Electronic Supplementary Information for by amines Rational … · 2014-07-16 · Electronic...

Electronic Supplementary Information for

Rational investigations in the ring opening of cyclic carbonates by amines

M. Blain,a,b L. Jean-Gérard,a R. Auvergne, b D. Benazet, c S. Caillol, b,* and B. Andriolettia,*

a ICBMS-UMR 5246 Université Claude Bernard-Lyon 1 Equipe de CAtalyse, SYnthèse et Environnement (CASYEN) Domaine Scientifique de la Doua-Bât. Curien/CPE, 2° étage aile C 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex-France.b Ecole Nationale Supérieure de Chimie de Montpellier 8, Rue de l’Ecole Normale, 34296 Montpellier-France.c JUXTA 5 rue de la Jalesie, BP 71039 25401 Audincourt cedex-France

Content :

1. General information

2. Synthesis of catalysts, carbonates and carbamates

3. General procedure for the GC/MS quantitative analysis of the carbonate aminolysis

4. General procedure for the NMR analysis of the carbonate aminolysis

5. Examples and spectrum of quantitative analysis from the publication

6. 1H NMR comparison of the aminolysis 1) in the presence of TBD (revealing traces of

impurities), 2) using the thiourea as an organocatalyst.

7. 1H and 13C NMR spectrum

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2014

1. General information

1H and 13C spectra were recorded on a Bruker ALS-300 or a Bruker ALS-400 spectrometers. The NMR chemical shifts are reported as δ in parts per million (ppm) relative to the traces of non-deuterated solvent (eg δ = 2.50 ppm for d6-DMSO or δ = 7.26 ppm for CDCl3). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet, br = broad), coupling constants (J) given in Hertz (Hz), integration and attribution. Low-resolution gas chromatography coupled with a mass spectrometry detector (GC-MS) was performed using a Shimadzu GCMS-QP2010S apparatus using a ZB5-HT column and helium as carrier gas. The quantitative GC-MS analyses were performed using an internal standard (diphenyl ether) and calibration charts. Flash column chromatographies were performed using normal phase silica gel (60 Å, particle size 40-63 μm) and monitored with thin-layer chromatographies using TLC plates GF254 purchased from Merck (0.25 mm). All the catalysts and IPDA were used as received. The thioureas were synthesized according to the reported literature procedure.1 Propylene carbonate (PC) was purified by distillation. 4-(methoxymethyl)-1,3-dioxolan-2-one, 4,6-dimethyl-1,3-dioxan-2-one and 4-phenyl-1,3-dioxolan-2-one were synthesized according to the reported literature procedure.2,3

2. Synthesis of catalysts, carbonates and carbamates

NH

NH

S

CF3

F3C

1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea was synthesized according to the literature procedure1: At room temperature, cyclohexanamine (0.534 g, 5.39mmol) was added dropwise to a stirred solution of 3,5-bis(trifluoromethyl)phenyl isothiocyanate (1.500 g, 5.53 mmol) in THF (10 mL). After stirring for 4 h at room temperature, the solvent was evaporated. The white residue was recrystallized from chloroform to give 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea as a white powder. Yield: 1.76 g (88%).

1H NMR (DMSO- d6, 400 MHz): δ 7.42 (s, 1H, 4-ArH), 7.29 (s, 2H, 2,6-ArH), 6.82 (s, 1H, ArNH), 5.19 (s, 1H, CyNH), 4.40 (br m, 1H, NCyH), 1.91-0.86 (m, 10H, CyH).

13C NMR (DMSO- d6, 100 MHz): δ 179.2, 142.0, 130.1 (q, J=33 Hz), 123.3 (q, J=273 Hz), 121.7, 115.8, 52.3, 31.6, 25.1, 24.4.

19F NMR (benzene-d6, 376 MHz): δ -63.5 (s, CF3).

Spectroscopic data were identical to those found in previous literature reports for this compound.1

NH

NH

S

CF3

F3C

1-(3,5-bis(trifluoromethyl)phenyl)-3-butylthiourea was synthesized according to the literature procedure1 : Butylamine (0.161g, 2.21 mmol) was added dropwise at room temperature to a stired solution of 3,5-bis(trifluoromethyl)phenyl isothiocyanate (0.500 g, 1.84 mmol) in dry THF (5 mL). After the solution was stirred for 4 h at room temperature, the solvent was evaporated. The white residue was recrystallized from cyclohexane to give 1-(3,5-bis(trifluoromethyl)phenyl)-3-butylthiourea as a white powder. Yield: 0.463g (77%).

m.p. = 101°C

1H NMR (DMSO-d6, 400 MHz): δ 10.02 (s, 1H, ArNH), 8.23 (s, 1H, BuNH), 8.23 (s, 2H, 2,6-ArH), 7.71 (s, 1H, 4-ArH), 3.49 (br m, 2H, N-CH2), 1.54 (m, 2H, CH2), 1.33 (m, 2H, CH2-CH3), 0.90 (t, 3H, J=7.3 Hz, CH3).

13C NMR (DMSO-d6, 100 MHz): δ 180.4, 142.0, 130.2, 123.3, 121.7, 115.9, 43.6, 30.3, 19.6, 13.7.

13C NMR (DMSO-d6, 100 MHz): δ 180.4, 142.0, 130.2 (q, J=33 Hz), 123.3 (q, J=273 Hz), 121.7, 115.9, 43.6, 30.3, 19.6, 13.7.

19F NMR (DMSO-d6, 282 MHz): δ -61.67 (s, CF3).

ESI-MS: calcd for [C13H15F6N2S (M + H+] 345.0855, found 345.0853

O

OOO

4-(methoxymethyl)-1,3-dioxolan-2-one : In a 50 mL round bottom flask at 0°C 4-(hydroxymethyl)-1,3-dioxolan-2-one (3.37 mL, 40 mmol) was added to a suspension of sodium hydride (60% w/w dispersion in mineral oil, 1.76g, 44 mmol) in dry THF (25 mL). After stirring at room temperature for 3 hours the mixture was cooled to 0°C and dimethyl sulfate (4.16mL, 44 mmol) was added. After stirring 15 hours at room temperature the mixture was quenched with water. The aqueous layer was extracted with EtOAc (4x100 mL). The combined organic phases were dried over MgSO4, and concentrated under reduced pressure. The crude residue was purified on a silica gel column chromatography using EtOAc /Heptane (70:30) to give 4-(methoxymethyl)-1,3-dioxolan-2-one as a colorless oil. Yield: 3.2g (60%).

1H NMR (DMSO-d6, 400 MHz): δ 4.92 (m, 1H, CH), 4.52 (dd, 1H, J=8.4Hz, J=8.4Hz, CH2-OC=O), 4.25 (dd, 1H, J=8.3Hz, J=5.9Hz, CH2-OC=O), 3.55 (m, 2H, CH2-OMe), 3.31 (s, 3H, CH3).

13C NMR (DMSO-d6, 100 MHz): δ 155.0, 75.4, 71.4, 66.0, 58.7.

Spectroscopic data were identical to those found in previous literature reports for this compound.4

O O

O

**

A/B

4,6-dimethyl-1,3-dioxan-2-one2 : In a 250 mL round bottom flask at 0°C, dry pyridine (19 mL, 230 mmol) was added to a solution of 2,4-pentanediol (4.21 mL, 38 mmol) in dry CH2Cl2

(80 mL), followed by the dropwise addition of a solution of triphosgene (6.77g, 23mmol) in dry CH2Cl2 (40mL). The mixture was then slowly warmed up to room temperature. The reaction was quenched with a saturated NH4Cl aqueous solution and the products were extracted with CH2Cl2 (5x25 mL). The combined organic layers were successively washed with 1M HCl (1x20mL), saturated NaHCO3 solution (2x25 mL), brine, dried over Na2SO4 and concentrated under reduced pressure. The crude residue was purified on a silica gel column chromatography using EtOAc /Heptane (50:50) to give the combined diastereoisomers A and B of 4,6-dimethyl-1,3-dioxan-2-one as a slightly yellow oil. Yield: 3.39 g (68%)

1H NMR (DMSO-d6, 400 MHz): δ 4.72 (m, 2H, CHA), 4.61 (m, 2H, CHB), 2.14 (ddd, 1H, J=14.1Hz, J=2.9Hz, J=2.9Hz, CH2B), 1.93 (dd, 2H, J=5.5Hz, J=5.5Hz, CH2A), 1.52 (ddd, 1H, J=14.1Hz, J=11.5Hz, J=2.9Hz, CH2B), 1.32 (d, 6H, J=6.4Hz, CH3A), 1.27 (d, 6H, J=6.3Hz, CH3B)

13C NMR (DMSO-d6, 100 MHz): δ 148.6, 148.6, 75.0, 72.6, 35.4, 32.8, 20.7, 20.4.

Spectroscopic data were identical to those found in previous literature reports for this compound5.

O

OOPh

4-phenyl-1,3-dioxolan-2-one3 : In a 270 mL reactor styrene oxide (6.0 g, 50 mmol) and LiBr (0.22 g, 2.5 mmol) were dissolved in DMF (100 mL). The atmosphere was replaced with CO2 (P=20 bar). The solution was then allowed to stand at 80 °C with continuous stirring for 12 h. The reaction media was diluted with EtOAc (300mL), extracted several times with brine, dried over Na2SO4 and concentrated under reduced pressure. The crude residue was purified on a silica gel column chromatography using EtOAc /Heptane (25:75) to give 4-phenyl-1,3-dioxolan-2-one as a white solid. Yield: 6.8g (83%).

1H NMR (DMSO-d6, 400 MHz): δ 7.55-7.35 (m, 5H, CHaromatic), 5.86 (dd, 1H, J = 7.9, J = 7.9 Hz, CH), 4.89 (dd, 1H, J = 7.9, J = 8.3 Hz, CH2), 4.42 (dd, 1H, J = 7.9, J = 8.3 Hz, CH2).

13C NMR (DMSO-d6, 100 MHz): δ 154.7, 136.2, 129.3, 128.9, 126.7, 77.8, 70.8.

Spectroscopic data were identical to those found in previous literature reports for this compound6.

General procedure for the synthesis of the carbamates

In a 10 mL reaction tube cyclohexanamine (2 equiv.) was added to the carbonate (1 equiv.). After stirring at 25°C for 15 hours the reaction mixture was purified on a silica gel column chromatography using EtOAc and Heptane to give the combined isomers.

HN O

OOH

HN O

OOH

BA

The reaction was performed with cyclohexyl amine (600µL, 5.21mmol) and propylene carbonate (220µL, 2.59mmol). The reaction mixture was purified on a silica gel column chromatography using a gradient of EtOAc in Heptane (4:1 to 1:0) to give the combined isomers 2-hydroxypropyl cyclohexylcarbamate A and 1-hydroxypropan-2-yl cyclohexylcarbamate B (58:42) isolated as colorless oil. Global yield: 416 mg (80%).

1H NMR (DMSO-d6 + D2O, 300 MHz): δ 7.00 (d, 1H, J=7.82 Hz, NHA), 6.91 (d, 1H, J=7.96 Hz, NHB), 4.59 (tq, 1H, J=6.39 Hz, J=6.22 Hz, CH3-CHB), 3.73 (m, 3H, CH3-CHA, O-CH2A), 3.49-3.12 (m, 4H, HO-CH2B, NCyHAB),1.80-0.95 (m, 20H, CyHAB), 1.08 (d, 3H, J=6.39 Hz, CH3B), 1.01 (d, 3H, J=6.01 Hz, CH3A)

13C NMR (DMSO-d6 + D2O, 100 MHz): δ 155.7, 155.4, 70.7, 68.9, 64.5, 64.0, 49.5, 32.8, 25.3, 24.8, 20.1, 17.1

HN O

OOH

HN O

OOH

BA

O

O

The reaction was performed with cyclohexyl amine (349µL, 3.0mmol) and 4-(methoxymethyl)-1,3-dioxolan-2-one (0.200g, 1.5mmol). The reaction mixture was purified on a silica gel column chromatography using a gradient of EtOAc in Heptane (2:3 to 1:1) to give the combined isomers 2-hydroxy-3-methoxypropyl cyclohexylcarbamate A and 1-hydroxy-3-methoxypropan-2-yl cyclohexylcarbamate B (75:25) isolated as white powder. Global yield: 304mg (87%).

1H NMR (DMSO-d6, 400 MHz): δ 7.06 (2H, NHA, NHB), 4.93 (d, 1H, J=5.2 Hz, OHA), 4.77 (t, 1H, J=5.6Hz, OHB), 4.67 (m, 1H, CHB), 3.86 (m, 2H, CH2A), 3.73 (m, 1H, CHA), 3.50-

3.38 (m, 4H, CH2B, CH2B), 3.35-3.15 (m, 10H, CH3A, CH2A, CHA,B-cyclohexyl), 1.82-1.45 (m, 10H, CH2A,B-cyclohexyl), 1.33-0.93 (m, 10H, CH2A,B-cyclohexyl).

13C NMR (DMSO-d6, 100 MHz): δ 155.4, 155.1, 73.9, 72.7, 71.2, 67.6, 65.3, 60.1, 58.5, 58.3, 49.4, 32.7, 25.2, 24.7.

HN O

OA/B

OH* *

The reaction was performed with cyclohexyl amine (0.2349g, 4.8mmol) and 4,6-dimethyl-1,3-dioxan-2-one (0.3087g, 2.4mmol). The reaction mixture was purified on a silica gel column chromatography with EtOAc and heptane (70:30) to give the distinct diastereoisomers A and B of 4-hydroxypentan-2-yl cyclohexylcarbamate (75:25) isolated as colorless liquids. Yield A: 199mg (36%), yield B: 333mg (60%).

4-hydroxypentan-2-yl cyclohexylcarbamate A

1H NMR (DMSO-d6, 400 MHz): δ 6.92 (d, 1H, J=5.2 Hz, NH), 4.76 (m, 1H, CH), 4.42 (d, 1H, J=4.9 Hz, OH), 3.63 (m, 1H, CH), 3.21 (m, 1H, CHcyclohexyl),1.77-0.96 (m, 12H, CH2cyclohexyl, CH), 1.13 (d, 3H, J=6.24 Hz, CH3),1.03 (d, 3H, J=6.18 Hz, CH3).

13C NMR (DMSO-d6, 100 MHz): δ 155.4, 67.4, 62.6, 49.3, 45.8, 32.7, 25.2, 24.7, 24.2, 21.2

4-hydroxypentan-2-yl cyclohexylcarbamate B

1H NMR (DMSO-d6, 400 MHz): δ 6.89 (d, 1H, J=7.9 Hz, NH), 4.76 (m, 1H, CH), 4.43 (d, 1H, J=4.9 Hz, OH), 3.63 (m, 1H, CH), 3.21 (m, 1H, CHcyclohexyl),1.78-0.97 (m, 12H, CH2cyclohexyl, CH), 1.13 (d, 3H, J=6.22 Hz, CH3),1.05 (d, 3H, J=6.14 Hz, CH3).

13C NMR (DMSO-d6, 100 MHz): δ 155.1, 67.5, 63.0, 49.3, 45.5, 32.8, 25.2, 24.7, 23.8, 20.0.

HN O

OOH

PhHN O

OOH

PHBA

The reaction was performed with cyclohexyl amine (0.362g, 3.6mmol) and 4-phenyl-1,3-dioxolan-2-one (0.300g, 1.83mmol). The reaction mixture was purified on a silica gel column chromatography using a gradient of EtOAc in Heptane (1:4 to 3:7) to give the distinct isomers 2-hydroxy-2-phenylethyl cyclohexylcarbamate A and 1-hydroxy-2-phenylethan-2-yl cyclohexylcarbamate B (60:40) isolated as white powders. Yield A: 257mg (53%), yield B: 171mg (35%)

2-hydroxy-2-phenylethyl cyclohexylcarbamate A

1H NMR (DMSO-d6, 400 MHz): δ 7.40-7.21 (m, 5H, CHaromatic), 7.07 (d, 1H, J = 7.9 Hz, NH), 5.48 (d, 1H, J=4.6 Hz, OH), 4.73 (m, 1H, CH), 3.97 (d, 2H, J=6 Hz, CH2), 3.23 (m, 1H, CHcyclohexyl), 1.87-1.43 (m, 5H, CH2cyclohexyl), 1.35-0.87 (m, 5H, CH2cyclohexyl).

13C NMR (DMSO-d6, 100 MHz): δ 155.3, 142.5, 128.0, 127.2, 126.3, 70.8, 68.6, 49.4, 32.6, 25.1, 24.7.

1-hydroxy-2-phenylethan-2-yl cyclohexylcarbamate B

1H NMR (DMSO-d6, 400 MHz): δ 7.41-7.22 (m, 5H, CHaromatic), 7.19 (d, 1H, J = 7.9 Hz, NH), 5.54 (dd, 1H, J=7.1, J=4.8 Hz, CH-Ph), 4.95 (t, J=5.6, 1H, ), 3.59 (m, 2H, CH2-OH), 3.20 (m, 1H, CHcyclohexyl), 1.874-1.43 (m, 5H, CH2cyclohexyl), 1.37-0.96 (m, 5H, CH2cyclohexyl).

13C NMR (DMSO-d6, 100 MHz): δ 154.9, 139.5, 128.1, 127.5, 126.3, 75.9, 64.5, 49.4, 32.7, 25.1, 24.6.

3. General procedure for following the aminolysis of carbonates by GC/MS quantitative analysis

In a typical procedure, carbonate (1 equiv), amine (1 equiv) and diphenyl ether (0.4 equiv) internal standard) were stirred together for the appropriate amount of with the quantity of catalyst used in the table in an open air reaction tube maintained at the temperature shown in the table.

General procedure for GC/MS analysis

An aliquot of the reaction medium was dissolved in CH2Cl2 (1.5mL), then filtered on Na2SO4 and celite and analyzed by GC/MS.

GC column temperature program: 50 °C for 1 minutes followed by a ramp at 8 °C/min to 180°C followed by a ramp at 40 °C/min to 300°C (4.5 minutes)

The conversion of propylene carbonate was calculated using calibration curves of propylene carbonate with PhOPh as internal standard.

General procedure for GC/MS analysis of samples containing Lewis acid

The samples for the GC/MS analysis were prepared as follow: An aliquot of the reaction medium was quenched with a saturated NaHCO3 aqueous solution (0.1mL), extracted twice with CH2Cl2 (1.5mL), then filtered on Na2SO4, celite and analyzed by GC/MS.

GC column temperature program: 50 °C for 1 minutes followed by a ramp at 8 °C/min to 180°C followed by a ramp at 40 °C/min to 300°C (4.5 minutes)

The conversion of propylene carbonate was calculated using calibration curves of propylene carbonate with PhOPh as internal standard.

4. General procedure for following the aminolysis of carbonates by NMR 5. In a typical procedure, carbonate (1 equiv), amine (1 equiv) and diphenyl ether (0.4 equiv)

internal standard) were stirred together for the appropriate amount of with the quantity of catalyst used in the table in an open air reaction tube maintained at 25°C.

The samples for NMR analysis were prepared as follow. A known quantity (~45mg) of the reaction mixture was introduced in an NMR tube together with a known quantity of a solution of acetonitrile (~5.9 g.L-1) in DMSO-d6 (~ 0.7 g) and analyzed by NMR.

6. Examples and spectrum of quantitative analysis from the publication

Figure 1 Conversion of PC with butyl amine 1h

O

OO

+

1eq 1eq

HN O

OOH

HN O

OOH

A

B

T=25°C, 1h

PhOPh (internal standard)

NH2

In an open air reaction tube were stirred together during 1h at 25°C propylene carbonate (220 L, 2.6 mmol), butyl amine (256 L, 2.6 mmol), PhOPh (0.0371g, 0.22mmol).

Procedure for GC/MS analysis

The calculated conversion of propylene carbonate is 80%.

O

OOO

HN O

OOH

HN O

OOH

Table 1 MgBr2 catalyzed aminolysis of CP with cyclohexyl amine 1h

NH2

O

OO

+ MgBr2

1eq 1eq 5 mol%

+

HN O

OOH

HN O

OOH

A

B

T=25°C, 1h


In an open air reaction tube were stirred together during 1h at 25°C propylene carbonate (220 L, 2.6 mmol), cyclohexyl amine (300 L, 2.6 mmol), PhOPh (0.0310g, 0.18mmol) and MgBr2 (0.0239g, 0.13mmol).

Procedure for GC/MS analysis of samples containing Lewis acid


NH2

O

OO

O

HN O

OOH

HN O

OOH

Table 2 Cyclohexyl thiourea catalyzes aminolysis of CP with cyclohexyl amine 1h

NH2

O

OO

+ Thiourea

1eq 1eq 5 mol%

+

HN O

OOH

HN O

OOH

A

B

T=25°C, 1h

In an open air reaction tube were stirred together during 1h at 25°C propylene carbonate (220 L, 2.6 mmol), cyclohexyl amine (300 L, 2.6 mmol), cyclohexyl thiourea (0.0479g, 0.13mmol).

Procedure for NMR analysis

For the NMR analysis, 0.0448g of reaction media was introduced in an NMR tube as well as 0.7438g of a solution of acetonitrile (5.91 g.L-1) in DMSO-d6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

111.

59

100.

00

99.6

7

42.0

8

72.5

6

35.3

4

The calculated conversion of propylene carbonate is 66% and the ratio A:B is 45:55

O

OO

HN O

OOH

HN O

OOH

A

B

CH3CN

Figure 2 Reaction of CP with the cyclohexyl amine at 50°C using TBD as catalyst 1h.

NH2

O

OO

+ TBD

1eq 1eq 5 mol%

+

HN O

OOH

HN O

OOH

A

B

T=50°C, 1h


In an open air reaction tube were stirred together during 1h at 50°C propylene carbonate (220 L, 2.6 mmol), cyclohexyl amine (300 L, 2.6 mmol), PhOPh (0.0343g, 0.20mmol) and TBD (0.018g, 0.13mmol).



NH2

O

OO

O

HN O

OOH

HN O

OOH

Figure 4: Reaction of CP with different amines in the presence of TBD 1h

O

OO

+ TBD

1eq 1eq 5 mol%

+

HN O

OOH

HN O

OOH

A

B

T=25°C, 1h


NH2

In an open air reaction tube were stirred together during 1h at 25°C propylene carbonate (220 L, 2.6 mmol), cyclohexyl amine (322 L, 2.6 mmol), PhOPh (0.0326g, 0.19mmol) and TBD (0.018g, 0.13mmol).



NH2

O

OO

O

HN O

OOH

HN O

OOH

Figure 5: Cyclohexyl thiourea catalyzed aminolysis of 4-(methoxymethyl)-1,3-dioxolan-2-one with cyclohexyl amine 1h

NH2

O

OO

+ Thiourea

1eq 1eq 5 mol%

+

HN O

OOH

HN O

OOH

A

B

T=25°C, 1hO

O

O

In an open air reaction tube were stirred together during 1h at 25°C 4-(methoxymethyl)-1,3-dioxolan-2-one (0.3433g, 2.6 mmol), cyclohexyl amine (300 L, 2.6 mmol), cyclohexyl thiourea (0.0479g, 0.13mmol).



0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

100.

00

104.

14

23.9

2

23.3

8

13.2

7

21.5

1

The calculated conversion of 4-(methoxymethyl)-1,3-dioxolan-2-one is 68%

O

OO O

HN O

OOH

HN O

OOH

A

B

O

OCH3CN

Figure 5: Cyclohexyl thiourea catalyzed aminolysis of 4,6-dimethyl-1,3-dioxan-2-one with cyclohexyl amine 1h

NH2

+ Thiourea

1eq 1eq 5 mol%

+

HN O

OA/B

T=25°C, 1hO O

O

OH

In an open air reaction tube were stirred together during 1h at 25°4,6-dimethyl-1,3-dioxan-2-one (0.3381g, 2.6 mmol), cyclohexyl amine (300 L, 2.6 mmol), cyclohexyl thiourea (0.0479g, 0.13mmol).



0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

-200

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

100.

00

42.8

9

105.

36

The calculated conversion of 4,6-dimethyl-1,3-dioxan-2-one is 57%

HN O

O

OH

A/B

CH3CN

O O

O

Figure 5: TBD catalyzed aminolysis of 4-phenyl-1,3-dioxolan-2-one with cyclohexyl amine 1h

NH2

+ TBD

1eq 1eq 5 mol%

+

HN O

O

AT=25°C, 1h OH

O

OOPh H

N O

OOH

Ph

Ph

B

In an open air reaction tube were stirred together for 1h at 25°4-phenyl-1,3-dioxolan-2-one (0.2132g, 1.3 mmol), cyclohexyl amine (150 L, 1.3 mmol), TBD (9mg, 0.065mmol).

The samples for NMR analysis were prepared as follow. A precise quantity of a solution of acetonitrile (~2.7 g.L-1) in DMSO-d6 (~ 3 g) was introduced in the reaction tube and stirred affording a homogenous solution. Then a sample of this solution was analysed by NMR.

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)

-200

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

100.

00

83.9

8

64.9

4

100.

71

88.9

2

51.7

8

87.4

9

31.8

3

85.7

4

The calculated conversion of 4-phenyl-1,3-dioxolan-2-one is 63%

O

OOPh

HN O

O

AOH

HN O

OOH

Ph

Ph

B

CH3CN

7. NMR 1H evidencing the presence of impurities when TBD is used. Comparison with the thiourea.

Figure 2 Comparison of the reaction of CP with the cyclohexyl amine at 100°C and 25°C using TBD as catalyst 1h.

0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.2f1 (ppm)

-200

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

New signals corresponding to impurities have appeared.

1H NMR of the reaction media at 25°C


Figure 2 Comparison of the reaction of CP with the cyclohexyl amine at 100°C and 25°C using Thiourea as catalyst 1h.

0.00.51.01.52.02.53.03.54.04.55.05.56.0f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

Absence of new signals.



8. 1H and 13C NMR spectrum

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

5.00

4.96

0.86

0.96

2.82

0.77

1.16

1.18

1.22

1.25

1.28

1.30

1.33

1.36

1.37

1.55

1.59

1.68

1.69

1.70

1.71

1.91

1.93

3.34

4.11

7.69

8.14

8.24

9.81

HN

HN

S

F3C

CF3

0102030405060708090100110120130140150160170180190200f1 (ppm)

-5000

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

5000024.4

325

.09

31.6

0

52.2

9

115.

7711

9.21

121.

7112

1.92

124.

6312

7.34

129.

6012

9.93

130.

2513

0.64

142.

05

179.

19

HN

HN

S

F3C

CF3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000

7500

3.00

2.06

2.01

1.74

0.96

2.81

0.85

0.89

0.90

0.92

1.29

1.31

1.32

1.34

1.36

1.38

1.50

1.52

1.54

1.56

1.58

3.35

3.48

3.50

7.71

8.23

10.0

2HN

HN

S

F3C

CF3

102030405060708090100110120130140150160170180190200f1 (ppm)

-2000

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

18000

19000

20000

13.7

1

19.6

5

30.3

1

43.5

7

115.

8911

9.24

121.

7912

1.95

124.

6612

7.37

129.

6713

0.00

130.

3213

0.65

142.

03

180.

44

HN

HN

S

F3C

CF3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

55000

60000

3.00

2.05

1.00

1.01

0.96

3.31

3.49

3.50

3.52

3.53

3.57

3.58

3.60

3.61

4.25

4.27

4.50

4.52

4.54

4.89

4.90

4.90

4.91

4.91

4.92

4.92

4.92

4.93

4.93

4.93

4.94

4.94

4.95

OO

O

O

102030405060708090100110120130140150160170180190200f1 (ppm)

0

5000

10000

15000

20000

25000

30000

3500058.7

3

66.0

5

71.4

4

75.4

4

154.

99

OO

O

O

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

18000

19000

20000

6.00

0.48

1.09

0.46

0.89

1.05

1.26

1.28

1.32

1.33

1.47

1.50

1.51

1.53

1.53

1.56

1.92

1.93

1.94

2.11

2.12

2.12

2.15

2.15

2.16

3.32

4.57

4.58

4.59

4.59

4.60

4.61

4.61

4.62

4.63

4.64

4.65

4.65

4.68

4.70

4.71

4.73

4.74

4.76

O O

O

**

A/B

0102030405060708090100110120130140150160170180190200f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

20.3

720

.71

32.8

035

.41

72.6

475

.01

148.

6214

8.64

O O

O

**

A/B

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

1.00

1.00

0.97

4.95

3.34

4.40

4.42

4.42

4.44

4.86

4.88

4.90

4.90

5.84

5.86

5.88

7.43

7.45

7.45

7.45

7.46

7.46

7.47

O

OOPh

0102030405060708090100110120130140150160170180190200f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

18000

70.8

4

77.8

0

126.

7312

8.93

129.

39

136.

29

154.

75

O

OOPh

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

7.97

4.95

3.48

1.22

0.56

0.85

1.02

1.04

1.07

1.09

1.13

1.15

1.19

1.23

1.27

1.50

1.54

1.63

1.69

1.74

3.20

3.21

3.23

3.32

3.34

3.36

3.38

3.41

3.70

3.72

3.75

3.79

4.55

4.57

4.59

4.61

4.63

4.65

6.90

6.93

6.99

7.02

HN O

OOH

HN O

OOH

BA

102030405060708090100110120130140150160170180190200f1 (ppm)

-20

0

20

40

60

80

100

120

140

160

180

200

220

240

17.0

820

.12

24.8

125

.31

32.8

3

49.4

9

64.0

064

.48

68.8

770

.73

155.

3915

5.67

HN O

OOH

HN O

OOH

BA

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-200

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

5.00

4.79

0.96

1.19

1.62

0.54

1.06

0.92

0.80

0.53

0.80

1.02

1.05

1.08

1.11

1.14

1.17

1.21

1.24

1.27

1.51

1.55

1.64

1.67

1.72

1.74

3.22

3.24

3.32

3.32

3.33

3.34

3.43

3.45

3.46

3.47

3.49

3.92

3.93

4.51

4.53

4.55

4.56

4.62

4.63

4.65

4.72

4.73

6.95

6.97

7.00

7.02

HN O

OOH

HN O

OOH

BA

OH

OH

0102030405060708090100110120130140150160170180190200f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

1500025.1

125

.64

33.1

539

.57

39.7

839

.99

40.2

040

.41

49.8

5

60.6

063

.30

65.8

470

.28

75.5

9

155.

7615

6.02

HN O

OOH

HN O

OOH

BA

OH

OH

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

21.8

8

21.3

5

24.4

7

4.23

3.14

6.28

0.98

1.00

3.08

3.57

1.04

1.07

1.10

1.14

1.17

1.20

1.23

1.51

1.52

1.55

1.64

1.65

1.66

1.67

1.68

1.71

1.74

3.23

3.25

3.26

3.27

3.28

3.29

3.34

3.42

3.43

3.43

3.82

3.88

4.64

4.66

4.67

4.68

4.69

4.76

4.77

4.79

4.93

4.94

5.75

7.04

7.06

7.08

HN O

OOH

HN O

OOH

BA

O

O

102030405060708090100110120130140150160170180190200f1 (ppm)

-2000

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

24000

26000

28000

30000

32000

34000

24.6

825

.19

32.7

0

49.4

3

58.3

558

.46

60.1

165

.26

67.6

571

.18

72.7

773

.94

155.

0715

5.43

HN O

OOH

HN O

OOH

BA

O

O

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

11.6

8

7.37

1.01

1.00

1.00

0.99

0.86

1.02

1.04

1.07

1.09

1.09

1.12

1.14

1.20

1.23

1.50

1.51

1.64

1.64

1.66

1.67

1.70

1.73

3.20

3.21

3.22

3.34

3.61

3.61

3.62

3.62

3.63

3.63

3.64

3.64

3.65

4.41

4.42

4.73

4.75

4.76

4.77

4.78

6.91

6.93

HN O

OA

OH* *

0102030405060708090100110120130140150160170180190200f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

18000

1900021.1

624

.18

24.6

925

.20

32.7

5

45.8

2

49.3

0

62.6

5

67.3

9

155.

40

HN O

OA

OH* *

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

11.4

71.

071.

095.

11

1.00

1.00

1.00

1.00

0.85

1.04

1.06

1.09

1.09

1.12

1.14

1.17

1.17

1.20

1.23

1.38

1.63

1.65

1.67

1.68

1.68

1.70

1.73

3.18

3.20

3.21

3.22

3.25

3.33

3.60

3.62

3.63

3.65

3.67

4.42

4.43

4.72

4.74

4.76

4.77

4.79

4.80

6.88

6.90

HN O

OB

OH* *

102030405060708090100110120130140150160170180190200f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

18000

20.4

023

.80

24.6

925

.21

32.7

9

45.4

9

49.3

0

62.9

8

67.5

1

155.

13

HN O

OB

OH* *

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000

7500

5.04

4.96

0.96

1.96

0.98

0.99

0.86

5.00

1.04

1.07

1.08

1.09

1.11

1.14

1.17

1.20

1.23

1.26

1.51

1.55

1.64

1.67

1.71

1.74

3.22

3.23

3.24

3.35

3.96

3.98

4.71

4.72

4.74

4.75

5.48

5.49

7.06

7.08

7.24

7.25

7.25

7.26

7.27

7.27

7.28

7.31

7.33

7.33

7.34

7.35

7.36

7.36

7.38

7.38

HN O

OOH

A

0102030405060708090100110120130140150160170180190200f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

24.7

125

.19

32.6

8

49.4

6

68.6

170

.86

126.

3212

7.24

128.

06

142.

55

155.

39

HN O

OOH

A

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

11.0

0

0.89

2.00

1.00

0.99

5.98

1.04

1.07

1.10

1.13

1.15

1.16

1.18

1.20

1.23

1.51

1.54

1.62

1.65

1.67

1.74

1.77

3.19

3.20

3.21

3.34

3.52

3.54

3.55

3.57

3.58

3.59

3.60

3.61

3.62

3.62

3.64

4.94

4.95

4.97

5.52

5.53

5.54

5.55

7.18

7.20

7.25

7.25

7.26

7.26

7.27

7.28

7.29

7.29

7.31

7.32

7.33

7.34

7.34

7.36

7.36H

N O

OOH

B

102030405060708090100110120130140150160170180190200f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

18000

19000

20000

21000

24.6

425

.18

32.7

0

49.4

6

64.5

8

75.9

4

126.

3912

7.50

128.

17

139.

51

154.

96HN O

OOH

B

(1) Pratt, R. C.; Lohmeijer, B. G. G.; Long, D. A.; Lundberg, P. N. P.; Dove, A. P.; Li, H.; Wade, C. G.; Waymouth, R. M.; Hedrick, J. L. Macromolecules 2006, 39, 7863–7871.

(2) Nogawa, M.; Sugawara, S.; Iizuka, R.; Shimojo, M.; Ohta, H.; Hatanaka, M.; Matsumoto, K. Tetrahedron 2006, 62, 12071–12083.

(3) Besse, V.; Foyer, G.; Auvergne, R.; Caillol, S.; Boutevin, B. J. Polym. Sci. Part A Polym. Chem. 2013, 3284–3296.

(4) Jeoshua, K.; Israel, R.; Shalom, S. J. Chem. Soc. Perkin Trans. 2 1972, 2019–2025.

(5) Reithofer, M. R.; Sum, Y. N.; Zhang, Y. Green Chem. 2013, 15, 2086–2090.

(6) Huang, J.; Shi, M. J. Org. Chem. 2003, 68, 6705–6709.

Electronic Supplementary Information for by amines Rational … · 2014-07-16 · Electronic...

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