected at 273 (2) K with a Bruker P4
four-circle diffractometer with graphite monochromator and
4.14. 1-(Trifluoromethanesulfonyl)-1-
(dimethyloxosulfuranylidene)-propan-2-one (3cc)
˚
Mo Ka radiation (l = 0.71073 A). A total of 2815 independent
Colorless solid; m.p. 144–146 8C. IR (KBr) n: 3026, 2935,
1605, 1353, 1283, 1215, 1174, 1150, 1061, 1017, 985, 699,
637 cmÀ1. 1H NMR (CDCl3) d: 3.67 (s, 6H), 2.42 (s, 3H, CH3).
19F NMR (CDCl3) d: À79.7 (s, 3F). MS m/z (%): 266 (M+, 10),
251 (15), 197 (44), 155 (70), 79 (26), 69 (17), 63 (25), 43 (100).
reflection were measured in range 2.278 < u < 25.008. The
structure was solved by directed methods and expanded using
Fourier techniques. The nonhydrogen atoms were refined
anisotropically, hydrogen atoms were included but not refined.

348
W. Pang et al. / Journal of Fluorine Chemistry 129 (2008) 343–348
Anal. Calcd for C6H9F3O4S2: C; 27.07, H; 3.41%. Found: C;
27.49, H; 3.48%.
Acknowledgements
The authors thank the National Natural Science Foundation
of China (NNSFC) (Nos. 20625205 and 20532040) for
financial support.
4.15. 1-(Trifluoromethanesulfonyl)-1-(1-oxo-tetrahydro-1-
l4-thiophen-1-ylidene)-propan-2-one (3cd)
Colorless solid; m.p. 148–150 8C. IR (KBr) n: 3045, 2976,
1628, 1352, 1263, 1197, 1134, 1047, 922, 762, 693, 609 cmÀ1
.
References
1H NMR (CDCl3) d: 4.05–3.90 (m, 2H), 3.85–3.73 (m, 2H),
2.57–2.47 (m, 2H), 2.44–2.31 (m, 5H). 19F NMR (CDCl3) d:
À90.1 (s, 3F). MS m/z (%): 292 (M+, 14), 277 (9), 231 (34), 181
(61), 105 (12), 88 (5), 69 (15), 55 (100), 43 (80). Anal. Calcd for
C8H11F3O4S2: C; 32.87, H; 3.79%. Found: C; 32.87, H; 3.68%.
X-ray data of 3cd C8H11F3O4S2: Mw = 292.29, CCDC no.
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˚
666345, Monoclinic, space group: P2(1)/c, a = 9.3534 (14) A,
[4] (a) B.M. Trost, M.R. Ghadiri, J. Am. Chem. Soc. 106 (1984) 7260–
7261;
˚
˚
b = 12.3263 (18) A, c = 10.1592 (15) A; a = 90.008, b = 96.144
(b) C.H. Xing, S.Z. Zhu, J. Org. Chem. 69 (2004) 6486–6488.
[5] (a) M. Ochiai, N. Tada, K. Murai, S. Goto, M. Shiro, J. Am. Chem. Soc.
128 (2006) 9608–9609;
3
3
˚
(5)8, g = 90.008; V = 1164.6 (3) A , Z = 4, Dc = 1.667 g/cm ,
˚
F(0 0 0) = 600. Radiation, Mo Ka (l = 0.71073 A). Crystal
dimension, 0.28 mm  0.25 mm  0.22 mm.
(b) K. Reichenbacher, H.I. Suss, J. Hulliger, Chem. Soc. Rev. 34 (2005)
22–30;
Intensity data were collected at 298 (2) K with a Bruker P4
four-circle diffractometer with graphite monochromator and Mo
(c) S.Z. Zhu, S.F. Zhu, G.F. Jin, Z.T. Li, Tetrahedron Lett. 46 (2005)
2713–2716;
˚
Ka radiation (l = 0.71073 A). A total of 2815 independent
(d) S.Z. Zhu, C.H. Xing, W. Xu, G.F. Jin, Z.T. Li, Cryst. Growth Des. 4
(2004) 53–56;
reflection were measured in range 2.748 < u < 27.558. The
structure was solved by directed methods and expanded using
Fourier techniques. The nonhydrogen atoms were refined
anisotropically, hydrogen atoms were included but not refined.
The final cycle of fullmatrix least-square refinement was base on
F2. The final R and wR value were 0.0430 and 0.1084,
respectively. All calculations were performed using the SHELX-
97 program.
(e) A.J. Mountford, D.L. Hughes, S.J. Lancaster, Chem. Commun. (2003)
2148–2149;
(f) J. Parsch, J.W. Engels, J. Am. Chem. Soc. 124 (2002) 5664–5672.
[6] (a) C.H. Xing, Ph.D. Dissertation, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, unpublished results, 2006.;
(b) S. Kenichiro, JP Patent 10142777 (1998).
[7] O. Meth-Cohn, E. Vuorinen, T.A. Modro, J. Org. Chem. 54 (1989)
4822–4827.