Supporting Information

Syntheses of Cyclic Carbonates with Amidinium Halide Catalysts in

Reusable, Reversible, Room-Temperature Ionic Liquids or
Acetonitrile
Tao Yu and Richard G. Weiss*
Department of Chemistry, Georgetown University
Washington, D.C. 20057-1227, USA
Email: weissr@georgetown.edu


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Figure S1. High pressure CO
2
generator and reaction cell (upper left) and temperature control
setup (upper right). The reaction cell is indicated by the arrow in both figures. The layout of the
components of the high pressure instrument is shown in the diagram at the bottom.

The stainless steel reaction cell, with three quartz windows, was designed and manufactured
at the University of Buenos Aires (Argentina). Super-ambient temperatures were achieved with
four cartridge electric heating elements and a rheostat in a system. Temperature was monitored
by an Omega HH503 microprocessor thermometer connected to a J-K-T thermocouple. High
pressure generators (Model: 50-6-15; Pressure rating: 15,000 psi; capacity per stroke: 20 mL),
valves and tubings were purchased from High Pressure Equipment Company (HIP),
Pennsylvania. The 0-25000 psi pressure gauge was purchased from McDaniel Controls, Inc.
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GC response factor calculations
F
i
(R-molar) = (area
refer
/mol
refer
)/(area
comp
/mol
comp
) (S1)
The response factor (F
i
(R-molar)) was calculated according to eq S1.
1
Here, area
refer
and
area
comp
are the areas of the peaks of a reference compound (biphenyl) and an a epoxide or a b
product, respectively. Mol
refer
and mol
comp
are the known (by preparation) concentrations of the
biphenyl and a or b, respectively. From a plot of area ratios versus composition ratios in samples
with known amounts of each, F
i
(biphenyl/b) and F
i
(biphenyl/a) were calculated; see Figure S2
for 2a and 2b, for example, where F
i
(biphenyl/2b) = 1.18 (R
2
= 0.998) and F
i
(biphenyl/2a) =
1.20 (R
2
= 0.999). Response factors for the other epoxides and cyclic carbonates are collected in
Table S1.
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
(I)


R
a
t
i
o

f
r
o
m

G
C
Weighted ratio

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0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
(II)


R
a
t
i
o

f
r
o
m

G
C
Weighted ratio

Figure S2. Linear fit of weight and GC peak ratios for biphenyl/2b (I) and biphenyl/2a (II). The
respective formulas are: Y = -0.02 + 1.18X for 2a and Y = 0.01 + 1.20X for 2b.

Table S1. GC response factors of 1a-4a and 1b-4b.
Substrate Response
Factor
Substrate Response
Factor
1a 1.16 1b 1.15
2a 1.20 2b 1.18
3a 1.12 3b 1.14
4a 1.08 4b 1.09

Characterizations of cyclic carbonates
4-Chloromethyl-1,3-dioxolan-2-one (1b):
1
H NMR: d = 3.75 - 3.81 (m, 2 H, ClCH
2
), 4.41 (dd, J
= 6.0, 9.0 Hz, 1 H, OCH
2
), 4.59 (dd, J = 8.4, 9.0 Hz, 1H, OCH
2
), 4.93 4.96 (m, 1 H, CHO);
13
C
NMR: 43.71, 66.90, 74.35, 154.30 ppm; IR: 1786 cm
-1
(C=O); MS (m/z 137 M
+
).

1
H NMR,
13
C NMR and mass spectra of 4-chloromethyl-1,3-dioxolan-2-one (1b)
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5 0 7 5 1 0 0 1 2 5 1 5 0 1 7 5
m / z
1 0 %
2 0 %
3 0 %
4 0 %
5 0 %
6 0 %
7 0 %
8 0 %
9 0 %
1 0 0 %
5 7 . 0
6 2 . 1
6 4 . 1
7 5 . 1
8 6 . 0
8 7 . 0
1 3 7 . 0
S p e c t r u m 1 A
4 . 5 3 0 m i n , S c a n : 3 3 1 , 5 0 : 6 5 0 , I o n : 2 5 5 1 u s , R I C : 7 2 6 9 6 B P : 8 7 . 0 ( 1 6 3 5 4 = 1 0 0 % ) ,


4-Phenoxymethyl-1,3-dioxolan-2-one (2b):
1
H NMR: 4.15 (dd, J = 3.6, 3.6 Hz 1H, OCH
2
), 4.24
(dd, J = 4.4, 4.4 Hz 1H, OCH
2
), 4.55 (dd, 1H, PhOCH
2
), 4.62 (t, J = 8.4 Hz, 1H,PhOCH
2
), 5.03
(m, 1H,OCH), 6.91 (d, J = 8.8Hz, 2H, Ph), 7.02 (t, J = 8.0 Hz,1H, Ph), 7.31 (t, J = 8.0 Hz, 2H,
Ph);
13
C NMR: 66.25, 66.88, 74.03, 114.55, 122.03, 129.70, 154.57, 157.73 ppm; IR:1786 cm
-1

(C=O); MS (m/z 194, M
+
).

1
H NMR,
13
C NMR and mass spectra of 4-phenoxymethyl-1,3-dioxolan-2-one (2b)
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5 0 1 0 0 1 5 0 2 0 0 2 5 0
m / z
2 5 %
5 0 %
7 5 %
1 0 0 %
5 1 . 2
6 5 . 2
7 7 . 2
7 9 . 1
9 5 . 2
1 0 7 . 0
1 9 4 . 0
1 9 5 . 0
S p e c t r u m 1 A
1 0 . 5 0 3 m i n , S c a n : 1 0 1 7 , 5 0 : 6 5 0 , I o n : 8 7 0 u s , R I C : 2 8 4 3 5 0 B P : 1 9 4 . 0


4-Phenyl-1,3-dioxolan-2-one (3b):
1
H NMR: d = 4.36 (t, J = 8.4 Hz, 1 H, OCH
2
), 4.82 (t, J = 8.4
Hz, 1 H, OCH
2
), 5.72 (t, J = 8.4 Hz, 1 H, OCH), 7.36 (m, 2 H, Ph), 7.44 (m, 3 H, Ph);
13
C NMR:
71.15, 77.97, 125.85, 129.25, 129.75, 135.80, 154.76 ppm; IR: 1780 cm
-1
(C=O); MS (m/z 164
M
+
).

1
H NMR,
13
C NMR and mass spectra of 4-phenyl-1,3-dioxolan-2-one (3b)
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5 0 1 0 0 1 5 0 2 0 0 2 5 0
m / z
1 0 %
2 0 %
3 0 %
4 0 %
5 0 %
6 0 %
7 0 %
8 0 %
9 0 %
1 0 0 %
5 0 . 1
5 1 .2
7 7 . 3
7 8 . 2
8 9 . 2
9 1 . 1
9 2 . 2
1 0 5 . 0
1 1 9 . 0
1 2 0 . 0
1 6 3 . 8
S p e c t r u m 1 A
8 .3 3 0 m i n , S c a n : 7 6 7 , 5 0 : 6 5 0 , I o n : 1 1 6 2 u s , R I C : 2 0 1 9 3 3 B P : 9 1 . 1


4,5-Tetramethylene-1,3-dioxolan-2-one (4b):
1
H NMR: d = 4.65 4.70 (m, 2 H, CHO), 1.86
1.90 (m, 4 H, CH
2
CHO), 1.581.64 (m, 2 H, CH
2
CH
2
), 1.381.44 (m, 2 H, CH
2
CH
2
);
13
C NMR:
19.13, 26.75, 75.67, 155.27 ppm; IR: 1790 cm
-1
; MS (m/z 142 M
+
).

1
H NMR,
13
C NMR and mass spectra of 4,5-tetramethylene-1,3-dioxolan-2-one (4b)
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5 0 1 0 0 1 5 0 2 0 0
m / z
1 0 %
2 0 %
3 0 %
4 0 %
5 0 %
6 0 %
7 0 %
8 0 %
9 0 %
1 0 0 %
4 0 . 2
4 1 .2
4 2 .1
5 4 .2
5 5 . 2
5 7 . 0
6 9 . 1
8 0 .1
8 3 . 0
1 4 3 . 0
S p e c t r u m 1 A
9 . 9 3 9 m i n , S c a n : 6 2 7 , 4 0 : 6 5 0 , I o n : 9 9 3 u s , R I C : 3 1 9 1 9 8 , B C B P : 4 1 . 2


Characterization of amidinium halide catalysts
1
H NMR,
13
C NMR MS and FT-IR spectra of C6-HCl
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5 0 7 5 1 0 0 1 2 5 1 5 0 1 7 5
m / z
0 %
5 %
1 0 %
1 5 %
2 0 %
2 5 %
3 0 %
5 5 . 2
1 1 6 2 4
5 6 . 1
1 0 0 4 4 3
5 7 . 0
2 0 4 2 1
6 9 . 1
3 8 6 2
8 5 . 1
7 6 5 4
9 9 . 2
2 2 6 6 4
1 1 3 . 2
1 6 8 7 5
1 2 6 . 1
3 2 5 3 5
1 2 7 . 2
4 9 0 4 1 5 5 . 2
4 0 3 7
1 7 1 . 2
1 0 2 8 3
S p e c t r u m 1 A
5 . 6 4 9 m i n , S c a n : 4 5 9 , 5 0 : 6 5 0 , I o n : 8 7 5 u s , R I C : 2 9 7 9 9 6 B P : 5 6 . 1


1
H NMR,
13
C NMR, MS and FT-IR spectra of C6-HBr
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5 0 7 5 1 0 0 1 2 5 1 5 0 1 7 5
m / z
0 %
5 %
1 0 %
1 5 %
5 1 . 0
2 3
5 4 . 0
5 1
5 5 . 2
1 9 0
5 6 . 1
1 7 7 9
6 8 . 1
2 4 5
7 0 . 0
7 2
7 1 . 0
1 2 9
7 3 .0
2 9
8 4 . 1
5 7
8 5 .0
1 2 7
8 6 . 0
1 6 6
9 7 . 1
2 6
9 9 . 0
3 0 8
1 0 0 . 1
9 4
1 1 3 . 2
2 7 3
1 1 4 . 1
5 4
1 2 6 . 2
5 3 5
1 2 7 .2
8 7
1 3 5 . 2
1 8
1 4 1 . 2
4 6
1 5 5 . 2
6 0
1 7 1 . 2
2 1
S p e c t r u m 1 A
5 . 6 5 1 m i n , S c a n : 4 5 9 , 5 0 : 6 5 0 , I o n : 2 5 0 0 0 u s , R I C : 5 2 3 7 B P : 5 6 . 1 ( 1 7 7 9 = 1 0 0 % ) ,


1
H NMR,
13
C NMR, MS and FT-IR spectra of C6-HI
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5 0 1 0 0 1 5 0 2 0 0
m / z
0 %
5 %
1 0 %
1 5 %
2 0 %
2 5 %
5 4 . 2
1 3 2 8
5 5 . 3
5 7 1 5
5 6 . 1
4 5 5 9 9
5 7 . 1
9 4 2 9
6 8 . 2
4 7 3 0
7 0 . 2
2 5 0 6
8 4 . 2
1 0 8 9
8 5 . 1
3 4 8 4
9 9 . 2
1 0 0 9 7
1 1 3 . 2
7 2 7 9
1 2 6 . 2
1 5 9 5 7
1 2 7 . 2
2 5 0 8
1 7 1 . 2
2 3 9 0
S p e c t r u m 1 A
5 . 6 4 7 m i n , S c a n : 4 5 9 , 5 0 : 6 5 0 , I o n : 1 9 9 0 u s , R I C : 1 3 4 9 6 3 B P : 5 6 . 1


Reactions at 1 atm pressure of CO
2

(1) C6 amidine (0.34 g, 2.0 mmol), and LiBr (0.44 g, 5.0 mmol) were added to a solution of
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cyclohexene oxide (3a) (2.0 g, 20 mmol) in 5.0 mL of DMF in a flask with a 1 cm teflon stir
bar. CO
2
(g) from a gas balloon was attached to the flask through a rubber stopper and the
reaction was allowed to stir at room temperature under CO
2
atmosphere for 72 h.
(2) C6 amidine (0.34 g, 2.0 mmol), and LiBr (0.44 g, 5.0 mmol) were added to a solution of
cyclohexene oxide (3a) (2.0 g, 20 mmol) in a flask with a 1 cm teflon stir bar. CO
2
(g) from
a gas balloon was attached to the flask through a rubber stopper and the reaction was allowed
to vigorously stir at room temperature under CO
2
atmosphere for 24 h.
(3) C6 amidine (0.34 g, 2.0 mmol), and C6-HBr (1.25 g, 5.0 mmol) were added to a solution of
cyclohexene oxide (3a) (2.0 g, 20 mmol) in a flask with a 1 cm teflon stir bar. CO
2
(g) from a
gas balloon was attached to the flask through a rubber stopper and the reaction was allowed
to vigorously stir at room temperature under CO
2
atmosphere for 24 h.

References

(1) J. Slemr, F. Slemr, H. DSouzac and R. Partridge, J. Chromatogr. A 2004, 1061, 7584.
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