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SUPPORTING INFORMATION

A Copper-mediated reverse aromatic Finkelstein reaction in ionic liquid

Anh T. H. Nguyen, Dat P. Nguyen, Ngan T. K. Phan, Dung T. T. Lam, Nam T. S. Phan,

Thanh Truong*

Department of Chemical Engineering, Ho Chi Minh University of Technology, VNU-HCM,

268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Vietnam

*Email: [email protected]

*To whom correspondence should be addressed: [email protected]

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mailto:[email protected]

mailto:[email protected]

Table of Contents

Section S1 Materials and Instrumentation S3

Section S2 Synthesis and Characterization of Ionic Liquids S4

Section S3 Calibration curve preparation S7

Section S4 Catalysis S9

Section S5 References S14

S2

Section S1. Materials and Instrumentation:

Reactions were performed in 2-dram vials using screw caps with 17 mm hole and white

silicone septum with white Teflon face (from SUPELCO). Column chromatography was

performed on 60Å silica gel (Sigma Aldrich). Gas chromatographic (GC) analyses were

performed using a Shimadzu GC 2010-Plus equipped with a flame ionization detector (FID)

and an SPB-5 column (length = 30 m, inner diameter = 0.25 mm, and film thickness = 0.25

µm). The temperature program for GC analysis heated samples from 100 °C for 1.0 minutes;

heated from 100 to 280 °C at 40 °C/min; held at 280 °C for 3 min. Inlet and detector

temperature were set constant at 280 °C. Diphenyl ether was used as internal standard to

calculate the GC yield of reaction. GC-MS analyses were performed on a Shimadzu GCMS-

QP2000 Plus chromatograph equipped with a Restek column (Rtx-XLB, 30 m × 0.25 mm

I.D.). The 1H and 13C NMR were recorded on a Brucker AV 500 MHz using residual solvent

peak as a reference. All procedures were performed under air atmosphere unless otherwise

noted.

All reagents and starting materials were obtained commercially from Merck, Sigma-Aldrich,

and Acros Organics and were used as received without any further purification unless

otherwise noted.

Table S1. ReagentsChemicals Origin Specification

1-methylimidazole Merck 99%

1-Bromobutane Merck 98%

1-Bromohexane Merck 98%

1-Bromooctane Merck 98%

Ethyl acetate Baker 99%

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Diethyl ether Baker 99%

Hexafluorophosphoric acid Acros Organics 60%

Tetrafluorophosphoric acid Acros Organics 48%

1-methylimidazole Merck 99%

p-xylene Merck 99%

4-bromoanisole Merck 98%

Methanol China 99.5%

Dichloromethane Merck 99.8%

Toluene Merck 99.9%

1-bromo-4-nitrobezene Sigma 99%

1-bromo-3-nitrobenzene Sigma 99%

1-bromo-2-nitrobenzene Sigma 99%

4-bromoanisole Acros Organics 98%

Dimethylformamide (DMF) Merck 99,8%

DMSO Merck 99.5%

DMA Merck 99.5%

NMP Merck 99.5%

Diglymer Merck 99.5%

4-iodoacetonphenone Sigma 99%



CuBr Sigma 99.9%

Iodo benzene Sigma 99%

1-iodo-4-nitrobenzene Sigma 98%

2-iodotoluene Sigma 98%

4-iodotoluene Sigma 99%

Diphenyl ether Sigma 98%

Na2SO4 Acros Organics 99%

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1,4-diiodobenzene Acros Organics 99%

1-iodonaphthalene Sigma 98%

1-bromo-4-fluorobenzene Sigma 99%

4-iodopyridine Sigma 99%

3-iodoindole Acros Organics 99%

All reactions or entries were run at least two times to minimize errors and the reported

numbers were the average values.

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Section S2. Synthesis of Ionic Liquids

1–Butyl–3–methylimidazolium bromide ([BMIM]Br

1H NMR (500 MHz, DMSO): δ = 0.887 (t, 3H; CH3), 1.249 – 1.257 (m, 2H; CH2CH3), 1.765

– 1.779 (m, 2H; CH2CH2CH3), 3.882 (s, 3H; N-CH3), 4.198 – 4.228 (m, 2H; N-CH2), 7.778

(t, 1H; N-CH=C), 7.856 (t, 1H; N-CH=C), 9.340 (s, 1H, N-CH=N).

1–Hexyl–3–methylimidazolium bromide ([HMIM]Br: 1-methylimidazole (20.5 g, 0.25 mol)

was mixed with 1-bromohexane (45.9 g, 0.28 mol) in a 250 mL round bottom flask equipped

with a flux condenser. The mixture was then irradiated in a microwave oven (Sanyo – EM

S2086W – 800W) at 80W, and stirred vigorously during the reaction time by the magnetic

stirrer. The irradiation was paused every 10 seconds to prevent overheating. The irradiation

was repeated for a total time of 6 minutes. After completion, the resulting mixture was

cooled down to room temperature, washed with ethyl acetate (100 mL × 3), and with diethyl

ether (100 mL × 3) to remove starting materials and undesired products. The residue of

volatile solvents was removed by a vacuum rotary evaporation at 50 oC to deliver 56.8 g of

product (93 % yield).

1H NMR (500 MHz, DMSO): δ = 0.848 (t, 3H, CH3); 1.248 – 1.280 (m, 6H, CH2CH2CH2);

1.769 – 1.790 (m, 2H, CH2); 3.863 (s, 3H, N–CH3); 4.171 (t, 2H,N–CH2); 7.730 – 7.740 (m,

1H, N–CH=C); 7.801 – 7.810 (m, 1H, N–CH=C); 9.240 (s, 1H, N–CH=N)

1–Octyl–3–methylimidazolium bromide ([OMIM]Br: 1-methylimidazole (20.5 g, 0.25 mol)

was mixed with 1-bromooctane (53.8 g, 0.28 mol) in a 250 mL round bottom flask equipped

with a flux condenser. The mixture was then irradiated in a microwave oven (Sanyo – EM

S2086W – 800W) at 80W, and stirred vigorously during the reaction time by the magnetic

stirrer. The irradiation was paused every 10 s to prevent overheating. The irradiation was

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repeated for a total time of 9 min. After completion, the resulting mixture was cooled down

to room temperature, washed with ethyl acetate (100 mL × 3), and with diethyl ether (100

mL × 3) to remove starting materials and undesired products. The residue of volatile solvents

was removed by a vacuum rotary evaporation at 50 oC to deliver 62.8 g of product (83 %

yield).

1H NMR (500 MHz, DMSO): δ = 0.840 (t, 3H, CH3); 1.211 – 1.250 (m, 10H,

CH2CH2CH2CH2CH2); 1.699 – 1.778 (m, 2H, CH2); 3.870 (s, 3H, N–CH3); 4.178 (t, 2H,N–

CH2); 7.740 – 4.780 (m, 1H, N–CH=C); 7.801 – 7.840 (m, 1H, N–CH=C); 9.295 (s, 1H, N–

CH=N)

In a typical procedure for preparation of 1–butyl–3–methylimidazolium

hexafluorophosphate: hexafluorophosphoric acid (40 mL, 0.288 mol) of was added to a

plastic conical flask containing 50 mL of cold distilled water. This mixture was stirred and

immersed in an ice bath (mixture I). The mixture of 1–butyl–3–methylimidazolium bromide

(50 g, 0.228 mol) with 50 mL of cold distilled water was also stirred and immersed in

another ice bath (mixture II). Next, the mixture I was added dropwise to mixture II in 10

minutes. The resulting mixture was continuously stirred in ice bath for 24 h. After

completion, the upper acidic aqueous layer was almost separated by decanting and the

bottom layer was washed by cold water until the almost excess acid was removed. The

acidity was tested by pH paper. The excess water was removed by a vacuum rotary

evaporation at 70 oC to delivery 53.3 g of product (83 % yield).

1H NMR (500 MHz, DMSO): δ = 0.905 (t, 3H, CH3); 1.262 (m, 2H, CH2CH3); 1.771 (m, 2H,

CH2CH2CH3); 3.846 (s, 3H, N–CH3); 4.157 (t, 2H, N-CH2); 7.668 (m, 1H, N–CH=C); 7.733

(m, 1H, N-CH=C); 9.071 (s, 1H, N-CH=N).

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Similar procedure was applied for the synthesis of 1–butyl–3–methylimidazolium

tetrafluoroborate ([BMIM]BF4) with 61 % yield.

Section S3. Calibration curve preparation

4’-Chloroacetophenone (16.3 mg) and diphenyl ether (14.8 mg) were weighted into two

distinct 50 mL volumetric flasks. Next, ethyl acetate was added into the flasks until the

volume reached 50 mL to dilute these substances. Portions of the two solutions were

withdrawn and added into five 8 mL vials as showed in Table S2.

Table S2. Calibration curve preparation for 4’-chloroacetophenone

Vial Volume (mL)4’-Chloroacetophenone Diphenyl ether

1 3 12 2 13 1 14 1 25 1 3

The vials was analyzed by GC and give the calibration curve (Figure 2).

Table S3. Calibration curve calculation for 4’-chloroacetophenone

Vial Formula1 Result (y axis) SPr/SIS (x axis)2

13 × mPr

m IS3.3041 2.5661

22 × mPr

m IS2.2027 1.5720

3m Pr

m IS1.1014 0.7540

4m Pr

2 × mIS0.5507 0.3367

5m Pr

3 × mIS0.3671 0.2254

1 mPr: Mass of 4’-chloroacetophenone (16.3 mg)mIS: Mass of diphenyl ether (14.8 mg)

2 Ratio between peak area of 4’-chloroacetophenone and peak area of diphenyl ether,

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Figure S1. Calibration curve for 4’-chloroacetophenone

From the calibration curve, GC yield of 4’-chloroacetophenone can be calculated by formula

(1):

GC yield (%) = mPr × 100%mPr '

= (SPr

SIS × 1.25815 + 0.13275) × mIS × 100%

mPr '

Where: mPr (mg): Mass of 4’-chloroacetophenone obtained

mPr’ (mg): Calculated mass of 4’-chloroacetophenone when yield = 100%

SPr: Peak area of 4’-chloroacetophenone in sample

SIS: Peak area of diphenyl ether in sample

(1)

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mIS (mg): Mass of diphenyl ether in sample

Section S4 Catalysis

Reaction kinetic

0 2 4 6 8 10 12 14 16 18 20 22 240.0

10.020.030.040.050.060.070.080.090.0

100.0

Reaction time (h)

GC

YIE

L (%

)

Fig. S2. Reaction kinetic

Effect of CuBr amount

1:0.5 1:0.85 1:1.2 1:1.4 1:1.60.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

4-iodoacetophenone/CuBr ratio

GC Y

IELD

(%)

Fig. S3. Effect of CuBr amount

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Recycling studies

MS of re-used [BMIM]Br: m/z = 357.07.

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Fig. S4. MS of reused [BMIM]Br

4-Bromoacetophenone

This compound is known.[1] Column chromatography using hexane: ethyl acetate = 9:1.

Product was achieved with 176.1 mg (89 % of yield).

1H NMR (500 MHz, CDCl3) δ, 2.585 (s, 3H), 7.6 (d, 2H, J = 9.0 Hz), 7.8 (d, 2H, J = 9.0 Hz).

MS: m/z = 200 [p-Br-C6H4-COCH3]+

1-Bromo-4-nitrobenzene

This compound is known [1]. Column chromatography using hexane: ethyl acetate = 4:1.


1H NMR (500 MHz, CDCl3) δ 7.68 (2H, d, J=8.6 Hz), 8.08 (2H, d, J=8.6 Hz).

MS: m/z = 203.

Methyl-4-bromobenzoate



1H NMR (500 MHz, CDCl3) δ 3.84 (s, 3H), 7.51 (d, J = 8.7 Hz, 2H), 7.83(d, J = 8.7 Hz, 2H)

MS: m/z = 216.

4-Bromoanisole

This compound is known [2]. Column chromatography using hexane: diethyl ether = 15:1.


1H NMR (500 MHz, CDCl3) δ 3.77 (s, 3H), 7.33 (d, J = 8.1 Hz, 2H), 6.79 (d, J = 8.1 Hz, 2H);

MS: m/z = 187.

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4-Bromotoluene

This compound is known. Column chromatography using hexane. Product was achieved

with 107.9 mg (64 % of yield). GC and GC-MS are identical with authentic compound.

3-Bromoacetophenone



1H NMR (500 MHz, CDCl3) δ: 2.62 (s, 3H), 7.36 (t, J = 7.8 Hz, 1 H), 7.66 – 7.70 (m, 1H),

7.84 – 7.89 (m, 1H), 8.09 (s, 1H).

MS: /z = 200 [m-Br-C6H4-COCH3]+

2-Bromobenzonitrile



1H NMR (500 MHz, CDCl3) δ: 7.50-7.41 (m, 2H), 7.69 (m, 2H).

MS: m/z = 183.

3-Bromoanisole



1H NMR (500 MHz, CDCl3) δ 3.80 (s, 3H), 6.80 - 6.85 (m, 1H), 7.05- 7.08 (m, 1H), 7.10 -

7.21 (m, 2H).

MS: m/z = 188.

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4-Chloroacetophenone



1H NMR (500 MHz, CDCl3) δ 2.586 (s, 3H), 7.4 (d, J = 9.0 Hz, 2H), 7.9 (d, J = 9.0 Hz,

2H).

MS: m/z = 154 [p-Cl-C6H4-COCH3]+

1-Chloronaphthalene



1H NMR (500 MHz, CDCl3) δ 7.30 (t, J = 7.8 Hz, 1H), 7.44 – 7.47 (m, 1H), 7.50 -7.56 (m,

2H), 7.69 (d, J = 7.8 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 8.0 Hz, 1H).

MS: m/z = 162.

1,4-dibromobenzene



1H NMR (500 MHz, CDCl3) δ 7.29 (s, 4H).

MS: m/z = 236.

1-bromo-4-iodobenzene



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1H NMR (500 MHz, CDCl3) δ 7.25 (d, J=8.2 Hz, 2H), 7.55 (d, J=8.2 Hz, 2H).

MS: m/z = 284.

1-Chloro-4-fluorobenzene

This compound is known. Column chromatography using pentane. Product was achieved

with 54.5 mg (42 % of yield). The identity of the product was confirmed by GC and GC-MS

analysis as compared to those of authentic sample.

1-Bromo-4-chlorobenzene

This compound is known.[4] Column chromatography using hexane. Product was achieved

with 112.0 mg (59 % of yield).

1H NMR (500 MHz, CDCl3) δ 7.08 (d, J=8.7 Hz, 2H), 7.25 (d, J=8.7 Hz, 2H).

MS: m/z = 192.

1-Bromo-2-phenylethylene



1H NMR (500 MHz, CDCl3) δ 6.74 (d, J = 13.8 Hz, 1H), 7.15 (d, J = 13.8 Hz, 1H), 7.28 -

7.35 (m, 5H).

MS: m/z = 184.

4-Chloropyridine



1H NMR (500 MHz, DMSO-d6) δ 7.43 – 7.47 (m, 2H), 8.52 – 8.55 (m, 2H).

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MS: m/z = 113.

3-Bromoindole



1H NMR (500 MHz, CDCl3) δ 7.18 (s, 1H), 7.20 – 7.24 (m, 2H), 7.29 – 7.34 (m, 1H), 7.60 –

7.63 (m, 1H), 8.10 (s, 1H).

MS: m/z = 197.

Section S5. References

[1] Arvela RK, Leadbeater NE. Fast and easy halide exchange in aryl halides. Synlett 2003; 8:1145–1148.[2] Cant AA, Bhalla R, Pimlott SL, Sutherland A. Nickel-catalysed aromatic Finkelstein reaction of aryl and heteroaryl bromides. Chem Commun 2012; 48:3993–3995.[3] Klapars A, Buchwald SL. Copper-catalyzed halogen exchange in aryl halides: an aromatic finkelstein reaction. J Am Chem Soc 2002;124:14844–14845.[4] Jin X, Davies RP. Copper-catalysed aromatic-Finkelstein reactions with amine-based ligand systems. Catal Sci Technol 2017;7:2110–2117.[5] Li L, Liu W, Zeng H, Mu X, Cosa G, Mi Z, Li CJ, Photo-induced metal-catalyst-free aromatic finkelstein reaction. J Am Chem Soc, 2015;137:8328–8331.[6] Chen M, Ichikawa S, Buchwald SL. Rapid and efficient copper-catalyzed finkelstein reaction of (hetero)aromatics under continuous-flow conditions . Angew Chem Int Ed 2015;54:263 – 266.

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1H-NMR OF [BMIM]Br

S17

13C-NMR OF [BMIM]Br

S18

1H-NMR OF [HMIM]Br

S19

13C-NMR OF [HMIM]Br

S20

1H-NMR OF [OMIM]Br

S21

13C-NMR of [OMIM]Br

S22

1H-NMR OF [BMIM]PF6

S23

13C-NMR OF [BMIM]PF6

4-Bromoacetophenone

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1-bromo-4-iodobenzene

S25


3-Bromoanisole

S26

4-Bromoanisole

4-Bromotoluene

S27

4-Chloroacetophenone

4-Chloroanisole

S28

1-Chloronapthalene

Methyl-4-bromobenzoate

S29

1-Bromo-4-nitrobenzene

Mass spectrometry

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4-Bromoanisole

4-Bromotoluene

S31

3-Bromoanisole

4-Chloroacetopheneone

S32

4-Chloroanisole


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1-Bromo-4-iodobenzene

4-Bromoacetophenone

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manganese-catalyzed oxidative c-c coupling reaction by ... · web viewdepartment of chemical...

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