Study of the reactions of fluorinated α,β-unsaturated carbonyl compounds with nitrogen and sulfur dinucleophiles

Article abstract of DOI:10.1016/S0022-1139(00)00402-4

The fluorinated α,β-unsaturated ketone 1,1,1-trifluoro-4-ethoxy-3-butene-2-one reacted with dinucleophiles such as 2-aminothiophenol and 2-amino-ethanethiol to give trifluoroacetyl substituted 4H-1,4-benzothiazine, or 4H-1,4-thiazine, while the reaction o

Full text of DOI:10.1016/S0022-1139(00)00402-4

Journal of Fluorine Chemistry 108 (2001) 51±56
Study of the reactions of ¯uorinated a,b-unsaturated carbonyl
compounds with nitrogen and sulfur dinucleophiles
Qianli Chua, Liping Songb, Guifang Jina, Shizheng Zhua,*
aShanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, PR China
bDepartment of Chemistry, Shanghai University, Shanghai 201800, PR China
Received 2 August 2000; accepted 14 November 2000
Abstract
The ¯uorinated a,b-unsaturated ketone 1,1,1-tri¯uoro-4-ethoxy-3-butene-2-one reacted with dinucleophiles such as 2-aminothiophenol
and 2-amino-ethanethiol to give tri¯uoroacetyl substituted 4H-1,4-benzothiazine, or 4H-1,4-thiazine, while the reaction of 5-tri¯uoroacetyl-
3,4-dihydro-2H-pyran or 4-tri¯uoroacetyl-2,3-dihydro-furan with 2-amino-phenthiol gave 3-(2,2,3-2H-benzothiazolyl)-2-(tri¯uoromethyl)-
tetrahydrofuran-2-ol or 3-(2-2,3-2H-benzothiazolyl)-2-(tri¯uoromethyl)- tetrahydro-2H-pyran-2-ol, respectively. # 2001 Elsevier Science
B.V. All rights reserved.
Keywords: Fluorinated a,b-unsaturated carbonyl compounds; Fluorinated heterocycles; Dinucleophiles; Nucleophilic reactions; Thiazine
1. Introduction
2. Result and discussion
In recent years, considerable attention has been concen-
trated on the development of new methodologies for the
synthesis of various ¯uorine-containing heterocycles, since
these compounds are now widely recognized as important
organic materials showing interesting biological activities
for their potential use in medicinal and agricultural scienti®c
®elds [1±4]. a,b-Unsaturated carbonyl compounds are of
wide interest because of their possible applications in the
preparation of various heterocycles [5,6]. In our previous
work, we have reported the reactions of a,b-unsaturated
5-Tri¯uoroacetyl-3,4-dihydro-2H-pyran (2a) or 4-tri-
¯uoroacetyl-2,3-dihydro-furan (2b) reacts with 2-ami-
nothiophenol (3a) to give the corresponding ¯uorinated
heterocycles 4a and 4b, respectively. Compound 4b was
easily recrystalized from petroleum ether:acetic ether (10:1)
to give ®ne crystals for analysis. Their structures were fully
characterized by spectroscopic methods and further con-
®rmed by X-ray diffraction (XRD) analysis.
Fig. 1 shows the molecular structure of 4b. Selected bond
lengths and bond angles are listed in Table 1.
ketones EtOCH=CHCOCF3 (1) and ꢀCH2†nOCHˆCCOCF3
(2) with some nitrogen nucleophiles [7,8]. Herein, we wish
to report a convenient synthesis of ¯uorinated 4H-1,4-ben-
zothiazine, 4H-1,4-thiazine and some other heterocycles
from the reaction of the ¯uorinated a,b-unsaturated ketones
with dinucleophiles such as 2-amino-phenthiol or 2-ami-
noethanethiol.
The possible reaction mechanism is as follows:
Under the same reaction conditions, 1,1,1-tri¯uoro-4-
ethoxy-3-butene-2-one EtOCH=CHCOCF3 (1) reacted
smoothly with 2-aminothiophenol (3a) or 2-aminophenol
* Corresponding author. Tel.: ‡86-21-6416-3300;
fax: ‡86-21-6416-6128.
E-mail address: zhusz@pub.sioc.ac.cn (S. Zhu).
0022-1139/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 4 0 2 - 4

52
Q. Chu et al. / Journal of Fluorine Chemistry 108 (2001) 51±56
Fig. 1. The molecular structure of 4b.
(3b) to form 4-(2-mercaptophenyl)amino-1,1,1-tri¯uoro-
methyl-3-butene-2-one (5a) or 4-(2-hydroxy-phenyl)a-
mino-1,1,1-tri¯uoromethyl-3-butene-2-one (5b), respect-
ively [8].
It is interesting that a further reaction occurred when 5a
was heated in DMSO. The product is a red solid 2-tri¯uor-
oacetyl-4H-1,4-benzothiazine (6) instead of the expected
product 1,1,1-tri¯uoro-3-(2-2,3-2H-benzothiazolyl)-2-pro-
panone (60). Recrystalization of 6 from CH3CN gave a good
crystal for XRD analysis. The bond lengths of N(1)±C(4)
1.332(5), C(3)±C(4) 1.357(5), C(2)±C(3) 1.403(5) and
C(2)±O(1) 1.226(4) showed that they are between single
bond and double bond. This should be attributed to the de-
localized conjugation p-bond system and the N±H±O inter-
Table 1
Selected bond lengths and bond angles of compound 4b
Ê
Bond length (A)
Bond angle (8)
S±C(1) 1.755(5)
S±C(7) 1.841(4)
C(1)±S±C(7) 91.2(2)
C(6)±N±C(7) 111.9(3)
S±C(7)±N 104.3(3)
O(1)±C(11) 1.450(5)
O(1)±C(12) 1.410(4)
O(2)±C(12) 1.399(4)
N±C(6) 1.413(5)
S±C(7)±C(8) 110.9(3)
N±C(7)±C(8) 115.4(3)
C(9)±C(8)±C(12) 109.6(3)
C(7)±C(8)±C(12) 113.9(3)
C(7)±C(8)±C(9) 113.4(3)
C(11)±O(1)±C(12) 114.5(3)
O(2)±C(12)±C(13) 109.3(3)
N±C(7) 1.482(5)
Ê
Ê
C(12)±C(13) 1.534(6)
C(8)±C(12) 1.554(5)
C(7)±C(8) 1.540(5)
molecular hydrogen bond (N±H, 0.95 A; H±O, 1.80 A). The
molecular structure is shown in Fig. 2 and selected bond
lengths and bond angels are summarized in Table 2.

Q. Chu et al. / Journal of Fluorine Chemistry 108 (2001) 51±56
53
The conversion of the 5a into 6 presumably proceeds
by a mechanism analogous to that reported previously
[9,10].
yield.
But 4-(2-hydroxyphenyl)amino-1,1,1-tri¯uoromethyl-3-
butene-2-one (5b) is stable, i.e. does not cyclize in DMSO
or HOAc at 1208C or in the presence of K2CO3.
Gorbunova [11] has reported that 2-tri¯uoromethylquino-
line was the product of heating C6H5NHCH=CHC(O)CF3
with polyphosphoric acid (PPA).
In our case, no analogous reaction is found.
The conversion also takes place in DMF in good yield,
however, no reaction occurred in CCl4.
1,1,1-Tri¯uoro-4-ethoxy-3-butene-2-one
directly with 2-aminothio-phenol (3a) to give 6 in 32%
(1)
reacts
Fig. 2. The molecular structure of 6.

54
Q. Chu et al. / Journal of Fluorine Chemistry 108 (2001) 51±56
Table 2
It is interesting that only in the presence of an inorganic
base in DMSO, was 1,1,1-tri¯uoro-4-(2-mercaptoethyla-
mino)-3-buten-2-one (8) converted to the 2-tri¯uoroace-
tyl-4H-1,4-thiazine (10). The reaction was carried out
under several different conditions and the results were
summarized in Table 3.
Selected bond lengths and bond angles of compound 6
Ê
Bond length (A)
Bond angle (8)
S(1)±C(3) 1.774(3)
S(1)±C(6) 1.758(4)
N(1)±C(4) 1.332(5)
N(1)±C(5) 1.410(4)
C(4)±C(3) 1.357(4)
C(3)±C(2) 1.403(5)
C(2)±C(1) 1.530(5)
O(1)±C(2) 1.226(4)
C(5)±C(6) 1.383(5)
C(6)±S(1)±C(3) 101.4(2)
C(5)±N(1)±C(4) 125.4(3)
N(1)±C(4)±C(3) 126.0(3)
S(1)±C(3)±C(4) 121.8(3)
C(4)±C(3)±C(2) 125.2(3)
S(1)±C(3)±C(2) 113.0(2)
C(3)±C(2)±O(1) 123.5(3)
C(3)±C(2)±C(1) 121.1(3)
C(1)±C(2)±O(1) 115.3(3)
As mentioned above, compound 6 could be synthesized
directly from the reaction of 1 with 3a, however, under the
same reaction conditions, 1 treated with 2-amino-etha-
nethiol (7) failed to give 10. Similarly, treatment of com-
pounds 9a and 9b in DMSO or HOAc led to decomposition.
In summary, we synthesized a series of ¯uorinated
heterocycles such as tri¯uoroacetyl-substituted 4H-1,4-
benzothiazine, 4H-1,4-thiazine, furan and pyran from the
When a,b-unsaturated ketones (1 and 2) were treated with
2-amino-ethanethiol (7), only the trans-form of 1,1,1-tri-
¯uoro-4-(2-mercaptoethylamino)-3-buten-2-one (8), 1,1,1-
tri¯uoro-5-hydroxy-3-((2-mercaptoethylamino)methylene)-
2-pentanone (9a) or 1,1,1-tri¯uoro-6-hydroxy-3-((2-mer-
captoethylamino)methylene)-2-hexanone
obtained in high yield, respectively.
(9b)
were
It is worth noting that compound 8 is partially converted
from the all trans isomer into the cis-form in DMSO but the
same conversion did not occur in CCl4. The ratio of trans-
and cis-form is nearly 4:5. But the cis-form could not be
isolated since it reverted to the trans-form when poured into
water. The same conversion was not observed when we
treated the compounds 9a and 9b in DMSO.
reactions of ¯uorinated a,b-unsaturated carbonyl com-
pounds with some dinucleophiles.
3. Experimental
Melting points are measured on a Temp-Melt. apparatus
and are uncorrected. 1H NMR (90 MHz) and 19F NMR
(54.6 MHz) spectra were recorded on a Varian-360L instru-
ment or Bruker AM-300 spectrometer with TMS and TFA
(dCFCl3 ˆ dTFA Ð 76.8 ppm) as the internal and external
Table 3
Conversion of compound 8 in different conditions
Entry
Catalyst (mol%)
Condition
Solvent
Yield of 10 (%)
Temperature (8C)
Time (h)
1
2
3
4
5
6
7
8
HOAc (20)
- - - -
DMSO
HOAc
100
120
100
100
80
8
8
No reaction
No reaction
Et3N (20)
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
8
No reaction
Pyridine (20)
KOH (20)
K2CO3 (100)
K2CO3 (20)
Na2CO3 (20)
8
No reaction
24
24
24
24
23
38
42
64
80
80
80

Q. Chu et al. / Journal of Fluorine Chemistry 108 (2001) 51±56
55
standard, respectively. IR spectra were obtained with an IR-
3.2. Reaction of 1 and 2 with 2-amino-ethanethiol
440 Shimadzu spectrophotometer on KBr disks. Low reso-
lution mass spectra was obtained on a Finnigan GC±MS
4021, an instrument. X-ray structure analysis was performed
with Rigaku AFC 7R diffractometer. Elemental analyses
were performed by this institute. Compound 1 was prepared
according to the literature method [12].
2-Amino-ethanethiol hydrochloride 7 (10 mmol) was
added into a 100 ml ¯ask containing a solution of KOH
(10 mmol) and EtOH (60 ml). After the mixture was stirred
for 0.5 h at room temperature, 1,1,1-tri¯uoro-4-ethoxy-3-
butene-2-one (1, 10 mmol) was added to the solution. After
this reaction mixture was stirred for 8 h at room temperature,
the solvent was evaporated in vacuum. The crude product
was separated by column chromatography to give the pure
product 8 in a yield of 94%.
3.1. Reaction of 2 with 2-amino-phenthiol (3a)
2-Aminothiophenol (3a, 5 mmol) was added to a 50 ml
¯ask containing a solution of 5-tri¯uoroacetyl-3,4-di-hydro-
2H-pyran (2a, 5 mmol) and toluene (30 ml). This reaction
mixture was stirred for 24 h at room temperature, and then
TLC was used to show that the reaction had ®nished. The
solvent was evaporated in vacuum. The crude product was
separated by column chromatography to give the pure
product 4a in a yield of 74% and by-product 2,20-dithio-
bis-benzenamine 11 which was identi®ed by its spectral data
[13] in a yield of 8%.
Similar treatment of 2a and 2b gave the corresponding
products 9a in a yield of 88% and 9b in a yield of 89%,
respectively.
3.2.1. trans-1,1,1-Trifluoro-4-(2-mercaptoethylamino)-3-
buten-2-one (8)
Mp: 109±1108C. Anal for C6H8F3NSO Calc.: N, 7.04%;
H, 4.02%; C, 36.18%; found: N, 6.88%; H, 3.72%; C,
36.41%; IR (nmax, cm 1): 3235 (m, N±H), 1647 (s, C=O),
1593 (s, C=C), 1200, 1136 (vs, C±F); dH: (90 MHz, CDCl3),
10.3 (br, NH), 7.2 (m, 1H), 5.4 (d, 1H), 3.7 (br, SH), 3.6 (m,
2H), 2.9 (m, 2H); dF: (60 MHz CDCl3), 76.7 (s, CF3); dH:
(90 MHz, DMSO-d6), 10.3 (br, NH), 7.5 (m, 1H), 5.4 (d,
1H), 3.7 (m, 2H), 3.0 (m, 2H), 3.0 (br, 1H); dF: (60 MHz,
At room temperature, similar treatment of 2-amino-
phenthiol (3a) with 2b gave 4b in a yield of 70% and 11
in a yield of 7%.
3.1.1. 3-(2-2,3-2H-Benzothiazolyl)-2-(trifluoromethyl)-
tetrahydro-furan-2-ol (4a)
‡
DMSO-d6), 76.7 (s, CF3); MS (m/z, %): 199 (M , 11.34),
‡
‡
‡
Mp: 120±1228C. Anal for C12H12F3NSO2 Calc.: N,
4.81%; H, 4.12%; C, 49.48%; found: N, 4.72%; H,
3.84%; C, 49.15%; IR (nmax, cm 1): 3310 (s, O±H), 3100
(s, N±H), 2948 (m, C±H), 1195, 1162 (vs, C±F); dH:
(90 MHz, D3CC(O)CD3), 6.7 (m, 4H), 5.5 (d, 1H), 4.0
(m, 2H), 3.2 (br, 2H), 2.7 (m, 1H), 2.0 (m, 2H); dF:
(60 MHz, D3CC(O)CD3), 83.8 (s, CF3); MS (m/z, %):
152 (M ±CH2SH, 73.07), 130 (M ±CF3, 11.75), 102 (M ±
COCF3, 30.86), 43 (CH2CH2NH, 100).
3.2.2. cis-1,1,1-Trifluoro-4-(2-mercaptoethylamino)-3-
buten-2-one (80)
dH: (90 MHz, DMSO-d6), 8.7 (br, NH), 7.9 (m, 1H), 5.5
(d, 1H), 3.7 (m, 2H), 3.0 (m, 2H), 3.0 (br, 1H); dF: (60 MHz,
DMSO-d6), 76.65 (s, CF3).
‡
‡
‡
291 (M , 6.94), 149 (C8H7NS , 4.17), 136 (C7H6NS , 100),
‡
108 (C6H4S , 12.30).
3.2.3. 1,1,1-Trifluoro-5-hydroxy-3-((2-mercaptoethyl-
amino)methylene)-2-pentanone (9a)
3.1.2. 3-(2-2,3-2H-Benzothiazolyl)-2-(trifluoromethyl)-
tetrahydro-2H-pyran-2-ol (4b)
Mp: 112±1148C. Anal for C8H12F3NSO2 Calc.: N, 5.76%;
H, 4.94%; C, 39.51%; found: N, 5.68%; H, 4.81%; C,
39.34%; IR (nmax, cm 1): 3380 (s, O±H), 3210 (s, N±H),
2946 (m, C±H), 1648 (m, C=O), 1583 (s, C=C), 1182, 1136
(vs, C±F); dH: (90 MHz, D3CC(O)CD3), 7.3 (s, 1H), 3.4 (m,
2H), 3.2 (m, 2H), 3.2 (br, 3H), 2.6 (m, 2H), 2.1 (m, 2H); dF:
(60 MHz, D3CC(O)CD3), 75.8 (s, CF3); MS (m/z, %): 243
Mp: 106±1088C. Anal for C13H14F3NSO2 Calc.: N,
4.59%; H, 4.59%; C, 51.15%; found: N, 4.65%; H,
4.63%; C, 51.32%; IR (nmax, cm 1): 3315 (s, O±H), 3102
(s, N±H), 2954 (m, C±H), 1274, 1142 (vs, C±F); dH:
(90 MHz, CDCl3), 6.9 (m, 4H), 5.8 (d, 1H), 4.8 (br, 2H),
3.8 (m, 2H), 2.0 (m, 1H), 1.7 (m, 4H); dF: (60 MHz CDCl3),
‡
‡
‡ ‡ ‡
80.8 (s, CF3); MS (m/z, %): 306 (M ±H, 2.42), 305 (M ,
‡
(M , 2.58), 242 (M ±H, 3.04), 196 (M ±CH2SH, 6.90), 167
‡
‡
‡
6.97), 136 (C7H6NS , 100), 108 (C6H4S , 13.18).
(M ±NHCH2CH2SH, 2.22), 88 (HSCH2CH2NHC , 100),
‡
XRD analysis data: Crystal system: trigonal, lattice type:
R-centered, no. of re¯ections used for unit cell determination
(2y range): 25 (18.3±21.68), space group: R3(#148), Z ˆ
69 (CF3 , 89.28).
3.2.4. 1,1,1-Trifluoro-6-hydroxy-3-((2-mercaptoethyl-
amino)methylene)-2-hexanone (9b)
Ê
Ê
Ê 3
18, a ˆ 22:094(4) A, c ˆ 15:235ꢀ3† A, V ˆ 6435ꢀ2† A ,
l ꢀMo Ka† ˆ 0:71069 A, Dc ˆ 1:553 g/cm3. Fꢀ0 0 0† ˆ
Mp: 118±1208C. Anal for C9H14F3NSO2 Calc.: N, 5.45%;
H, 5.45%; C, 42.02%; found: N, 5.42%; H, 5.34%; C,
42.23%; IR (nmax, cm 1): 3380 (s, O±H), 3212 (s, N±H),
2948 (m, C±H), 1648 (m, C=O), 1585 (s, C=C), 1194, 1124
(vs, C±F); dH: (90 MHz, D3CC(O)CD3), 7.3 (s, 1H), 3.4 (m,
2H), 3.1 (m, 2H), 3.1 (br, 1H), 2.9 (br, 2H), 2.6 (m, 2H), 2.0
Ê
1
3114:00, Rˆ0:052, Rwˆ 0:061, m ꢀMo Ka† ˆ 2:72 cm
.
Crystal dimensions: 0:20 mm  0:20 mm 0:30 mm. (Data
were measured at 293 K on a Rigaku AFC 7R diffractometer
with graphite monochromated Mo Ka radiation and a 12 kW
rotating anode generator.)

56
Q. Chu et al. / Journal of Fluorine Chemistry 108 (2001) 51±56
(m, 2H), 1.2 (m, 2H); dF: (60 MHz, D3CC(O)CD3), 75.8
(s, CF3); MS (m/z, %): 257(M , 12.88), 256 (M ±H, 37.10),
3.3.2. 4-Trifluoroacetyl-4H-1,4-thiazines (10)
‡
‡
Mp: 162±1648C. Anal for C6H6F3NSO Calc.: N, 7.11%;
H, 3.05%; C, 36.55%; found: N, 7.06%; H, 2.80 1%; C,
36.22%; IR (nmax, cm 1): 3210 (s, N±H), 3020 (m, C±H),
1585 (m, C=O), 1560 (m, C=C), 1150, 1125 (vs, C±F); dH:
(90 MHz, D3CC(O)CD3), 8.1 (s, 1H), 3.7 (m, 2H), 3.0 (m,
2H); dF: (60 MHz, D3CC(O)CD3), 75.9 (s, CF3); MS (m/z,
‡
‡
239 (M ±H2O, 8.51), 210 (M ±CH2SH, 75.91), 88
‡
‡
(HSCH2CH2NHC , 100), 69 (CF3 , 98.93).
3.3. Conversion of 5a or 8 in DMSO
‡
‡
‡
At room temperature, 4-(2-mercaptophenyl)amino-1,1,1-
tri¯uoromethyl-3-butene-2-one (5a, 5 mmol) was added to a
25 ml ¯ask containing 15 ml DMSO. After being stirred for
about 8 h at 608C, 19F NMR indicated that the reaction was
®nished, the reaction mixture was poured into water. The
crude product was separated by ®ltration and it was puri®ed
by column chromatography to give the pure red product 2-
tri¯uoroacetyl-4H-1,4-benzothiazines (6) in a yield of 90%.
Similar treatment of 1,1,1-tri¯uoro-4-(2-mercaptoethyla-
mino)-3-buten-2-one (8) in the presence of inorganic base o
give the corresponding product 2-tri¯uoroacetyl-4H-1,4-
thiazine (10).
%): 198 (M ±H, 19.26), 197 (M , 100), 128 (M ±CF3,
‡
80.01), 100 (M ±COCF3, 42.45).
Acknowledgements
The authors thank the National Natural Science Founda-
tion of China (NNSFC) (No. 20032010, 20072049) and
Innovation Foundation of the Chinese Academy of Sciences
for ®nancial support.
References
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Industrial Applications, Ellis Horwood, London, 1979.
[2] R. Filler, Y. Kobayashi, Biomedicinal Aspects of Fluorine Chemistry,
Kodansha & Elsevier Biomedical, Tokyo, 1982.
[3] J.T. Welch, Tetrahedron 43 (1987) 3123.
3.3.1. 4-Trifluoroacetyl-4H-1,4-benzothiazine (6)
Mp: 1828C (decomposition temperature). Anal for
C10H6F3NSO Calc.: N, 5.71%; H, 2.45%; C, 48.98%; found:
N, 4.70%; H, 2.21%; C, 48.82%; IR (nmax, cm 1): 3238 (s,
N±H), 1587 (m, C=O), 1560 (m, C=C), 1192, 1129 (vs, C±
F); dH: (90 MHz, DMSO-d6), 10.1 (br, NH), 7.5 (d, 1H), 7.0
(m, 4H); dF: (60 MHz, DMSO-d6), 75.9 (s, CF3); MS (m/z,
[4] R. Filler, Y. Kobayashi, L.M. Yagupolskii, Organofluorine Com-
pounds in Medicinal Chemistry and Biomedical Applications,
Elsevier, Amsterdam, 1993.
[5] M.G. Gorbunova, I.I. Gerus, V.P. Kukhar, J. Fluorine Chem. 65
(1993) 25.
‡
‡
‡
%): 245 (M , 28.83), 244 (M ±H, 100), 176 (M ±CF3,
‡
‡
21.39), 148 (M ±COCF3, 73.78), 69 (CF3 , 7.12).
[6] M.A.P. Martins, A.F.C. Flores, G.P. Bastos, N. Zanatta, H.G.
Bonacorso, J. Heterocyclic Chem. 36 (1999) 837.
[7] S. Zhu, C. Xu, G. Qin, Q. Chu, Y. Xu, Monatshefte fuÈr Chemic. 130
(1999) 671.
XRD analysis data: Crystal system: triclinic, lattice type:
primitive, no. of re¯ections used for unit cell determination
(2y range): 21(13.6±25.68), space group: P1(#2), Z ˆ 2,
[8] Q. Chu, Y. Wang, S. Zhu, Synth. Commun. 30 (2000) 677.
[9] S. Miyano, N. Abe, K. Sumoto, J. Chem. Soc., Chem. Commun.
(1975) 760.
Ê
Ê
Ê
a ˆ 10:688ꢀ2† A, b ˆ 10:976ꢀ4† A, c ˆ 10:272ꢀ3† A, a ˆ
Ê 3
111:12ꢀ3†, bˆ95:54ꢀ2†, g ˆ 111:00ꢀ2†, V ˆ 1013:5ꢀ6† A ,
l ꢀMo Ka† ˆ 0:71069 A, Dc ˆ 1:607 g/cm3. Fꢀ0 0 0† ˆ
Ê
[10] G. Liso, G. Trapani, A. Latrofa, P. Marchini, J. Heterocyclic Chem.
18 (1981) 279.
1
496:00, R ˆ 0:047, Rw ˆ 0:060, m ꢀMo Ka† ˆ 3:38 cm
.
[11] I.I. Gerus, M.G. Gorbunova, V.P. Kukhar, J. Fluorine Chem. 69
(1994) 195.
Crystal dimensions: 0:20 mm  0:20 mm  0:30 mm. (Data
were measured at 293 K on a Rigaku AFC 7R diffractometer
with graphite monochromated Mo Ka radiation and a 12 kW
rotating anode generator.)
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