Supporting Information] Copper-Catalyzed Aerobic Alcohol … · 2013. 8. 13. · S1 [Supporting Information]Copper-Catalyzed Aerobic Alcohol Oxidation under Air in Neat Water by Using

S1

[Supporting Information]

Copper-Catalyzed Aerobic Alcohol Oxidation under Air in Neat

Water by Using a Water-Soluble Ligand

Guofu Zhang,*† Xingwang Han,† Yuxin Luan,† Yong Wang,† Xin Wen,† Chengrong Ding,† Li

Xu,*‡ Jianrong Gao†

†College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, ‡Department of Chemistry, Zhejiang University, Hangzhou 310027, People’s Republic of China. Fax: (+86)-571-8832-0147; Tel: (+86)-571-8832-0147; E-mail: *[email protected]; [email protected]

Table of Contents ------------------------------------------------------------------------------------------------------------------

General Expermental ......................................................................page S2

Experimental Sections................................................................page S3-S8

a) General Procedures for Synthesis of Pytl-β-CD

b) General Experimental Procedure for the Copper-Catalyzed Aerobic Alcohol Oxidation in Neat Water under Air

c) General Experimental Procedure for the Reuse of Cu/pytl-β-CD in the p-Tolylmethanol Oxidation

NMR Characterization Data and Figures of Products……......page S9-S31

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

S2

General Experimental

All reagents were purchased from commercial suppliers and used without purification

unless otherwise stated. All alcohols were purchased from Aladdin reagent Co., LTD

(Shanghai). β-Cyclodextrin, 2-ethynylpyridine, copper salts were purchased from

Sigma-Adrich Company. Column chromatography was performed with silica gel

(300-400 mesh) produced by Qingdao Marine Chemical Factory, Qingdao (China).

GC-MS analysis of determination of conversion was performed on the instrument of

Agilent 7890 GC-QQQ. NMR spectra were recorded on Bruker AVANCE III

500MHz instrument with TMS as internal standard. The FT-IR spectra were recorded

from KBr pellets in the range of 4000-400 cm-1 on Nicolet 6700.


S3

Experimental Sections.

a) General Experimental Procedures for Synthesis of Pytl-β-CD

(1) Synthesis of 6-O-Monotosyl-β-CD (I). β-Cyclodextrin (35.0 mmol) and NaOH

(500.0 mmol) were dissolved in water (800.0 mL) in a 2.0 L three-neck round-bottom

flask equipped with a magnetic stirrer. The temperature was maintained around

0-5 °C. p-Toluenesulfonyl chloride (TsCl, 140.0 mmol) was added, and the suspen-

sion was stirred vigorously for 4 h. Then the unreacted TsCl was removed by filtra-

tion. After that, the pH of filtrate was adjusted to neutral by the addition of hydro-

chloric acid, the product began to precipitate. Subsequently, the mixture was filtered,

washed with water, dried in vacuum and recrystallized by water. The final pure

6-O-monotosyl-β-CD was dried overnight in vacuum at 60 °C. Yield: 10.9644 g

(White solid, 24.3%). 1H NMR (500 MHz, DMSO-d6): δ (ppm) 7.77-7.72 (m, 2H),

7.45-7.40 (m, 2H), 5.73 (s, 14H), 4.85-4.77 (m, 7H), 4.50-4.32 (m, 6H), 3.67-3.53 (m,

28H), 3.51-3.29 (m, overlaps with HDO), 2.43 (s, 3H).

Figure S1. 1HNMR spectrum of 6-O-Monotosyl-β-CD.


S4

(2) Synthesis of 6-Monodeoxy-6-Monoazido-β-CD (II). 6-O-monotosyl-β-CD (5.0

mmol) and sodium azide (10.0 mmol) were dissolved in anhydrous DMF (30.0 mL).

The mixture was stirred at 75 °C for 4 h, after which H2O (20.0 mL) and acetone

(400.0 mL) were added orderly. Then, the product began to precipitate. After that, the

product was filtrated and washed with acetone twice (2×400.0 mL). The

6-monodeoxy-6-monoazido- β-CD was obtained as white solid powder after dried in

vacuum at 60 °C overnight. Yield: 5.4288 g (white powder, 93.6%). According to

FT-IR spectra, the absorption band at 2105.5 cm-1 clearly indicates the successful at-

tachment of azido group onto the β-cyclodextrin. 1H NMR (500 MHz, DMSO-d6): δ

(ppm) 5.81-5.63 (m, 14H), 4.88-4.83 (m, 7H), 4.56-4.45 (m, 6H), 3.77-3.56 (m, 28H),

3.40-3.29 (m, overlaps with HDO).

Figure S2. 1H NMR spectrum of 6-monodeoxy-6-monoazido-β-CD.


S5

FXCSMon Nov 19 16:08:00 2012 (GMT+08:00)E:\dingchengrong\121119\11.18 N3-CD-ok.SPA

443.

653

0.3

580.

8664

.270

6.77

56.486

2.8

945.

810

30.91

079.

31155

.6

1414

.3

1659

.8

2105

.5

2928

.1

-10

0

10

20

30

40

50

60

70

80

90%

T

1000 2000 3000 4000 Wavenumbers (cm-1)

Figure S3. FT-IR spectrum of 6-monodeoxy-6-monoazido-β-CD

(3) Synthesis of Pytl-β-CD. Under nitrogen atmosphere,

6-monodeoxy-6-monoazido-β-CD (3.0 mmol), 2-ethynylpyridine (3.6 mmol), sodium

ascorbate (0.6 mmol) and CuSO4 (0.3 mmol) were added into a 100 mL Schlenk tube

and dissolved in deaerated DMSO/H2O (v/v, 1/1, 40.0 mL). The resulting mixture

was stirred at room temperature for 24 h. After the reaction, water (20.0 mL) was

added. The obtained solution was poured into acetone (400.0 mL) and the desired tri-

azole functionalized β-CD (pytl-β-CD) began to precipitate. After the mixture had

been filtrated, washed with acetone (until the copper content was beyond the detection

limit of ICP-MS), dried under vacuum, pytl-β-CD was obtained as white solid powder.

Yield: 3.4880 g (white powder, 92.1%). From the FT-IR, the absorption band at

2105.5 cm-1 disappeared and showed a new band at 1604.8 cm-1, which was assigned

to the C=C vibration of the triazole ring and implied the completion of click pro-

cess. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 8.59 (d, 1H), 8.56 (s, 1H), 8.03 (d,

1H), 7.90 (t, 1H), 7.35 (t, 1H), 5.90-5.61 (m, 14H), 4.93-4.71 (m, 7H), 4.54-4.41 (m,

6H), 3.94-3.57 (m, 28H), 3.46-3.26 (m, overlaps with HDO); ESI-MS: 1263.4 (The

major ion was assigned to the [pytl-β-CD +H]+ species).

“ N3 “


S6

FXCSTue Sep 18 14:38:43 2012 (GMT+08:00)E:\dingchengrong\120918\cat-SZ-ok.SPA

530.

358

3.070

8.4755.

1872.

394

6.4

1033

.310

80.3

1155

.9

1365

.414

22.6

1636

.6

2926

.6

30

40

50

60

70

80

90

100

%T

1000 2000 3000 4000 Wavenumbers (cm-1)

Figure S4. FT-IR spectrum of ptyl-β-CD.


S7

44x10x10

00

0.0.2

0.0.4

0.0.6

0.0.8

11

1.1.2

1.1.4

1.1.6

1.1.8

22

2.2.2

1263.41263.4

250.0250.0

330.3330.3

696.2696.2

Figure S5. ESI-MS spectrum of ptyl-β-CD.

Figure S6. Partial 1H NMR spectrum of ptyl-β-CD.

b) General Experimental Procedure for the Copper-Catalyzed Aero-bic Alcohol Oxidation in Neat Water under Air.

A mixture of alcohol (1.0 mmol), Cu(OAc)2·H2O (0.05 mmol), pytl-β-CD (0.05

mmol), TEMPO (0.05 mmol), Na2CO3 (1.0 mmol), H2O (4.0 mL) was added to a 100

mL tube, which was vigorously stirred in air under reflux for 10-24 h. After the reac-

tion, the product was extracted with CH2Cl2 (3×2.0 mL). The combined organic

phase was washed by water (3.0 mL) and dried by anhydrous MgSO4. After concen-

tration in vacuum, the residue was purified by column chromatography to afford the

desired aldehyde. The pure product was subjected to 1H NMR and 13C NMR analy-

sis.

c) General Experimental Procedure for the Reuse of Cu/pytl-β-CD in the p-Tolylmethanol Oxidation

A mixture of p-tolylmethanol (1.0 mmol), Cu(OAc)2·H2O (0.05 mmol), pytl-β-CD

(0.05 mmol), TEMPO (0.05 mmol), Na2CO3 (1.0 mmol), H2O (4.0 mL) was added to

a 100 mL tube, which was vigorously stirred in air under reflux. After the reaction, the

[ptyl-β-CD+H]+


S8

product was extracted with CH2Cl2 (3×2.0 mL). The combined organic phase was

washed by water (3.0 mL) and dried by anhydrous MgSO4. After concentration in

vacuum, the residue was purified by column chromatography to afford aldehyde. The

pure product was subjected to 1H NMR and 13C NMR analysis. The next run was

performed by adding fresh alcohol (1.0 mmol) and TEMPO (0.05 mmol) to the aque-

ous media.


S9

NMR Characterization Data and Figures of Products

O

Benzaldehyde (Table 2, entry 1) 1H NMR (500 MHz, CDCl3): δ

7.53(t, J = 7.8 Hz, 2H), 7.61-7.65(m, 1H), 7.87-7.90(m, 2H), 10.02(s, 1H). 13C NMR

(125 MHz, CDCl3): δ 128.9, 129.7, 134.4, 136.4, 192.3.

H3C

O

4-Methylbenzaldehyde (Table 2, entry 2) 1H NMR (500 MHz,

CDCl3): δ 2.44(s, 3H), 7.34(d, J = 8.0 Hz, 2H), 7.78(d, J = 8.0 Hz, 2H), 9.97(s,

1H). 13C NMR (125 MHz, CDCl3): δ 21.8, 129.7, 129.8, 134.2, 145.5, 191.9.

MeO

O

4-Methoxybenzaldehyde (Table 2, entry 3) 1H NMR (500 MHz, CDCl3): δ 3.90(s, 3H), 7.00-7.03(m, 2H), 7.83-7.87(m, 2H), 9.89(s, 1H). 13C

NMR (125 MHz, CDCl3): δ 55.5, 114.3, 129.9, 131.9, 164.6, 190.8.

O

1-Naphthaldehyde (Table 2, entry 4) 1H NMR (500 MHz, CDCl3): δ

7.57(t, J = 7.5 Hz, 2H), 7.66-7.70(m, 1H), 7.89(d, J = 8.0 Hz, 1H), 7.93(dd, J1= 8.0,

1.5 Hz, 1H), 9.26(d, J = 9.0 Hz, 1H), 10.37(s, 1H). 13C NMR (125 MHz, CDCl3): δ

124.7, 126.8, 128.3, 128.9, 130.3, 131.2, 133.5, 135.1, 136.4, 193.3.

H3CCH3

O

3,4-Dimethylbenzaldehyde (Table 2, entry 5) 1H NMR (500

MHz, CDCl3): δ 2.30(d, J = 4.0 Hz, 6H), 7.25(d, J = 8.0 Hz, 1H), 7.58(t, J = 14.0 Hz,

2H), 9.89(s, 1H). 13C NMR (125 MHz, CDCl3): δ 19.4, 20.0, 127.5, 130.0, 130.4,

134.4, 137.3, 144.1, 192.0.

H3COOCH3

O

3,4-Dimethoxybenzaldehyde (Table 2, entry 6) 1H NMR (500


S10

MHz, CDCl3): δ 3.94(d, J = 13.5 Hz, 6H), 6.97(d, J = 8.0 Hz, 1H), 7.39(d, J = 2.0 Hz,

2H), 7.43-7.45(q, 1H), 9.84(s, 1H). 13C NMR (125 MHz, CDCl3): δ 55.9, 56.1, 108.9,

113.4, 126.8, 130.1, 149.6, 154.4, 190.8.

OMe

O

2-Methoxybenzaldehyde (Table 2, entry 7) 1H NMR (500 MHz, CDCl3): δ 3.95(s, 3H), 7.00-7.07(m, 2H), 7.55-7.60(m, 1H), 7.84-7.86(q, 1H), 10.49(s,

1H). 13C NMR (125 MHz, CDCl3): δ 55.5, 111.6, 120.6, 125.0, 128.5, 135.9, 161.8,

189.8.

Cl

O

2-Clorobenzaldehyde (Table 2, entry 8) 1H NMR (500 MHz, CDCl3): δ 7.34(t, J = 7.5 Hz, 1H), 7.39-7.42(q, 1H), 7.47-7.51(m, 1H), 7.86-7.88(q, 1H),

10.43(s, 1H). 13C NMR (125 MHz, CDCl3): δ 127.1, 129.2, 130.4, 132.3, 135.0,

137.7, 189.5.

Cl

O

3-Clorobenzaldehyde (Table 2, entry 9) 1H NMR (500 MHz, CDCl3): δ 7.47(t, J = 7.8 Hz, 1H), 7.57-7.60(m, 1H), 7.74-7.77(m, 1H), 7.84(t, J = 1.7 Hz, 1H),

9.96(s, 1H). 13C NMR (125 MHz, CDCl3): δ 127.9, 129.2, 130.3, 134.3, 135.4, 137.8,

190.7.

Cl

O

4-Clorobenzaldehyde (Table 2, entry 10) 1H NMR (500 MHz, CDCl3): δ 7.49-7.53(dt, J = 9.5, 7.5 Hz, 2H), 7.81-7.84(m, J = 13.0 Hz, 2H), 9.96(s,

1H). 13C NMR (125 MHz, CDCl3): δ 129.4, 130.8, 134.7, 140.9, 190.8.

Br

O

4-Bromobenzaldehyde (Table 2, entry 11) 1H NMR (500 MHz, CDCl3): δ 7.69-7.72(q, 2H), 7.75-7.78(m, 2H), 9.99(s, 1H). 13C NMR (125 MHz,

CDCl3): δ 129.9, 131.0, 132.4, 135.0, 191.0.

O2N

O

4-Nitrobenzaldehyde (Table 2, entry 12) 1H NMR (500 MHz,


S11

CDCl3): δ 8.09(dd, J = 7.0, 2.0 Hz, 2H), 8.41(d, J = 8.5 Hz, 2H), 10.17(s, 1H). 13C

NMR (125 MHz, CDCl3): δ 124.3, 130.4, 140.0, 151.1, 190.2.

F

O

4-Fluorobenzaldehyde (Table 2, entry 13) 1H NMR (500 MHz, CDCl3): δ 7.16-7.20(m, 2H), 7.87-7.90(m, 2H), 9.94(s, 1H). 13C NMR (125 MHz,

CDCl3): δ 116.3, 132.4, 133.0, 164.8, 191.6.

Cl Cl

O

2,4-Diclorobenzaldehyde (Table 2, entry 14) 1H NMR (500 MHz, CDCl3): δ 7.37(q, J = 10.0 Hz, 1H), 7.47(d, J = 2.0 Hz, 1H), 7.86(d, J = 8.5 Hz,

1H), 10.40(s, 1H). 13C NMR (125 MHz, CDCl3): δ 127.9, 130.3, 130.4, 130.9, 138.5,

141.0, 188.4.

N

O

3-Nicotinaldehyde (Table 2, entry 15) 1H NMR (500 MHz, CDCl3): δ 7.46-7.50(q, 1H), 8.15-8.18(m, 1H), 8.82-8.84(q, 1H), 9.07(d, J = 2.0 Hz, 1H),

10.10(s, 1H). 13C NMR (125 MHz, CDCl3): δ 124.0, 131.4, 135.7, 151.9, 154.6,

190.6.

SO 2-Thiopheneformaldehyde (Table 2, entry 16) 1H NMR (500 MHz,

CDCl3): δ 7.18-7.21(q, 1H), 7.74-7.75(q, 1H), 7.77(dd, J = 3.5, 1.5 Hz, 1H), 9.91(d, J

= 1.5 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 128.2, 135.0, 136.3, 143.8, 182.9.

OO 2-Furaldehyde (Table 2, entry 17) 1H NMR (500 MHz, CDCl3): δ

6.53-6.55(q, 1H), 7.20(t, J = 1.8 Hz, 1H), 7.63(d, J = 1.0 Hz, 1H), 9.58(s, 1H). 13C

NMR (125 MHz, CDCl3): δ 112.5, 121.2, 148.1, 152.9, 177.8.

O

Cinnamaldehyde (Table 2, entry 18) 1H NMR (500 MHz,

CDCl3): δ 6.71(q, J = 7.5 Hz, 1H), 7.42(d, J = 2.0 Hz, 1H), 7.43(d, J = 2.0 Hz, 2H),


S12

7.45(d, J = 2.5 Hz, 1H), 7.55(d, J = 2.5 Hz, 1H), 7.56(d, J = 2.0 Hz, 1H), 9.69(d, J =

7.0 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 128.5, 129.1, 131.2, 134.0, 152.7, 193.8. O

Acetophenone (Table 2, entry 19) 1H NMR (500 MHz, CDCl3): δ 2.62(s, 3H), 7.47(t, J = 7.5 Hz, 2H), 7.57(t, J = 7.5 Hz, 1H), 7.97(d, J = 7.5 Hz,

2H). 13C NMR (125 MHz, CDCl3): δ 26.5, 128.2, 128.4, 133.0, 137.0, 198.0.


S13

Figure 1. 1H NMR and 13C NMR spectra of benzaldehyde.


S14

Figure 2. 1H NMR and 13C NMR spectra of p-tolualdehyde.


S15

Figure 3. 1H NMR and 13C NMR spectra of 4-methoxybenzaldehyde.


S16


S17

Figure 4. 1H NMR and 13C NMR spectra of 1-naphthaldehyde


S18

Figure 5. 1H NMR and 13C NMR spectra of 3,4-dimethylbenzaldehyde


S19

Figure 6. 1H NMR and 13C NMR spectra of 3,4-dimethoxybenzaldehyde


S20

Figure 7. 1H NMR and 13C NMR spectra of 2-methoxybenzaldehyde.


S21

Figure 8. 1H NMR and 13C NMR spectra of 2-chlorobenzaldehyde


S22

Figure 9. 1H NMR and 13C NMR spectra of 3-chlorobenzaldehyde


S23

Figure 10. 1H NMR and 13C NMR spectra of 4-chlorobenzaldehyde.


S24

Figure 11. 1H NMR and 13C NMR spectra of 4-bromobenzaldehyde.


S25

Figure 12. 1H NMR and 13C NMR spectra of 4-nitrobenzaldehyde.


S26

Figure 13. 1H NMR and 13C NMR spectra of 4-fluorobenzaldehyde.


S27

Figure 14. 1H NMR and 13C NMR spectra of 2,4-dichlorobenzaldehyde.


S28

Figure 15. 1H NMR and 13C NMR spectra of 3-nicotinaldehyde.


S29

Figure 16. 1H NMR and 13C NMR spectra of 2-thiophenecarboxaldehyde.


S30

Figure 17. 1H NMR and 13C NMR spectra of furfural.


S31

Figure 18. 1H NMR and 13C NMR spectra of cinnamaldehyde.


S32

Figure 19. 1H NMR and 13C NMR spectra of acetophenone.


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Supporting Information] Copper-Catalyzed Aerobic Alcohol … · 2013. 8. 13. · S1 [Supporting Information]Copper-Catalyzed Aerobic Alcohol Oxidation under Air in Neat Water by Using