J.A. Barten et al. / Journal of Fluorine Chemistry 11352002) 101±103
103
obtained on a Varian MAT CH7A instrument at 70 eV. All
reactions and manipulations were conducted under atmo-
sphere of dry nitrogen. The X-ray structural study was carried
out on a Siemens P4 diffractometer using graphite mono-
chromated Mo Ka radiation ꢀl 71:073 pm). Crystal data
for6,colorless crystals,C H F NO, M 439:30,triclinic,
58). Yield: 2:0 g 4:6 mmol ꢀ46%). HRMS for C H F -
1
7 15 10
NO: calc: 439.09940,found: 439.09974.
4.4. 1-Trifluoromethyl-1,2,2,3,3,4,4,-heptafluoro-7-
phenyl-7-isopropylamino-hept-6-en-ꢀ-one 57)
1
7 15 10
P-1, a 920:5ꢀ2, b 1027:9ꢀ3, c 1127:4ꢀ3 pm, a
Compound 5 ꢀ1.5 g,3.4 mmol) was allowed to stand for 2
weeks in a sealed tube at room temperature. The colorless
crystals obtained were recrystallized from n-hexane. The mp
3
1
10:99, b 105:688, g 96:758, V 0:9312ꢀ4 nm ; ®nal
1 2
R values [I > 2sꢀI)], R 0:0755, wR 0:1928; R values
79 8C. H NMR ꢀCDCl ): 1.2 ꢀiPr,6H,d, 3JHH 6.5),3.7 ꢀ iPr,
1
ꢀ
0
all re¯ections), R 0:1141, wR 0:2187; 0:5 mm Â
1
2
3
3
:4 mm  0:3 mm with Z 2,re¯ections measured 2913,
1H,qq, JHH 6.4 Hz,6.5),5.4 ꢀ=CH,1H,s),5.5 ꢀCHF,1H,
2
3
3
dtq, JHF 37.4, JHF 21.2, JHF 11.0),7.5 ꢀPh,5H,m),11.3
1
9
ꢀNH,1H,brs).
3
F NMR ꢀCDCl ): À74.3 ꢀCF ꢀ5),3F,ddt,
3
3
4
JFF 11.1, JFF 3.1), À120.2 ꢀCF ꢀ2),2F,m),124.5 ꢀCF ꢀ1),
2 2
4.1. 1,1,1,3,4,4,ꢀ,ꢀ,ꢀ-nonafluoro-2-trifluoromethyl-2,3-
epoxypentane 51) and 2-isopropyliminopropane 52a)
2F,m),124.8 ꢀCF ꢀ3),2F,ABMX-system, J 295.1),216.2
2 AB
ꢀCFꢀ4),1F,dqt, 3JFF 4.1). 13C NMR ꢀCDCl ): 24.2 ꢀ2CH ,
3
3
1
2
2
s),47.6 ꢀCH,s),83.1 ꢀCFH,dqt,
JCF 201.2, JCF 34.3, JCF
2
-Isopropyliminopropane ꢀ2a) ꢀ1.5 g,15 mmol) and 4.8 g
34.7),92.1 ꢀ=CH,s),110.6 ꢀCꢀ1)F 2,tt, 1JCF 264.8, 2JCF
30.3),111.5 ꢀCꢀ2)F ,tqu, 1JCF 268.3, J 31.2),112.7
2
ꢀ
1
1
15 mmol) compound 1 in 20 ml Et O at 22 8C for 24 h gave
.8 g ꢀ4.3 mmol) ꢀ29%) enamino ketone 3 [7] and
,1,1,2,3,3,3-hexa¯uoropropane.
2
2
CF
ꢀCꢀ3)F ,ttd, 1J 281.0, J 31.6, J 24.1),120.4 ꢀCF 3,
2
2
2
CF CF CF
1
2
qd, JCF 281.8, JCF 25.6),127.5 ꢀ m-Ph,s),129.3 ꢀ o-Ph,s),
30.8 ꢀp-Ph,s),134.5 ꢀ i-Ph,s),169.8 ꢀ=C±N,s),177.2 ꢀC=O,
1
2
4.2. 2,3,3,4,4,ꢀ,ꢀ-Heptafluoro-1-trifluoromethyl-
cyclopent-1-ene oxide 54)
CF
t, J 23.7). MS: m/e ꢀ% 439 ꢀM ,40),420 ꢀ M À F,9),
378 ꢀM À F, iPr),C H F NO ꢀ439.10) C,46.48; H,3.44;
1
7 15 10
F,43.25. Found: C,46.40; H,3.40; F,44.05%.
1
-Tri¯uoromethyl-2,3,3,4,4,5,5-hepta¯uoro-cyclopen-
tene ꢀ26.0 g,100 mmol) were added dropwise to an aqueous
NaOCl solution at room temperature ꢀcf. ref. [14]). The
mixture was stirred for 2 h,the lower layer separated,
Acknowledgements
washed with water and dried over MgSO . Distillation gave
4
A.A.K.isgratefultotheDeutscheForschungsgemeinschaft
for ®nancial support ꢀGrant 436 RUS 17/115/99),J.A.B. to
the DAAD for a travel grant ꢀPWA Grant,415-ra-esh).
2
4.1 g ꢀ87 mmol) ꢀ87%) of the epoxide 4. The bp 52 8C. 19F
2
NMRꢀCDCl ): À72.6 ꢀCF ,3F,s); À185.6 ꢀCF,1F,d, JFFA00
3
3
1
5.4); À127.9 ꢀCF ,2F,AB-system,
J
268.6); À131.3
2
AB
ꢀ
CF ,2F,AB-system, J
2
0
0
246.7); À134.6 ꢀCF ,2F,ABX-
A B
2
system, J 00 00 250.6). MS: m/z ꢀ%): 278 ꢀM ,6),259
References
A B
ꢀ
3
9
M À F,17),209 ꢀ M À CF ,65),15i9 ꢀ M À C F ,
3
2 5
F ,69),
4
[1] H. Kawa,F. Yamaguchi,N. Ishikawa,J. Fluor. Chem. 20 ꢀ1982) 475.
[2] H.A. Hammouda,N. Ishikawa,Bull. Chem. Soc. Jpn. 51 ꢀ1978) 3091.
9),131 ꢀC F ,86),109 ꢀC F O ,30),109 ꢀC
3
5
3
3
2
3 ꢀC3F3 ,45),69 ꢀCF 3 ,100),47 ꢀCFO ,25). Anal. calc.
[
[
3] Q.-C. Mir,C.-Y. Guo,R.L. Kirchmeier,J.M. Shreeve,J. Org. Chem.
9 ꢀ1994) 173.
for C F O ꢀ278.00): C,25.90; F,68.35. Found: C,25.84; F,
6
10
5
6
8.37%.
4] V.M. Rogovik,N.I. Delyagina,E.I. Mysov,V.F. Cherstkov,S.R.
Sterlin,L.S. German,Bull. Acad. Sci. USSR Div. Chem. Sci. ꢀEngl.
Transl.) 39 ꢀ1990) 1870.
0
4.3. 2,3,3,4,4,ꢀ,ꢀ-Heptafluoro-1-trifluoromethyl-1-52 -
isopropyliminopropane) cyclopentan-1-ol 55)
[
[
5] A.Y. Zapevalov,T.I. Filyakova,N.V. Peschanskii,M.I. Kodess,I.P.
Kolenko,J. Org. Chem. USSR ꢀEngl. Transl.) 25 ꢀ1989) 492.
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To compound 2b ꢀ1.6 g,10 mmol) in 20 ml diethylether
.8 g ꢀ10 mmol) epoxide 4 was added dropwise and stirred
2
for 12 h. All volatiles were removed under reduced pressure
[7] J.A. Przyborowski,E. Lork,G.-V. RoÈschenthaler,J. Fluor. Chem. 104
2000) 207.
8] G. Simchen,A. Schmidt,Synthesis ꢀ1997).
ꢀ
[
and the remaining yellow compound 5 distilled. The bp
À2
[9] R.W. Lang,P.F. Wenk,Helv. Chim. Acta 71 ꢀ1988) 596.
4 8C ꢀ10 hPa). H NMR ꢀCDCl ): 1.2 ꢀiPr,6H,d, 3JHH
1
9
3
[
10] R. Lindermann,S. Kirollos,Tetrahedron Lett. 31 ꢀ1990) 2689.
6
.2),2.4 ꢀCH ,2H,AB-System, JAB 25.5),3.6 ꢀ iPr,1H,sep,
2
[11] A.Ya. Zapevalov,T.I. Filyakova,I.P. Kolenko,M.I. Kodess,J. Org.
Chem. USSR ꢀEngl. Transl.) 22 ꢀ1986) 80.
3
19F NMR
JFF 11:8, JFF 6:0), À125.8
261.1), À126.3 ꢀCF ,2F,AB-
JHH 6.2),7.3 ꢀPh,5H,m),7.8 ꢀOH,1H,s).
3
4
[
[
[
12] J. March,Advanced Organic Chemistry,4th Edition,Wiley,New
York,1992,pp. 601±603.
ꢀ
ꢀ
CDCl ): À74.3 ꢀCF ,3F,dt,
3
3
CF ,2F,AB-system,
2
J
AB
2
13] A.J.C. Wilson,International Tables for Crystallography,Vol. C,
Kluwer Academic Publishers,Dordrecht,1995,p. 685.
14] I.P. Kolenko,T.I. Filyakova,A.Ya. Zapevalov,E.P. Lur'e,Bull. Acad.
Sci. USSR,Div. Chem. Sci. ꢀEngl. Transl.) 28 ꢀ1979) 2509.
system, J
2
4
0
0
242.5), À128.5 ꢀCF ,2F,AB-system,
J
00 00
A B
A B
2
53.6), À186.5 ꢀCF,1F,m). MS: m/e ꢀ% 439ꢀM ,100),
3 3
24 ꢀM À CH ,62),370 ꢀ M À CF ,12),104 ꢀPhCO
,