T. Okazoe et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 8 (2007) 1615
ꢁ
The same operation was repeated 6 times, then nitrogen gas was
supplied for 2 h. The combined reaction mixture was concentrated
to give the crude liquid. Then, the crude liquid (2500 g) was
autoclave, a cooler maintained at ꢂ10 C was installed. After sup-
plying nitrogen gas for 2 h, 50% F2/N2 was supplied for 2 h at
a flow rate of 64.4 L h . While supplying 50% F2/N2 at the same
ꢂ1
ꢁ
put into the above autoclave, circulated and stirred again at 25 C.
After supplying nitrogen gas for 2 h, 50% F2/N2 gas was supplied
flow rate, 18 (1200 g, 2.56 mol) was injected over 24 h. The crude
liquid (1400 g) was extracted from the reactor. The same operation
was repeated 9 times, then nitrogen gas was supplied for 2 h.
The combined reaction mixture was concentrated to give the crude
liquid. Then, the crude liquid (2090 g) was put into the above
autoclave, circulated and stirred again at 40 C. After supplying
nitrogen gas for 2 h, 50% F2/N2 was supplied for 2 h at a flow
rate of 142 L h . Then, while supplying 50% F2/N2 at the same
ꢂ1
for 2 h at a flow rate of 42.0 L h . Then, while supplying 50%
F2/N2 at the same flow rate, 11b (1440 g, 2.68 mol) was injected
over a period of 24 h, and then nitrogen gas was supplied for
ꢁ
2
h. A crude liquid (4190 g) was obtained. The desired product
19
was quantified by F NMR (internal standard: C6F6), and the
yield of 12b was 94%. The product 12b decomposed on silica-
gel column and partly decomposed even in a distillation process
so that the crude product was directly used for the next step.
ꢂ1
flow rate, 18 (1200 g, 2.56 mol) was injected over a period of
24 h, and then nitrogen gas was supplied for 2 h. A liquid (3650 g)
was obtained, and the yield of 19 determined by GC and
NMR analysis was 83%. 19F NMR (282.7 MHz, CDCl3) ꢀ: ꢂ63:1
to ꢂ65:0 (2F), ꢂ75:5 to ꢂ76:5 (3F), ꢂ79:0 to ꢂ80:5 (1F), ꢂ81:9
(3F), ꢂ82:1 (3F), ꢂ86:0 to ꢂ88:0 (1F), ꢂ110:0 to ꢂ115:5 (2F),
ꢂ130:0 (2F), ꢂ130:5 to ꢂ133:5 (2F), ꢂ135:0 to ꢂ138:0 (1F).
19
F NMR (376.0 MHz, CDCl3) ꢀ: ꢂ78:5 to ꢂ80:0 (7F), ꢂ80:7
(
3F), ꢂ81:9 to ꢂ82:8 (8F), ꢂ84:8 to ꢂ86:3 (1F), ꢂ130:2 (2F),
þ
ꢂ132:2 (1F), ꢂ143:1 (1F), ꢂ145:4 (1F): HRMS (EI ) m=z ¼
þ
6
44:9422, calcd for C12F23O4½M ꢂ Fꢃ : m=z ¼ 644:9429.
Synthesis of Hexafluoroacetone (HFA) (14): Into an Inconel
column (inner diameter = 14 mm, length = 1 m), potassium fluo-
ride (10–20 mesh, 50 g) was packed and set in a salt bath, and the
þ
35
þ
HRMS (CI ) m=z ¼ 610:8915, calcd for C11 Cl2F19O3½M ꢂ Fꢃ :
m=z ¼ 610:8921.
ꢁ
16
internal temperature of the salt bath was adjusted to 200 C. To
this reactor, a mixture of 12b and 13b in a ratio of 8:2 obtained in
the same manner as above was fed for 2 h at a rate of 60 g h by
means of a metering pump. At the outlet of the reactor, a reflux
Synthesis of CF2ClCFClCF2COCF3 (15): The crude
dichloropolyfluoro ester 19 (24.8 g) obtained above and potassium
ꢂ1
ꢁ
fluoride powder (1.17 g) were heated at 130 C for 2 h and at
ꢁ
140 C for 1.5 h, while stirring vigorously. After cooling, a liquid
sample (21.7 g) was recovered and analyzed by GC-MS. The yield
of 15 from 19 was determined by GC and found to be 85%.
ꢁ
condenser at ꢂ20 C was installed, and the mixture was separated
into a gas sample and a liquid sample. The gas sample (23.2 g)
was collected in a collecting container made of a fluorocarbon
resin, and the liquid sample (95.8 g) was recovered in a glass trap.
The gaseous sample was analyzed by GC-MS and found to be
HFA (yield from 12b was 97%). From the liquid sample, 2b
We would like to thank Professor Richard D. Chambers for
helpful discussions.
(
69.5 g) was recovered by distillation.
Preparation of CH2ClCHClCH2CH(CH3)OCOCF(CF3)-
References
OCF2CF2CF3 (18): 4-Penten-2-ol (16, 13.1 kg, 152 mol) was
stirred, while bubbling nitrogen gas, and 2a (54.3 kg, 164 mol)
was charged over 5 h, while maintaining the internal temperature
1
a) T. Hiyama, Organofluorine Compounds, Springer,
Berlin, 2000. b) R. D. Chambers, Fluorine in Organic Chemistry,
2nd ed., Oxford, 2004. c) P. Kirsh, Modern Fluoroorganic
ꢁ
at from 25 to 30 C. After completion of the charging, the reaction
ꢁ
mixture was stirred for 70 h at from 30 to 50 C, while bubbling
nitrogen gas. The obtained crude liquid of 17 (58.3 kg) was used
for the next step without purification. The purity by GC was
2
a) S. Rosen, Reactions of Fluorine in Inert Media in
3
1
9
7%. H NMR (300.4 MHz, CDCl3) ꢀ: 1.32 (d, J ¼ 6:0 Hz, 3H),
.30 to 2.50 (m, 2H), 5.07 to 5.21 (m, 3H), 5.61 to 5.76 (m, 1H).
F NMR (282.7 MHz, CDCl3) ꢀ: ꢂ79:6 (1F), ꢂ81:3 (3F), ꢂ82:0
3F), ꢂ86:3 (1F), ꢂ129:4 (2F), ꢂ131:5 (1F).
Methoden Org. Chem. (Houben-Weyl), 4th ed., ed. by B. Baasner,
H. Hagemann, J. C. Tatlow, Georg Thieme Verlag, Stuttgart,
1999, Vol. E10a, pp. 167–187. b) W. W. Schmiegel, Organic
Fluoropolymers in Chemistry of Organic Fluorine Compounds
II, ed. by M. Hudlicky, A. E. Pavlath, American Chemical
Society, Washington, DC, 1995, pp. 97–112.
2
1
9
(
Into a 5-L flask equipped with a reflux condenser adjusted at
ꢁ
2
0 C, 17 (5000 g, 12.6 mol) obtained above was charged, and
ꢁ
the reactor was cooled to ꢂ30 C. Then, chlorine gas was continu-
4
5
J. Hutchinson, G. Sandford, Top. Curr. Chem. 1997, 193, 1.
R. J. Lagow, Reactions of Fluorine in the Presence of
ously bubbled into the reaction solution, while maintaining
ꢁ
the internal temperature at under 10 C. When the reaction pro-
Solvents, in Methoden Org. Chem. (Houben-Weyl), 4th ed., ed.
by B. Baasner, H. Hagemann, J. C. Tatlow, Georg Thieme Verlag,
Stuttgart, 1999, Vol. E10a, pp. 194–200.
6
Patent 5093432, 1992.
ceeded and no more heat generation was observed, the tempera-
ture of the reactor was raised to room temperature and nitrogen
gas was bubbled in the reaction solution for 24 h to obtain a crude
liquid (5900 g). The compound 18 was found to have formed
T. R. Bierschenk, T. Juhlke, H. Kawa, R. J. Lagow, U.S.
1
in 95% yield by GC analysis. H NMR (300.4 MHz, CDCl3) ꢀ:
7
1
.42 (d, J ¼ 6:3 Hz, 3H), 1.86 to 2.51 (m, 2H), 3.52 to 3.84 (m,
1
9
2
H), 3.97 to 4.09 (m, 1H), 5.34 to 5.59 (m, 1H). F NMR (282.7
MHz, CDCl3) ꢀ: ꢂ80:4 (1F), ꢂ81:9 (3F), ꢂ82:5 (3F), ꢂ86:7 (1F),
8
þ
ꢂ130:2 (2F), ꢂ132:3 (1F): HRMS (CI ) m=z ¼ 448:9772, calcd
for C11H935Cl2F10O3½M ꢂ Fꢃ : m=z ¼ 448:9769.
þ
Large-Scale Synthesis of CF2ClCFClCF2CF(CF3)OCOCF-
9
(
and having an external circulation tubular type reactor, 2b (2510
g) was circulated and stirred at 25 C. At the gas outlet of the
CF3)OCF2CF2CF3 (19): Into a 3-L autoclave made of nickel
10 T. Okazoe, K. Watanabe, M. Itoh, D. Shirakawa,
ꢁ