Y. Ohtsuka et al. / Journal of Fluorine Chemistry 161 (2014) 34–40
39
4
. Experimental
4.2.4. Hydroformylation in an autoclave
[Rh(OH)(cod)] (0.006 mmol), Xantphos (0.036 mmol), DMF (7 mL)
4.1. General techniques
2
and the DMF solution of TFP (3 mL, 0.5 mol/L, TFP 1.5 mmol) were
charged together in a 100 mL autoclave. After purging the autoclave
1
13
19
31
3
H, C, F and P NMR spectra were recorded in CDCl on
13
1
19
Bruker a DRX-500 ( C 125 MHz) and a DRX-250 ( H 250 MHz,
F
2
with 50/50 CO/H mixed gas, the autoclave was sealed under 1.0 or
2
35 MHz) spectrometers using tetramethylsilane as an internal
1.5 atm at room temperature. For example, the volume of CO or H
2
1
13
reference for H and C NMR and fluorotrichloromethane as an
wasca. 45 mLunder1.0 atm, whichcorrespondstoca. 1.2equivalent
to TFP. The mixture was then heated at 80 8C for 2 h. After cooling to
1
9
external reference for F NMR. The chemical shifts are expressed
in ppm ( ). The multiplicities are indicated by brs (broad singlet), d
doublet), t (triplet), q (quartet) and m (multiplet). The F NMR
1
9
d
0 8C, an aliquot of the mixture was analyzed F NMR spectroscopy
and GC. The same procedure as the reactions under atmospheric
pressure, where the reaction was performed after preparation step
(i) followed by step (ii), afforded lower yield and selectivity, 39% and
80/20, than entry 1 of Table 6.
1
9
(
yields were calculated with 2,2,2-trifluoroethanol as an internal
standard. Gas chromatography (GC) analyses were performed
using a Shimadzu GC-14A with CP-Volamine (60 m  0.32 mm).
All the commercially available reagents were used without further
purification.
4.3. Characterization of products
4
4
.2. Reaction procedures of hydroformylation
All the products are known compounds and are given a CAS
number. These compounds except 4,4,5,5,6,6,7,7,7-nonafluoro-
heptanal have been already characterized by H, C and F NMR
[3b]. The NMR data agreed with this reported data.
1
13
19
.2.1. Quantitative analyses of product
The quantitative analyses of the starting material and products
19
in the liquid phase were mainly carried out by the F NMR spectral
analyses. Prior to the analyses, the calibration curve was
established with five authentic samples of TFB and TFMP; each
of concentration was adjusted according to that in the reaction
mixture, [TFB]/[TFMP] = 91, 95, 97, 99 and 99.5. We confirmed that
4.3.1. 4,4,4-Trifluorobutanal (CAS No. 406–87-1)
1
Colorless liquid. H NMR (CDCl
J = 7.5 Hz, 2H), 9.81 (brs, 1H).
3
)
d
2.46 (m, 2H), 2.77 (t,
C NMR (CDCl 26.4 (q,
CF = 30.4 Hz), 36.3 (q, JCF = 2.5 Hz), 126.4 (q, CF = 275.6 Hz),
1
3
3
) d
J
J
19
19
the peak area ratio of TFB to TFMP in F NMR spectrum is
approximately equal to the molar ratio of the authentic samples.
Furthermore, the quantitative analyses by GC also supported the
198.0. F NMR (CDCl
3
)
d
À66.7.
4.3.2. 3,3,3-Trifluoro-2-methylpropanal (S: CAS No. 189638-88-8, R:
19
accuracy of the F NMR spectral analyses.
CAS No. 189638-87-7)
1
Colorless liquid. H NMR (CDCl
3
)
d
1.33 (d, J = 7.2 Hz, 3H), 3.10
) d 7.3 (q, JCF = 2.6 Hz), 50.5
1
3
4.2.2. Hydroformylation in 1 atm of 50/50 CO/H
2
mixed gas
(m, 1H), 9.77 (m, 1H). C NMR (CDCl
(q, JCF = 25.9 Hz), 125.5 (q, JCF = 279.7 Hz), 195.0 (q, JCF = 3.0 Hz).
NMR (CDCl
À68.5.
3
19
The reaction apparatus was equipped to a gas buret or a balloon.
A Rh precursor (0.001–0.01 mmol), a ligand (0.006–0.06 mmol)
and a solvent (5 mL) were charged in the reaction apparatus. After
F
3
) d
purging the apparatus with 50/50 CO/H
mixed gas was charged and sealed under atmospheric pressure.
The amounts of CO and H were ca. 25 mmol under the standard
condition, respectively. The reaction mixture was stirred at 80 8C
for 1 h (preparation step (i)) and then 5 mL of the solution of TFP
2
mixed gas, ca. 1.2 L of
4.3.3. 4,4,5,5,6,6,7,7,7-nonafluoroheptanal (CAS No. 1262646-38-7)
1
Colorless liquid. H NMR (CDCl
3
)
d
2.47 (m, 2H), 2.83 (t,
C NMR (CDCl 23.4 (t,
), 34.5 (t, JCF = 2.8 Hz, –CH CHO), 100–130
À81.2 (m, 3F), À114.6
1
3
2
J = 7.5 Hz, 2H), 9.84 (brs, 1H).
CF = 22.4 Hz, –CH
(m, –C ), 197.4 (–CHO). F NMR (CDCl
(m, 2F), À124.5 (m, 2F), À126.1 (m, 2F).
3
) d
J
2
C
4
F
9
2
1
9
4
F
9
3
) d
(
0.5 mol/L, TFP 2.5 mmol) was added through a septum using a
syringe. [CO] or [H ]/[TFP] was ca. 10. The mixture was further
heated for 15 h (reaction step (ii)). After cooling to 0 8C, an aliquot
2
4.3.4. 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
heptadecafluoroundecenal (CAS No. 42028-44-4)
19
of the mixture was analyzed by F NMR spectroscopy. The analysis
of gas phase was performed by GC. The aldehydes in the gas phase
were confirmed to be very small (<0.1%). The reactions in Table 7
were carried out by the further addition of the DMF solution of TFP
after 2 h reaction.
1
Colorless liquid. H NMR (CDCl
3
)
d
2.47 (m, 2H), 2.83 (t,
C NMR (CDCl 23.5 (t,
17), 34.5 (–CH CHO), 100–130 (m, –C
197.3 (–CHO). F NMR (CDCl
À80.7 (t, J = 10.0 Hz, 3F), À114.7
m, 2F), À121.7 (m, 2F), À121.9 (m, 4F), À122.7 (m, 2F), À123.5 (m,
2F), À126.1 (m, 2F).
1
3
J = 7.5 Hz, m), 9.84 (brs, 1H).
CF = 22.5 Hz, –CH
3
) d
J
2
C
8
F
2
8
F17),
1
9
3
) d
(
4.2.3. Hydroformylation in 1 atm of 60/40–80/20 CO/H
2
mixed gas
A reaction apparatus was equipped to a gas buret or a balloon.
A Rh precursor (0.001–0.01 mmol), a ligand (0.001–0.01 mmol)
and DMF (5 mL) were charged in the reaction apparatus. After
Appendix A. Supplementary data
perging the apparatus with CO/H
gas was charged and sealed under atmospheric pressure. For
2
mixed gas, ca. 1.8 L of mixed
example, 80/20 CO/H
and 18.7 mmol of H
2
mixed gas contains ca. 56.3 mmol of CO
under the standard conditions, which
2
correspond to [CO]/[TFP] = ca. 22 and [H
respectively. The mixture was heated at room temperature or
0 8C for 1 h and then 5 mL of the DMF solution of TFP (0.5 mol/L,
2
]/[TFP] = ca. 7.5,
References
8
[1] The patents and papers published after 2011 are listed below.;
TFP 2.5 mmol) was charged through a septum using a syringe.
(
(
a) T. Kagawa, K. Kawada, JP 201313151452.;
b) M. Didiuk, K.J. Filipski, A. Guzman-Perez, E.C. Lee, J.A. Pfefferkorn, B. Stevens, M.
The mixture was further heated for 15 h. After cooling to 0 8C, an
1
9
aliquot of the mixture was analyzed by F NMR spectroscopy
and GC. The analysis of the gas phase was performed by GC. The
aldehydes in the gas phase were confirmed to be very small
Tu, WO 2013014569.;
c) I R.M. Borzilleri, Z.-W. Cai, A.J. Tebben, H.L. Perez, L. Zhang, G.M. Schroeder, D.D.
Wei, WO 2012162365.;
d) L. Provins, Y. Quesnel, WO 2012143117.;
(e) D. Swinnen, C. Jorand-Lebrun, P. Gerber, S. Kulkarni, EP 2508526.;
(
(
(
<0.1%).