SULFATED TUNGSTATE AS HYDROXYL ACTIVATOR FOR PREPARATION OF BENZYL, INCLUDING P-METHOXYBENZYL ETHERS OF ALCOHOLS AND PHENOLS

Kamlesh V. Katkar, Sachin D. Veer and Krishnacharya G. Akamanchi*

*Department of Pharmaceutical Sciences and Technology,

Institute of Chemical Technology, Matunga, Mumbai 400 019.kgap@rediffmail.com ; kg.akamanchi@ictmumbai.edu.in

SUPPORTING INFORMATION

Contents

A) Experimental

B) Analytical Data

C) IR and 1H NMR Spectral Copies

D) References

1

A) Experimental

a) Reagents:

All chemicals were purchased from Spectrochem Pvt. Ltd. India and were used without further

purification.

b) Preparation of sulfated tungstate1

Anhydrous sodium tungstate (32.9g, 0.1mol) was added portionwise, maintaining the temperature

between 0 to 5 °C, to a stirred solution of chlorosulfonic acid (23.2g, 0.2mol) in chloroform (150 ml)

contained in a 250ml round bottom flask fitted with CaCl2 drying tube, placed in an ice bath. After

completion of addition, the mixture was stirred further for 1 h. A yellowish-white solid obtained was

filtered, washed repeatedly with deionized water until filtrate was neutral and free from chloride ions

(detected by AgNO3 test) and dried in an oven for 2 h at 100 °C to get 34g of sulfated tungstate.

c) General method for the preparation:

Sulfated tungstate (10 wt%) was added to a mixture of p-methoxybenzyl alcohol (1g, 7.25mmol) and n-

butanol (1.34g, 18.11mmol) the reaction mixture was stirred at 80 °C for 1h. The progress of the reaction

was monitored by TLC. After completion of the reaction, the reaction mixture was diluted with EtOAc

(15ml) and filtered to recover the catalyst. Organic layer was concentrated under reduced pressure,

residue obtained was purified by chromatography on silica gel (#60-120) with n-hexane/EtOAc (90:10) as

eluent to get pure p-methoxybenzyl ether as colourless oil.

B) Analytical data:

Table 3. Synthesis of different p-methoxybenzylic ether

Entry 1) 1-methoxy-4-(methoxymethyl) benzene21

2

Yield: 80%, Colorless liquid; bp 203-204°C (lit 203-205 °C); Rf 0.75 (n-hexane/EtOAc, 90:10); IR 2933,

2856, 1097 cm-1; 1H NMR (200 MHz; CCl4; Me4Si): δ = 7.27-7.23 (d, J=8.0 Hz, 2H), 6.89-6.85 (d, J=8.0

Hz, 2H), 4.39 (s, 2H), 3.81 (s, 3H), 3.35 (s, 3H).

Entry 2) 1-(ethoxymethyl)-4-methoxybenzene21

Yield: 85%, Colorless liquid; bp 229-230°C (lit 230°C); Rf 0.75 (n-hexane/EtOAc, 90:10); IR 2931,

2863, 1229, 1098 cm-1; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.27-7.23 (d, J=8.0 Hz, 2H), 6.88-6.84

(d, J=8.0 Hz, 2H), 4.43 (s, 2H), 3.80 (s, 3H), 3.55-3.45 (m, 2H), 1.27-120 (t, 3H).

Entry 3) 1-methoxy-4-(propoxymethyl)benzene25

Yield: 90%, Colorless liquid; bp 243-244°C (lit 244-245°C); Rf 0.75 (n-hexane/EtOAc, 90:10); IR 2934,

2865, 1231, 1097 cm-1; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.28-7.24 (d, J=8.0 Hz, 2H), 6.90-6.96

(d, J=8.0 Hz, 2H), 4.42 (s, 2H), 3.82 (s, 3H), 3.39-3.34 (t, 2H), 1.51-1.47 (m, 2H), 0.93-0.87 (t, 3H).

Entry 4) 1-(butoxymethyl)-4-methoxybenzene24

Yield: 92%, Colorless liquid; bp: 260-262°C (lit 262-263°C); Rf 0.75 (n-hexane/EtOAc, 90:10); IR

2931, 2863, 1229, 1098 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.27-7.24 (d, J=8.64 Hz, 2H),

6.89-6.86 (d, J=8.64 Hz, 2H), 4.43 (s, 2H), 3.80 (s, 3H), 3.45-3.41 (t, 2H), 1.64-1.59 (m, 2H), 1.41-1.35

(m, 2H), 0.90-0.84 (t, 3H).

Entry 5) 1-methoxy-4-((pentyloxy)methyl)benzene24

3

Yield: 87%, Colorless liquid; bp 280°C (lit 279-280°C); Rf 0.75 (n-hexane/EtOAc, 90:10); IR 2938,

2866, 1225, 1097 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.29-7.26 (d, J=8.64 Hz, 2H), 6.90-6.87

(d, J=8.64 Hz, 2H), 4.41 (s, 2H), 3.82 (s, 3H), 3.44-3.41 (t, 2H), 1.60-1.55 (m, 2H), 1.40-1.36 (m, 2H),

1.31-1.27 (m, 2H), 0.90-0.85 (t, 3H).

Entry 6) 1-(isopropoxymethyl)-4-methoxybenzene25

Yield: 88%, Colorless liquid; bp 237°C (lit 237-238°C); Rf 0.87 (n-hexane/EtOAc, 90:10); IR 2932,

2871, 1104 cm-1; Colorless liquid; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.27-7.23 (d, J=8.0 Hz, 2H),

6.87-6.83 (d, J=8.0 Hz, 2H), 4.43 (s, 2H), 3.79 (s, 3H), 3.68-3.62 (m, 1H), 1.22-1.18 (d, 6H).

Entry 7) 1-(tert-butoxymethyl)-4-methoxybenzene16

Yield: 85%, Colorless liquid; bp 243-244°C (lit 244-245°C); Rf 0.87 (n-hexane/EtOAc, 90:10); IR 2974,

2869, 1247, 1062 cm-1; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.27-7.23 (d, J=8.0 Hz, 2H), 6.87-6.84

(d, J=8.0 Hz, 2H), 4.37 (s, 2H), 3.80 (s, 3H), 1.29 (s, 9H).

Entry 8) 1-((cyclopentyloxy)methyl)-4-methoxybenzene24

Yield: 88%, Colorless liquid; bp 297°C (lit 297-298°C); Rf 0.75 (n-hexane/EtOAc, 90:10); IR 2938,

2866, 1225, 1097 cm-1; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.26-7.22 (d, J=8.64 Hz, 2H), 6.87-6.83

(d, J=8.64 Hz, 2H), 4.42 (s, 2H), 3.81 (s, 3H), 2.90 (m, 1H), 1.76-1.41 (m, 8H).

Entry 9) 1-((cyclohexyloxy)methyl)-4-methoxybenzene24

4

Yield: 83%, Colorless liquid; bp 315°C (lit 315-316°C); Rf 0.75 (n-hexane/EtOAc, 90:10); IR 2938,

2866, 1225, 1097 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.27 (d, J=8.64 Hz, 2H), 6.86 (d, J=8.64

Hz, 2H), 4.40 (s, 2H), 3.80 (s, 3H), 2.80 (m, 1H), 1.72-1.43 (m, 10H).

Entry 10) 4-((4-methoxybenzyl)oxy)butan-1-ol27

Yield: 80%, Colorless liquid; bp 323-324°C (lit 323-325°C); Rf 0.15 (n-hexane/EtOAc, 90:10); IR 3335,

2958, 2871, 1227, 1080 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.26-7.24 (d, J=8.0 Hz, 2H), 6.90-

6.88 (d, J=8.0 Hz, 2H), 4.45 (s, 2H), 3.80 (s, 3H), 3.64-3.61 (t, 2H), 3.50-3.46 (t, 2H), 1.66-1.61 (m, 4H).

Entry 11) 4-((4-methoxybenzyl)oxy)but-2-en-1-ol25

Yield: 83%, Colorless liquid; bp 121°C (lit 121-122°C); Rf 0.15 (n-hexane/EtOAc, 90:10); IR 3335,

2957, 2870, 1247, 1088 cm-1; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.31-7.27 (d, J=8.0 Hz, 2H), 6.93-

6.89 (d, J=8.0 Hz, 2H), 5.90-5.71 (m, 2H), 4.42 (s, 2H), 4.21-4.08 (t, 2H), 3.85 (s, 3H), 1.80 (s, 2H),.

Entry 12) 1-((allyloxy)methyl)-4-methoxybenzene28

Yield: 85%, Colorless liquid; bp 248-249°C (lit 248-250°C); Rf 0.74 (n-hexane/EtOAc, 90:10); IR 3089,

2975, 2868, 1250, 1097 cm-1; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.25-7.21 (d, J=8.0 Hz, 2H), 6.87-

6.83 (d, J=8.0 Hz, 2H), 5.60-5.56 (m, 1H), 5.40-5.38 (dd, 1H), 5.26-5.23 (dd, 1H), 4.40 (s, 2H), 3.85 (s,

3H).

Entry 13) 1-methoxy-4-((undec-10-en-1-yloxy)methyl)benzene27

5

Yield: 87%, Colorless liquid; bp 374°C (lit 373-374°C); Rf 0.77 (n-hexane/EtOAc, 90:10); IR 3089,

2975, 2868, 1250, 1097 cm-1; 1H NMR (200 MHz; CDCl3; Me4Si): δ = 7.27-7.23 (d, J=8.0 Hz, 2H), 6.89-

6.85 (d, J=8.0 Hz, 2H), 5.80-5.76 (m, 1H), 5.07 (dd, 1H), 5.01 (dd, 1H), 4.40 (s, 2H), 3.80 (s, 3H), 3.42 (t,

2H), 2.19 (m, 2H), 1.51 (m, 2H), 1.43 (m, 2H), 1.29 (s, 10H).

Entry 14) 1-methoxy-4-((pent-4-yn-1-yloxy)methyl)benzene28

Yield: 80%, Colorless liquid; bp 292-293°C (lit 292-293°C); Rf 0.70 (n-hexane/EtOAc, 90:10); IR 3295,

2934, 2858, 1247, 1102 cm-1; 1H NMR(400 MHz; CDCl3; Me4Si): δ = 7.20 (d, J=8.64 Hz, 2H), 6.90 (d,

J=8.72 Hz, 2H), 4.40 (s, 2H), 3.80 (s, 3H), 3.40 (t, 2H), 2.82 (t, 1H), 2.41 (t, 2H), 1.63 (m, 2H).

Table 4. Etherification of different classes of benzylic alcohols

Entry 1) (butoxymethyl)benzene5

Yield: 88%, Colorless liquid; bp 219-220°C (lit 219-220°C); Rf 0.71 (n-hexane/EtOAc, 90:10); IR 2933,

2856, 1206, 1097 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.45-7.30 (m, 5H), 4.54 (s, 2H), 3.43-

3.47 (t, 2H), 1.68-1.59 (m, 2H), 0.94-0.87 (t, 3H).

Entry 2) 1-(butoxymethyl)-4-methylbenzene5

Yield: 90%, Colorless liquid; bp 229-230°C (lit 228-230°C); Rf 0.71 (n-hexane/EtOAc, 90:10); IR 2946,

2878, 1235, 1104 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.21-7.19 (d, J=8.0 Hz, 2H), 7.15-7.13

(d, J=8.64 Hz, 2H), 4.40 (s, 2H), 3.40-4.34 (t, 2H), 2.34 (s, 3H), 1.56-1.47 (m, 2H), 1.35-1.26 (m, 2H),

0.95-0.88 (t, 3H).

Entry 3) 1-(butoxymethyl)-4-chlorobenzene15

6

Yield: 82%, Colorless liquid; bp 263-264°C (lit 264-265°C); Rf 0.34 (n-hexane/EtOAc, 90:10); IR 2944,

2878, 1221, 1098 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.32-7.30 (d, J=8.0 Hz, 2H), 7.24 (d,

J=8.4 Hz, 2H), 4.43 (s, 2H), 3.44 (t, 2H), 1.51 (m, 2H), 1.45 (m, 2H), 0.90 (t, 3H).

Entry 4) 4-(butoxymethyl)phenol20

Yield: 80%, Colorless liquid; bp 288-290°C (lit 289-290°C); Rf 0.11 (n-hexane/EtOAc, 90:10); IR 3335,

2958, 2871, 1227, 1080 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.21-7.19 (d, J=8.50 Hz, 2H),

6.79-6.77 (d, J=8.56 Hz, 2H), 5.55 (s, 1H), 4.42 (s, 2H), 3.49-3.42 (t, 2H), 1.62-1.49 (m, 2H), 1.39-1.29

(m, 2H), 0.94-0.87 (t, 3H).

Entry 5) 4-(butoxymethyl)-2-methoxyphenol5

Yield: 83%, Colorless liquid; bp 240-241°C (lit 241-242°C); Rf 0.91 (n-hexane/EtOAc, 90:10); IR 3348,

2961, 2856, 1243, 1095 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 6.89–6.79 (m, 3H), 5.58 (s, 1H),

4.42 (s, 2H), 3.89 (s, 3H), 3.49-3.42 (t, 2H), 1.64−1.50 (m, 2H), 1.41−1.33 (m, 2H), 0.92-0.86 (t, 3H).

Entry 6) (1-propoxyethyl)benzene19

Yield: 88%, Colorless liquid; bp 255°C (lit 254-255°C); Rf 0.90 (n-hexane/EtOAc, 90:10); IR 2956,

2868, 1100 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.35–7.26 (m, 5H), 4.44-4.36 (m, 1H), 3.33-

3.29 (t, 2H), 1.51-1.49 (d, 3H), 1.47−1.32 (m, 2H), 0.91-0.88 (t, 3H).

Entry 7) (1-butoxyethyl)benzene15

Yield: 90%, Colorless liquid; bp 225-226°C (lit 226-228°C); Rf 0.90 (n-hexane/EtOAc, 90:10); IR 2960,

2871, 1104 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.33–7.26 (m, 5H), 4.45-4.36 (m, 1H), 3.33-

3.28 (t, 2H), 1.57−1.47 (m, 2H), 1.48-1.44 (d, 3H), 1.37−1.30 (m, 2H), 0.92-0.88 (t, 3H).

7

Entry 8) 1-(1-butoxyethyl)-4-methylbenzene21

Yield: 87%, Colorless liquid; bp 248°C (lit 248-249°C); Rf 0.90 (n-hexane/EtOAc, 90:10); IR 2933,

2856, 1206, 1097 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.21–7.13 (m, 4H), 4.40-4.33 (m, 1H),

3.28-3.23 (t, 2H), 2.35 (s, 3H), 1.57−1.52 (m, 2H), 1.46-1.41 (d, 3H), 1.37−1.32 (m, 2H), 0.90-0.86 (t,

3H).

Entry 9) 1-(1-butoxyethyl)-4-chlorobenzene19

Yield: 82%, Colorless liquid; bp 243-244°C (lit 244-245°C); Rf 0.90 (n-hexane/EtOAc, 90:10); IR

2932, 2871, 1092, 540 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.30 (d, J=8.48 Hz, 2H), 7.24 (d,

J=8.4 Hz, 2H), 4.36 (m, 1H), 3.77 (m, 2H), 1.57−1.52 (m, 2H), 1.40 (d, 3H), 1.37−1.32 (m, 2H), 0.88 (t,

3H).

Entry 10) (ethoxymethylene)dibenzene5

Yield: 81%, Colorless liquid; bp 287-288°C (lit 288-290°C); Rf 0.84 (n-hexane/EtOAc, 90:10); IR 2933,

2856, 1206, 1097cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.37-7.22 (m, 10H), 5.35 (s, 1H),

3.61−3.50 (m, 2H), 1.28 (t, 3H).

Entry 11) (propoxymethylene)dibenzene5

Yield: 86%, Colorless liquid; bp 305-306°C (lit 305-306°C); Rf 0.88 (n-hexane/EtOAc, 90:10); IR 2933,

2856, 1097cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.33-7.20 (m, 10H), 5.36 (s, 1H), 3.55−3.47 (m,

2H), 1.55−1.47 (m, 2H), 0.90 (t, 3H).

8

Entry 12) (butoxymethylene)dibenzene5

Yield: 89%,Colorless liquid; bp 321-322°C (lit 320-321°C); Rf 0.85 (n-hexane/EtOAc, 90:10); IR 2932,

2871, 1104cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.37-7.20 (m, 10H), 5.27 (s, 1H), 3.45 (t, 2H),

1.68−1.62 (m, 2H), 1.49−1.39 (m, 2H), 0.90 (t, 3H).

Entry 13) ((prop-2-yn-1-yloxy)methylene)dibenzene30

Yield: 85%,Colorless liquid bp 243-244°C (lit 244-245°C); Rf 0.82 (n-hexane/EtOAc, 90:10); IR 3290,

3029, 2359, 1185, 1069cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.27-7.16 (m, 10H), 5.32 (s, 1H),

3.67 (m, 1H), 1.20 (d, J=6Hz, 6H).

Entry 14) (3-butoxyprop-1-en-1-yl)benzene28

Yield: 82%, Colorless liquid; bp 289°C (lit 288-289°C); Rf 0.69 (n-hexane/EtOAc, 90:10); IR 2933,

2856, 1610, 1104 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.40-7.24 (m, 5H), 6.65 (d, 1H), 6.25

(m, 1H), 4.05 (d, 2H), 3.37 (t, 2H), 1.59−1.52 (m, 2H), 1.47−1.40 (m, 2H), 0.90 (t, 3H).

Table 5. PMB protection of phenols in presence of sulfated tungstate

Entry 1) 1-methoxy-4-((pentyloxy)methyl)benzene16

Yield: 90%, White solid; mp: 89-91 ºC (lit 91-93°C) ; Rf 0.36 (n-hexane/EtOAc, 90:10); IR νmax(KBr)

2933, 2856, 1206, 1097 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.34-7.29 (m, 2H), 7.04-6.98 (m,

5H), 6.94-6.90 (m, 2H), 5.10 (s, 2H), 3.82 (s, 3H).

Entry 2) 1-methoxy-4-((p-tolyloxy)methyl)benzene17

9

Yield: 85%, White solid; mp:87-89 ºC (lit 88-89°C); Rf 0.36 (n-hexane/EtOAc, 90:10); IR νmax(KBr)

2926, 2854, 1247, 1099 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.18-7.12 (m, 2H), 7.02-6.98 (m,

2H), 6.94-6.87 (m, 4H), 5.12 (s, 2H), 3.80 (s, 3H), 2.35 (s, 3H).

Entry 3) 1-(tert-butyl)-4-((4-methoxybenzyl)oxy)benzene17

Yield: 86%, White solid; mp:90-92 ºC (lit 91-92°C); Rf 0.33 (n-hexane/EtOAc, 90:10); IR νmax(KBr)

2960, 2871, 1092 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.38-7.32 (m, 2H), 7.00-6.97 (m, 2H),

6.94-6.90 (m, 4H), 5.16 (s, 2H), 3.80 (s, 3H), 1.29 (s, 9H).

Entry 4) 1-methoxy-4-((4-methoxybenzyl)oxy)benzene17

Yield: 85%, White solid; mp:121-123 ºC(lit 123-124°C) ; Rf 0.36 (n-hexane/EtOAc, 90:10); IR

νmax(KBr) 2957, 2857, 1248, 1037 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.00-6.97 (m, 2H),

6.94-6.88 (m, 6H), 5.12 (s, 2H), 3.83 (s, 6H).

Entry 5) 1,3-dichloro-2-((4-methoxybenzyl)oxy)benzene17

Yield: 78%, White solid; mp:155-157 ºC(lit 155-157°C) ; Rf 0.52 (n-hexane/EtOAc, 90:10); IR

νmax(KBr) 2960, 2873, 1274, 1090 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.53-7.51 (d, 2H),

7.21-7.20 (t, 1H), 6.94-6.88 (m, 4H), 5.14 (s, 2H), 3.80 (s, 3H).

Entry 6) 4-((4-methoxybenzyl)oxy)phenol18

10

Yield: 72%, White solid; mp:134-135 ºC(lit 134-135°C) ; Rf 0.34 (n-hexane/EtOAc, 90:10); IR

νmax(KBr) 3406, 2936, 2838, 1248, 1034 cm-1; 1H NMR (400 MHz; CDCl3; Me4Si): δ = 7.10-7.00 (m,

4H), 6.96-6.85 (m, 4H), 5.30 (br, 2H), 5.14 (s, 2H), 3.80 (s, 3H).

Entry 7) N-(4-((4-methoxybenzyl)oxy)phenyl)acetamide18

Yield: 70%, White solid; mp:140-142 ºC(lit 141-142°C); Rf 0.03 (n-hexane/EtOAc, 90:10); IR

νmax(KBr) 3394, 1647, 1063 cm-1 1H NMR (400 MHz; CDCl3; Me4Si):δ = 7.53-7.50 (m, 2H), 7.02-6.92

(m, 6H), 5.30 (br, 1H), 5.16 (s, 2H), 3.80 (s, 3H), 2.04 (s, 3H).

Entry 8) 1-((4-methoxybenzyl)oxy)naphthalene18

Yield: 80%, Brown solid; mp:111-113 ºC (lit 112-113°C); Rf 0.27 (n-hexane/EtOAc, 90:10); IR

νmax(KBr) 2974, 2871, 1206, 1091 cm-1 1H NMR (400 MHz; CDCl3; Me4Si):δ = 8.30-8.28 (m, 1H),

8.07-8.02 (m, 1H), 7.65-7.54 (m, 5H), 7.01-6.91 (m, 4H), 5.30 (br, 2H), 5.10 (s, 2H), 3.80 (s, 3H).

11

[C] Selected IR and 1H Spectral Copies

(1) 1-methoxy-4-(methoxymethyl)benzene (Table 3, entry 1)IR

1HNMR

12

(2) 1-(ethoxymethyl)-4-methoxybenzene (Table 3, entry 2)

IR

1HNMR

O

MeO

13

(3) 1-(butoxymethyl)-4-methoxybenzene (Table 3, entry 4)

IR

14

1HNMR

(4) 1-(isopropoxymethyl)-4-methoxybenzene (Table 3, entry 6)

15

IR

1HNMR

(5) 1-(tert-butoxymethyl)-4-methoxybenzene (Table 3, entry 7)

IR

16

1HNMR

(6) 4-((4-methoxybenzyl)oxy)butan-1-ol (Table 3, entry 10)

O

MeO

17

IR

1HNMR

(7) 4-((4-methoxybenzyl)oxy)but-2-en-1-ol (Table 3, entry 11)

18

IR

1HNMR

O

MeO

OH

19

(8) 1-methoxy-4-((pent-4-yn-1-yloxy)methyl)benzene (Table 3, entry 14)

IR

1HNMR

20

(9) (butoxymethyl)benzene (Table 1, entry 1)

IR

1HNMR

21

(10) (butoxymethyl)benzene (Table 4, entry 4)

IR

1HNMR

22

(11) (1-butoxyethyl)benzene (Table 4, entry 7)

IR

1HNMR

23

(12) (1-butoxyethyl)benzene (Table 4, entry 8)

IR

1HNMR

24

3) Reference:

1. Chaudhari, P. S.; Salim, S. D.; Sawant, R. V.; Akamanchi, K. G. Green Chem. 2010, 12, 1707-1709.

2. Firouzabadi, H.; Iranpoor, N.; Jafari, A. A. J.Mol. Catal. A: Chem. 2005, 227, 97-100.

3. Corma, A.; Renz, M. Angew. Chem., Int. Ed. 2007, 46, 298-300.4. Rao, K. T. V.; Rao, P. S. N.; Sai Prasad, P. S.; Lingaiah, N.; Catal. Commun.

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