1,1,3,3,3-Pentafluoro-2-pentafluorophenyl-1,2-epoxypropane and trimethylphosphite: Unusual 1,4-dioxan-2,5-dione ring formation

Article abstract of DOI:10.1016/S0022-1139(01)00569-3

1,1,3,3,3-Pentafluoro-2-pentafluorophenyl-1,2-epoxypropane 1 reacted with trimethylphosphite giving two diastereomers, (Z)- and (E)-3,6-bis(trifluoromethyl)-3,6-bis(pentafluorophenyl)-1,4-dioxan-2,5-dione 2a, b in a 1:1 ratio, cyclodimerisation product of

Full text of DOI:10.1016/S0022-1139(01)00569-3

Journal of Fluorine Chemistry 114 12002) 99±101
Short communication
1,1,3,3,3-Penta¯uoro-2-penta¯uorophenyl-1,2-epoxypropane
and trimethylphosphite: unusual 1,4-dioxan-2,5-dione ring formation
a
Alexander A.Kadyrov , Dmitrii Silaev , Eli Breuer , Gerd-Volker Roschenthaler
a
c
b,*
È
aNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova, 117813Moscow, Russia
bInstitute of Inorganic & Physical Chemistry, University of Bremen, Leobener Strasse, D-28334 Bremen, Germany
cDepartment of Medicinal Chemistry, School of Pharmacy, The Hebrew University of Jerusalem, P.O. Box 12065, Jerusalem 91120, Israel
Received 12 September 2001; accepted 20 November 2001
Abstract
1,1,3,3,3-Penta¯uoro-2-penta¯uorophenyl-1,2-epoxypropane 1 reacted with trimethylphosphite giving two diastereomers, 1Z)- and 1E)-
3,6-bis1tri¯uoromethyl)-3,6-bis1penta¯uorophenyl)-1,4-dioxan-2,5-dione 2a, b in a 1:1 ratio, cyclodimerisation product of the intermediately
generated a-lactone 4.Compounds 2a, b were hydrolysed to furnish 3,3,3-tri¯uoro-2-hydroxy-2-12,3,4,5,6-penta¯uorophenyl)propionic acid
5. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: 1,1,3,3,3-Penta¯uoro-2-penta¯uorophenyl-1,2-epoxypropane; Trimethylphosphite; Methylphosphonic acid ¯uoride; 3,6-Bis1tri¯uoromethyl)-3,6-
bis1penta¯uorophenyl)-1,4-dioxan-2,5-dione; 3,3,3-Tri¯uoro-2-hydroxy-2-12,3,4,5,6-penta¯uorophenyl)propionic acid
1. Introduction
itself rearranges to form the corresponding phosphonic ester
¯uoride and compound 3 ®nally splitting off methyl ¯uoride.
The resulting corresponding a-lactone 4 dimerises to furnish
the two possible diastereomeric dioxane-diones 2a, b in a
1:1 ratio 1the synthesis and some reactions, except cyclo-
dimerisation of per¯uorinated a-lactones with similar struc-
Earlier we have shown that the reaction of per¯uorinated
epoxides with trialkylphosphites generally results into the
formation of ¯uorinated phosphorus ylides concomitant
with C±C and C±O bond cleavage in the epoxide ring system
[1±3], which was found in the case of 1,1,3,3,3-penta¯uoro-
2-penta¯uorophenyl-1,2-epoxypropane 1 and triethylpho-
sphite [2].
ture was described earlier [6,7]).Mass spectra and 19F, 13
C
NMR data are in very good agreement with the proposed
structure.The formation of FP1OMe) 2 and FP1O)1OMe)Me
1
was con®rmed by H, 19F and 31P NMR [8,9].The two
diastereomers 2a, b can be clearly distinguished on the basis
of their 13C NMR data, since all resonances appear pairwise.
Also, the 19F resonances were observed as two sets of signals
for the CF3 group and of the different ¯uorine nuclei in the
phenyl rings.
Hydrolysis of dioxane-diones 2a, b quantitatively 119F
and 1H NMR) forms 3,3,3-tri¯uoro-2-hydroxy-2-12,3,4,5,6-
penta¯uorophenyl)propionic acid, which can be used as a
reagent for further transformations 1cf.[11]).
2. Results and discussion
Surprisingly, the reaction of 1,1,3,3,3-penta¯uoro-2-pen-
ta¯uorophenyl-1,2-epoxypropane 1 with trimethylphosphite
1Scheme 1) leads to the formation of the liquid, moisture-
sensitive 1Z)- and 1E)-3,6-bis1tri¯uoromethyl)-3,6-bis1pen-
ta¯uorophenyl)-1,4-dioxan-2,5-dione 2a, b in good yield.It
is known that the reaction of 1,2-epoxyper¯uoropropane
with tri¯uoropyruvate in the presence of tris1dimethylami-
do)phosphate 1HMPT) leads to the formation of a dioxane
[4,5].Probably there will be a MeO/F exchange with tri-
methylphosphite to give dimethyl¯uorophosphite which
3. Experimental
NMR spectra were obtained on a Bruker AC 80 instru-
ment operating at 75.39 MHz 119F, internal standard CCl3F)
and
200.13 MHz for H 1internal standard TMS), 188.31 MHz
a Bruker DPX-200 spectrometer operating at
1
* Corresponding author.Tel:. ‡49-421-218-2493;
fax: ‡49-421-218-4267.
for 19F and 50.32 MHz for 13C, internal standard TMS).
È
E-mail address: gvr@chemie.uni.bremen.de 1G.-V. Roschenthaler).
0022-1139/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 1 0 1 ) 0 0 5 6 9 - 3

100
A.A. Kadyrov et al. / Journal of Fluorine Chemistry 114 ;2002) 99±101
Scheme 1.
High®eld shifts from TMS and CCl3F were given negative
signs.MS spectra were obtained on a Varian MAT CH7A
instrument at 70 eV.
3.2. 3,3,3-Trifluoro-2-hydroxy-2-;2,3,4,5,6-
pentafluorophenyl)propionic acid 5
1E,Z)-3,6-Bis1tri¯uoromethyl)-3,6-bis1penta¯uorophenyl)
-1,4-dioxan-2,5-dione 2a, b 10.03 g) and 0.5 ml H2O was
3.1. E,Z-3,6-Bis;trifluoromethyl)-3,6-bis-
pentafluorophenyl-1,4-dioxane-2,5-dione 2a, b
heated 4 h at 80 8C.Evaporation of the CDCl extract
3
gave 0.020 g of solid 5; mp 141±142 8C [10].NMR: 19F:
4
Trimethylphosphite 11.6 g, 12.9 mmol) and 2.0 g
16.4 mmol) of 1 were heated at 60 8C for 20 h.Distillation
gave 1.57 g 184%) of 2a, b 1bp 78±80 8C/0.01 Torr). MS: m/
d ˆ À77:0 1CF3, t, JFF ˆ 17:2 Hz), À139.1 12F, m),
1
À154.2 11F, m), À163.3 1F, m). H: 4.67 s; 4.69 br.s.
‡ ‡
e
[C6F51CF3)C1O)C ], 248 [C6F51CF3)C ], 198 [C6F51CF3)-
1%): 584 1M ), 292 [C6F51CF3)C1O)CO ], 276
‡
‡
Acknowledgements
‡
‡
‡
‡
C ±CF2], 195 [C6F5C1O) ], 179 1C6F5C ), 167 1C6F5 ), 93
‡
‡
1C3F7 ), 69 1CFF3 ), 28 1CO).HRMS: calculated
mass ˆ 583:9541.Found mass ˆ 583:9537.Analysed cal-
culated for C18F16O4 1584.17): C, 37.00; F, 52.04%. Found:
C, 36.94; F, 52.17%.
We are grateful to the German±Israel Foundation for
®nancial support 1Grant I-618-20.5/1999).
2a: NMR: 19F: d ˆ À75:8 1CF3, t, JFF ˆ 11:8 Hz),
4
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