4.4 Supplemental materialdownloads.hindawi.com/journals/jchem/2017/6267036.f1.docx · Web viewSolvent-free Henry and Michael reactions with nitroalkanes promoted by potassium carbonate

Solvent-free Henry and Michael reactions with nitroalkanes promoted by

potassium carbonate as a versatile heterogeneous catalyst

Supplementary Material

Table of Contents

4.4 Supplemental material..........................................................................................................1

4.4.1 Analytical data and spectra for β-nitroalcohols.............................................................1

4.4.2 Analytical data and spectra for Michael mono-adducts..............................................20

4.4 Supplemental material

4.4.1 Analytical data and spectra for β-nitroalcohols

3. (Table 1 Entry 5). 2-nitro-3-hexanol. Translucent Liquid; IR (neat): νmax 3421, 2962, 2933, 2875,

2852, 1552, 1720 cm-1; 1H NMR (250 MHz, CDCl3) δ 0.92-1.0 (t, 3H), δ 1.31-1.66 (m, 7H), δ 2.14-

2.19 (dd, J = 6.71 Hz, J = 4.88 Hz, 1H), δ 3.87-3.98 (m, 0.5H), δ 4.16-4.25 (m, 0.5H), δ 4.46-4.61

(m, 1H).

1

3b. 2-methyl-2-nitro-3-hexanol. Translucent Liquid, IR (neat): νmax 3438, 2973, 2938, 2860, 1548,

1721 cm-1; 1H NMR (250 MHz, CDCl3) δ 0.90-1.01 (t, J = 7.33 Hz, 3H), 1.20-1.50 (m, 3H), 1.52-1.75

(m, 7H), 2.17-2.27 (d, 1H, J = 6.71 Hz), 3.95-4.10 (m, 1H). 13C NMR (62.9 MHz, CDCl3) δ 92.3, 75.8,

33.6, 23.7, 20.3, 19.6, 13.8.

2

3

3c. 1-nitro-2-propanol. Translucent Liquid; IR (neat): νmax 3412, 2981, 2937, 1556, 1708 cm-1; 1H

NMR (250 MHz, CDCl3) δ 1.28-1.34 (d, J = 6.71 Hz, 3H), δ 2.57-2.64 (d, J = 6.71 Hz, 1H), δ 4.37-

4.42 (m, 2H) δ 4.45-4.60 (m, 1H).

4

3d. 2-nitro-1-phenyl-1-propanol. Translucent Liquid; IR (neat): νmax 3527, 2995, 2943, 2902, 1548,

3064, 3034, 1700 cm-1; 1H NMR (250 MHz, CDCl3) δ 1.35-1.52 (2d, J = 6.71 Hz, J = 7.32 Hz, 3H), δ

2.51 (2d, J = 4.27 Hz, J = 3.05 Hz, 1H), δ 4.66-4.84 (m, 1H), δ 5.05 (2d, J = 9.16 Hz, 1H), δ 7.3-7.5

(m, 5H).

5

3e. 3-methyl-3-nitro-2-butanol. Translucent Liquid; IR (neat): νmax 3433, 2987, 2945, 2881, 1544,

1718 cm-1; 1H NMR (250 MHz, CDCl3) δ 1.20-1.25 (d, J = 6.72 Hz, 3H), δ 1.55-1.59 (d, J = 5.5 Hz,

6H), δ 2.29-2.36 (d, J = 5.5 Hz, 1H), δ 4.20-4.30 (m, J = 6.1 Hz, 1H). 13C NMR (62.9 MHz, CDCl3) δ

92.3, 71.9, 23.7, 19.9, 17.8.

6

3f. 3-nitro-1-phenyl-2-pentanol. Translucent Liquid; IR (neat): νmax 3421, 2976, 2937, 2881, 1548,

3086, 3062, 3030, 1707 cm-1; 1H NMR (250 MHz, CDCl3) δ 0.95-1.06 (dt, J = 7.33 Hz, 3H), δ 1.85-

2.26 (m, 2H), δ 2.71-2.94 (m, 3H), δ 4.07-4.30 (m, 1H), δ 4.37-4.47 (m, 1H), δ 7.18-7.46 (m, 5H).

7

3g. 3-nitro-4-octanol. Translucent Liquid; IR (neat): νmax 3431, 2958, 2935, 2873, 2862, 1548, 1712

cm-1; 1H NMR (250 MHz, CDCl3) δ 0.89-1.03 (tt, J = 7.33, 6H), δ 1.23-1.58 (m, 4H), δ 1.79-2.30 (m,

3H), δ 3.84-4.08 (m, 1H), δ 4.33-4.45 (m, 1H).

8

3h. 4-nitro-1-phenyl-3-heptanol. White solid, M.P.: 54-59 oC; IR (neat): νmax 3528, 3103, 3062,

2986, 2970, 1552 cm-1. 1H NMR (250 MHz, CDCl3) δ 7.36-7.16 (m, 5H), 4.54-4.41 (m, 1H), 4.10-

3.78 (2m, 1H), 2.98-2.61 (m, 2H), 2.50-2.22 (2m, 1H), 2.15-1.64 (m, 4H), 1.43-1.24 (sext, 2H, J =

7.32 Hz), 0.94 (t, 3H, J = 7.32 Hz). 13C NMR (62.9 MHz, CDCl3) δ 140.9, 128.6, 128.5, 92.7, 71.3,

35.3, 32.5, 31.6, 19.0, 13.4.

9

3i. 4-nitro-5-decanol. Pale Yellow Liquid, IR (neat): νmax 3527, 3421, 2958, 2933, 2873, 2852, 1550

cm-1; 1H NMR (250 MHz, CDCl3) δ 4.53-4.41 (m, 2H), 4.03 (s, 0.29H), 3.87 (s, 0.71H), 2.30 (s, 1H),

1.83-1.67 (m, 3H), 1.63-1.24 (m, 19H), 1.00-0.86 (2t, 12H, J = 7.32 Hz). 13C NMR (62.9 MHz, CDCl3)

δ 92.7, 92.1, 72.5, 72.1, 33.6, 33.2, 32.5, 31.6, 31.5, 30.0, 25.3, 25.0, 22.5, 19.3, 19.1. 13.9, 13.5, 13.4.

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 0

10

11

3j. 2-nitro-1-(4-nitrophenyl)hexan-1-ol. Yellow Liquid; IR (neat): νmax 3527, 3508, 3113, 3082,

2958, 2931, 1556, 1519 cm-1; 1H NMR (250 MHz, CDCl3) δ 8.31-8.23 (dd, 4H, J = 8.55 Hz and 2.45

Hz), 7.62-7.55 (dd, 4H, J = 8.54 Hz and 2.44 Hz), 5.33 (d, 1H, J = 9.76 Hz and 3.66 Hz), 5.17 (d, 1H,

J = 7.94 Hz), 4.74-4.60 (m, 2H), 3.03 (s, 1H), 2.82 (s, 1H), 2.30-1.65 (m, 4H), 1.51-1.12 (m, 8H),

0.98-0.75 (2t, 6H, J = 6.1 Hz). 13C NMR (62.9 MHz, CDCl3) δ 148.4, 148.1, 145.7, 145.6, 127.9,

127.3, 124.2, 123.9, 93.2, 92.7, 74.5, 73.5, 30.0, 27.9, 27.6, 27.4, 22.0, 21.8, 13.6, 13.6.

12

3k. 2-nitro-1-phenylethanol. Dark Red Liquid; IR (neat): νmax 3529, 3431, 3421, 3064, 3032, 2920,

1556 cm-1; 1H NMR (250 MHz, CDCl3) δ 7.45-7.33 (m, 1H), 5.48 (dd, 1H, J = 3.66 Hz and J = 9.16

Hz), 4.68-4.48 (m, 2H), 2.80 (s, 1H). 13C NMR (62.9 MHz, CDCl3) δ 138.2, 129.1, 126.0, 81.3, 71.0.

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 0

13

14

3l. 2-nitro-1-cyclohexylethanol. Yellow Liquid, IR (neat): νmax 3417, 2924, 2852, 1556, 1523 cm-1; 1H NMR (250 MHz, CDCl3) δ 4.57-4.37 (m, 2H), 4.17-4.06 (m, 1H), 2.43 (br, 1H), 1.88-1.40 (m, 7H),

1.36-1.00 (m, 4H). 13C NMR (62.9 MHz, CDCl3) δ 79.4, 72.9, 41.5, 28.9, 28.0, 26.1, 25.9, 25.8.

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 0

15

16

3m. 1-(4-methoxyphenyl)-2-nitroethanol. Dark Red Liquid; IR (neat): νmax 3462, 3007, 2962, 2937,

1176, 1556, 1548 cm-1; 1H NMR (250 MHz, CDCl3) δ 7.33 (d, 2H, J = 8.55 Hz), 6.93 (d, 2H, J = 8.54

Hz), 5.46-5.37 (dd, 1H, J = 2.44 Hz and J = 9.16 Hz), 4.66-4.44 (m, 2H), 3.82 (s, 3H), 2.72 (s, 1H). 13C

NMR (62.9 MHz, CDCl3) δ 160.1, 130.3, 127.3, 115.0, 81.3, 70.7, 55.4.

17

3n. 2-nitro-1-(4-nitrophenol)ethanol. Red Liquid, IR (neat): νmax 3520, 3477, 3113, 3082, 2972,

2924, 1556, 1519 cm-1; 1H NMR (250 MHz, CDCl3) δ 8.31-8.24 (d, 2H, J = 8.55 Hz), 7.67-7.60 (d,

2H, J = 8.53 Hz), 5.66-5.57 (quin, 1H, J = 3.66 Hz), 4.67-4.53 (m, 2H), 3.38-3.33 (d, 1H, J = 3.66 Hz). 13C NMR (62.9 MHz, CDCl3) δ 148.2, 145.2, 127.0, 124.2, 80.7, 70.0.

18

3o. 1-bromo-1-nitro-2-propanol. Pale Yellow Liquid, IR (neat): νmax 3408, 3387, 2983, 2937, 1560

cm-1.; 1H NMR (250 MHz, CDCl3) δ 5.95 (d, 0.32H, J = 3.66 Hz), 5.74 (d, 0.68H, J = 7.94 Hz), 4.53-

4.36 (m, 1H), 2.20 (s, 1H), 1.46 (d, 2.04H, J = 6.1 Hz), 1.37 (d, 0.96H, J = 6.1 Hz). 13C NMR (62.9

MHz, CDCl3) δ 86.4, 82.5, 69.9, 69.1, 19.4, 18.8.

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 0

( p p m)01 02 03 04 05 06 07 08 09 0

19

4.4.2 Analytical data and spectra for Michael mono-adducts

8a. Methyl 4-nitrobutanoate. Pale Green Liquid, IR (neat): νmax 2906, 1732, 1556 cm-1; 1H NMR

(250 MHz, CDCl3) δ 4.56-4.45 (t, 2H, J = 6.72 Hz), 3.72 (s, 3H), 2.53-2.45 (t, 2H, J = 6.72 Hz), 2.4-

2.25 (quin, 2H, J = 6.71 Hz). 13C NMR (62.9 MHz, CDCl3) δ 172.4, 74.4, 51.9, 30.3, 22.4.

20

21

8b. Methyl 4-nitrohexanoate. Colourless Liquid, IR (neat): νmax 2962, 2937, 2877, 2850, 1735, 1544

cm-1; 1H NMR (250 MHz, CDCl3) δ 4.55-4.43 (m, 1H), 3.7 (s, 3H), 2.5-1.73 (m, 6H), 1.02-0.94 (t, 3H,

J = 7.32 Hz). 13C NMR (62.9 MHz, CDCl3) δ 172.4, 89.2, 51.9, 30.0, 28.3, 27.2, 10.1.

22

23

8c. Methyl 4-methyl-4-nitropentanoate. Colourless Liquid, IR (neat): νmax 2993, 2954, 2975, 2850,

1737, 1728, 1546 cm-1; 1H NMR (250 MHz, CDCl3) δ 3.70 (s, 3H), 2.39-2.22 (m, 4H), 1.6 (s, 6H). 13C

NMR (62.9 MHz, CDCl3) δ 172.6, 87.3, 51.9, 35.4, 29.1, 25.8.

24

25

8d. Methyl 4-nitroheptanoate. Pale Yellow Liquid, IR (neat): νmax 2962, 2937, 2877, 1735, 1550,

1541 cm-1; 1H NMR (250 MHz, CDCl3) δ 4.51-4.64 (m, 1H), 3.70 (s, 3H), 1.90-2.49 (m, 5H), 1.63-178

(m, 1H), 1.45-1.28 (m, 2H), 0.99-0.91 (t, 3H, J = 7.33 Hz). 13C NMR (62.9 MHz, CDCl3) δ 172.4,

87.6, 51.9, 35.9, 30.0, 28.6, 19.0, 13.4.

26

27

8e. Methyl 4-nitrononanoate. Colourless Liquid, IR (neat): νmax 2962, 2931, 1737, 1552, 1548 cm-1; 1H NMR (250 MHz, CDCl3) δ 4.61-4.48 (sept, 1H, J = 4.88 Hz), 3.70 (s, 3H), 2.48-1.90 (m, 5H), 1.80-

1.65 (m, 1H), 1.38-1.24 (m, 6H), 0.97-0.82 (m, 3H). 13C NMR (62.9 MHz, CDCl3) δ 172.4, 87.9, 51.9,

33.9, 31.1, 30.0, 28.7, 25.4, 22.3, 13.9.

28

29

8f. 3-(1-nitroethyl)cyclohexanone. Pale Yellow Liquid, IR (neat): νmax 2947, 2872, 1712, 1544 cm-1; 1H NMR (250 MHz, CDCl3) δ 4.57-4.34 (m, 1H), 2.53-2.06 (m, 5H), 2.02-1.83 (m, 1H), 1.82-1.37 (m,

6H). 13C NMR (62.9 MHz, CDCl3) δ 208.6, 208.4, 87.0, 86.9, 43.7, 43.3, 42.5, 42.3, 40.9, 40.8, 27.5,

27.0, 24.4, 24.2, 16.3, 16.2.

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 0

( p p m)02 04 06 08 01 0 01 2 01 4 01 6 01 8 02 0 0

30

8g. 3-(2-nitropropan-2-yl)cyclohexanone. Pale Yellow Solid, M. P.: 49–55 oC. IR (Nujol): νmax 1724,

1544 cm-1; 1H NMR (250 MHz, CDCl3) δ 2.50-2.39 (m, 2H), 2.38-2.23 (m, 2H), 2.20-2.06 (m, 2H),

1.87-1.75 (m, 1H), 1.72-1.60 (m, 1H), 1.59 (s, 3H), 1.57 (s, 3H), 1.51-1.33 (m, 1H). 13C NMR (62.9

MHz, CDCl3) δ 208.9, 90.7, 46.7, 42.7, 40.8, 26.1, 24.5, 23.6, 22.6.

31

8h. 3-(1-nitropropyl)cyclohexanone. Yellow Liquid, IR (neat): νmax 2943, 2887, 1714, 1556, 1541 cm-

1; 1H NMR (250 MHz, CDCl3) δ 4.41-4.25 (m, 1H), 2.55-2.38 (m, 2H), 2.37-2.07 (m, 4H), 2.06-1.73

(m, 3H), 1.72-1.35 (m, 2H), 1.01-0.93 (dt, 3H, J = 7.32 Hz and J = 2.44 Hz). 13C NMR (62.9 MHz,

CDCl3) δ 208.6, 208.6, 94.3, 43.9, 43.4, 41.6, 41.4, 41.0, 40.9, 27.7, 27.5, 24.5, 24.2, 24.1, 10.4, 10.3.

32

8i. 3-(1-nitroethyl)cyclopentanone. Colourless Liquid, IR (neat): νmax 2980, 2943, 2904, 1734, 1544

cm-1;

Diastereomer 1 - 1H NMR (250 MHz, CDCl3) δ 4.58-4.46 (m, 1H), 2.83-2.63 (m, 1H), 2.52-2.08 (m,

4H), 2.01-1.87 (m, 1H), 1.78-1.63 (m, 1H), 1.62-1.56 (d, 3H, J = 6.72 Hz). 13C NMR (62.9 MHz,

CDCl3) δ 215.3, 87.0, 41.3, 41.0, 38.1, 26.6, 18.0.

33

34

Diastereomer 2 - 1H NMR (250 MHz, CDCl3) δ 4.57-4.46 (m, 1H), 2.83-2.64 (m, 1H), 2.49-2.00 (m,

6H), 1.64 (d, 3H, J = 6.72 Hz). 13C NMR (62.9 MHz, CDCl3) δ 215.3, 87.1, 42.0, 41.2, 38.3, 25.8,

17.3.

35

36

8j. 3-(1-nitropropyl)cyclopentanone. Pale yellow Liquid, IR (neat): νmax 2974, 2939, 2916, 2883,

1747, 1556, 1539 cm-1;

Diastereomer 1 - 1H NMR (250 MHz, CDCl3) δ 4.42-4.30 (dt, 1H, J = 9.77 Hz and J = 3.66 Hz), 2.83-

2.64 (m, 1H), 2.48-1.83 (m, 6H), 1.73-1.52 (m, 2H), 1.01 (t, 3H, J = 7.32 Hz). 13C NMR (62.9 MHz,

CDCl3) δ 215.4, 94.2, 41.4, 40.3, 38.0, 26.6, 26.0, 10.2.

Diastereomer 2 - 1H NMR (250 MHz, CDCl3) δ 4.40-4.28 (dt, 1H, J = 9.76 Hz and J = 3.67 Hz), 2.82-

2.62 (m, 1H), 2.53-1.62 (m, 8H), 1.00 (t, J = 7.33 Hz, 3H). 13C NMR (62.9 MHz, CDCl3) δ 215.3,

94.1, 41.8, 40.1, 38.3, 26.0, 25.0, 10.1.

0. 01. 02. 03. 04. 05. 06. 07. 0

( p pm)

020406080100120140160180200220

( ppm)

37

8k. 4-nitropentanenitrile. Yellow Liquid, IR (neat): νmax 2995, 2945, 2899, 2249, 1556 cm-1; 1H

NMR (250 MHz, CDCl3) δ 4.78-4.64 (m, 1H), 2.53-2.31 (m, 3H), 2.17-2.03 (m, 1H), 1.64 (d, 3H, J =

6.72 Hz), 13C NMR (62.9 MHz, CDCl3) δ 117.8, 81.4, 30.3, 19.1, 14.3.

( p p m)0 . 00 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 0

38

( p p m)01 02 03 04 05 06 07 08 09 01 0 011 01 2 0

39

8l. 4-methyl-4-nitropentanenitrile. Pale Yellow Liquid, IR (neat): νmax 2993, 2943, 2875, 2250, 1533

cm-1; 1H NMR (250 MHz, CDCl3) δ 2.46-2.28 (m, 4H), 1.67 (s, 6H), 13C NMR (62.9 MHz, CDCl3) δ

118.4, 86.7, 35.8, 25.7, 12.0.

40

41

8m. 4-nitrohexanenitrile. Yellow Liquid, IR (neat): νmax 2976, 2941, 2883, 2249, 1546 cm-1; 1H NMR

(250 MHz, CDCl3) δ 4.62-4.48 (m, 1H), 2.57-2.28 (m, 3H), 2.19-1.98 (m, 1H), 1.97-1.78 (m, 2H), 1.02

(t, 3H, J = 7.33 Hz). 13C NMR (62.9 MHz, CDCl3) δ 117.8, 88.0, 28.8, 27.0, 14.3, 10.0.

42

43

8n. Methyl 3-methyl-4-nitropentanoate. Colourless Liquid, IR (neat): νmax 2978, 2954, 1732, 1548

cm-1; 1H NMR (250 MHz, CDCl3) δ 4.69-4.53 (m, 1H), 3.72-3.69 (2s, 3H), 2.72-2.18 (m, 3H), 1.55-

1.48 (2d, 3H, J = 6.71 Hz), 1.05-1.00 (2d, 3H, J = 6.71 Hz). 13C NMR (62.9 MHz, CDCl3) δ 172.1,

171.9, 86.5, 86.4, 51.8, 37.3, 37.1, 34.5, 34.4, 16.3, 15.6, 15.5, 15.4.

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 0

44

45

8o. Methyl 3-methyl-4-nitrohexanoate. Colourless Liquid, IR (neat): νmax 2976, 2954, 2883, 1730,

1552, 1544 cm-1; 1H NMR (250 MHz, CDCl3) δ 4.50-4.34 (m, 1H), 3.70 (2s, 3H), 2.61-2.41 (m, 2H),

2.35-2.16 (m, 1H), 2.15-1.92 (m, 1H), 1.91-1.68 (m, 1H), 1.04 (2d, 3H, J = 6.71 Hz), 0.97 (t, 3H, J =

7.32 Hz). 13C NMR (62.9 MHz, CDCl3) δ 172.1, 94.1, 93.6, 51.8, 51.7, 37.5, 37.1, 33.6, 33.4, 24.2,

24.1, 16.3, 15.5, 10.5, 10.4.

46

47

8p. Dimethyl-2-nitropentanedioate. Yellow Liquid. IR (neat): νmax 2960, 1736, 1560, 1535 cm-1; 1H

NMR (250 MHz, CDCl3) δ 5.33 (m, 1H), 3.85 (s, 3H), 3.71 (s, 3H), 2.60-2.35 (m, 4H). 13C NMR

(62.9 MHz, CDCl3) δ 171.9, 164.7, 86.6, 53.7, 52.0, 29.4, 25.4.

48

49

8q. 5-nitro-4-phenyl-2-hexanone. Pale Yellow Liquid. IR (neat): νmax 3062, 3032, 2941, 2902, 1714,

1556, 1541 cm-1; 1H NMR (250 MHz, CDCl3) δ 7.38-7.16 (m, 5H), 4.83-4.70 (dq, 1H, J = 6.72 Hz and

9.76 Hz), 3.77-3.65 (dt, 1H, J = 9.76 Hz and 4.28 Hz) 3.04-2.90 (dd, 1H, J = 9.77 Hz and 17.09 Hz),

2.80-2.66 (dd, 1H, J = 4.27 Hz and 17.09 Hz), 2.02 (s, 3H), 1.32 (d, 3H, J = 6.71 Hz). 13C NMR (62.9

MHz, CDCl3) δ 204.9, 138.4, 129.1, 128.2, 127.9, 46.3, 45.4, 30.4, 17.8.

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 0

50

( p p m)02 04 06 08 01 0 01 2 01 4 01 6 01 8 02 0 0

51