1

Supporting Information

Phosphonium ionic liquids: design, synthesis and evaluation of biodegradability

Farzad Atefi, M. Teresa Garcia, Robert D. Singer and Peter J. Scammells

Table of Contents 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium bromide 2a 3 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium bromide 2a 4 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium bromide 2a 5 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium bromide 3a 6 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium bromide 3a 7 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium bromide 3a 8 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium bromide 4a 9 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium bromide 4a 10 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium bromide 4a 11 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(acetoxybutyl))phosphonium iodide 5a 12 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(acetoxybutyl))phosphonium iodide 5a 13 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(acetoxybutyl))phosphonium iodide 5a 14 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium triflimide 2b 15 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium triflimide 2b 16 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium triflimide 2b 17 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium octylsulfate 2c 18 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium octylsulfate 2c 19 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium octylsulfate 2c 20 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium triflimide 3b 21 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium triflimide 3b 22 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium triflimide 3b 23 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium octylsulfate 3c 24 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium octylsulfate 3c 25 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium octylsulfate 3c 26 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium triflimide 4b 27 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium triflimide 4b 28 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium triflimide 4b 29 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium octylsulfate 4c 30 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium octylsulfate 4c 31 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium octylsulfate 4c 32 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(acetoxybutyl))phosphonium triflimide 5b 33 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(acetoxybutyl))phosphonium triflimide 5b 34 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(acetoxybutyl))phosphonium triflimide 5b 35 1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(acetoxybutyl))phosphonium octylsulfate 5c 36 13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(acetoxybutyl))phosphonium octylsulfate 5c 37 31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(acetoxybutyl))phosphonium octylsulfate 5c 38 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium bromide 7a 39 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium bromide 7a 40 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium bromide 7a 41 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium bromide 8a 42 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium bromide 8a 43 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium bromide 8a 44 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium bromide 9a 45 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium bromide 9a 46 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium bromide 9a 47 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium iodide 10a 48 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium iodide 10a 49

2

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium iodide 10a 50 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexylallylphosphonium bromide 11a 51 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexylallylphosphonium bromide 11a 52 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexylallylphosphonium bromide 11a 53 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(methoxymethyl)phosphonium chloride 12a 54 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(methoxymethyl)phosphonium chloride 12a 55 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(methoxymethyl)phosphonium chloride 12a 56 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium bromide 13a 57 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium bromide 13a 58 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium bromide 13a 59 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium triflimide 7b 60 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium triflimide 7b 61 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium triflimide 7b 62 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium octylsulfate 7c 63 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium octylsulfate 7c 64 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium octylsulfate 7c 65 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium triflimide 8b 66 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium triflimide 8b 67 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium triflimide 8b 68 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium octylsulfate 8c 69 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium octylsulfate 8c 70 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium octylsulfate 8c 71 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium triflimide 9b 72 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium triflimide 9b 73 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium triflimide 9b 74 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium octylsulfate 9c 75 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium octylsulfate 9c 76 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium octylsulfate 9c 77 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium triflimide 10b 78 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium triflimide 10b 79 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium triflimide 10b 80 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium octylsulfate 10c 81 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium octylsulfate 10c 82 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium octylsulfate 10c 83 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexylallylphosphonium triflimide 11b 84 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexylallylphosphonium triflimide 11b 85 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexylallylphosphonium triflimide 11b 86 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexylallylphosphonium octylsulfate 11c 87 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexylallylphosphonium octylsulfate 11c 88 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexylallylphosphonium octylsulfate 11c 89 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(methoxymethyl)phosphonium triflimide 12b 90 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(methoxymethyl)phosphonium triflimide 12b 91 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(methoxymethyl)phosphonium triflimide 12b 92 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(methoxymethyl)phosphonium octylsulfate 12c 93 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(methoxymethyl)phosphonium octylsulfate 12c 94 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(methoxymethyl)phosphonium octylsulfate 12c 95 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium triflimide 13b 96 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium triflimide 13b 97 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium triflimide 13b 98 1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium octylsulfate 13c 99 13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium octylsulfate 13c 100 31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium octylsulfate 13c 101

3

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium bromide (2a)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.14

4.12

4.10

3.89

3.85

2.73

2.69

2.65

2.61

1.92

1.80

1.68

1.66

1.64

1.61

1.50

1.46

1.42

1.37

1.33

1.30

1.24

0.96

0.93

0.91

2.00

1.95

2.98

5.93

6.01

5.06

15.29

2.90

4

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium bromide (2a)

ppm (t1)

255075100125150

5

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium bromide (2a)

ppm (t1)

-75-50-250255075

35.3

6

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium bromide (3a)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.18

4.16

4.14

3.90

3.85

2.74

2.70

2.66

2.62

1.92

1.79

1.70

1.67

1.65

1.63

1.61

1.50

1.46

1.42

1.37

1.33

1.32

1.30

1.24

0.90

0.88

0.86

2.00

2.00

3.13

6.29

6.63

5.34

19.40

2.99

7

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium (3a)

ppm (t1)

255075100125150

8

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium bromide (3a)

ppm (f1)

-50-250255075

35.3

9

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium bromide (4a)

ppm (t1)

0.501.001.502.002.503.003.504.004.50

4.17

4.15

4.13

3.88

3.84

2.73

2.69

2.65

2.61

1.92

1.79

1.70

1.67

1.62

1.60

1.50

1.46

1.41

1.37

1.32

1.30

1.28

1.26

0.86

0.84

2.00

2.00

3.17

6.34

6.59

5.39

3.19

23.63

10

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium bromide (4a)

ppm (t1)

255075100125150

11

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium bromide (4a)

ppm (f1)

-75-50-250255075

35.3

12

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(acetoxybutyl))phosphonium iodide (5a)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.09

4.07

4.05

2.62

2.58

2.54

2.49

2.35

2.31

2.29

2.25

2.01

1.88

1.77

1.72

1.69

1.66

1.51

1.47

1.44

1.41

1.37

1.34

2.00

3.61

2.03

3.07

6.31

8.09

6.36

14.51

13

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(acetoxybutyl))phosphonium iodide (5a)

ppm (t1)

255075100125150

14

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(acetoxybutyl))phosphonium iodide (5a)

ppm (f1)

-50-2502550

34.2

15

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium triflimide (2b)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.15

4.13

4.10

3.85

3.80

2.70

2.66

2.62

2.58

1.91

1.81

1.71

1.69

1.67

1.64

1.62

1.50

1.46

1.41

1.37

1.32

1.30

1.26

1.24

0.96

0.94

0.91

2.00

1.92

2.94

5.81

6.30

5.26

15.37

3.12

16

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium triflimide (2b)

ppm (t1)

255075100125150

17

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium triflimide (2b)

ppm (f1)

-50-250255075

35.2

18

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium octylsulfate (2c)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.14

4.12

4.10

3.86

3.81

3.69

3.66

3.64

2.69

2.65

2.62

2.58

1.91

1.80

1.70

1.69

1.66

1.64

1.62

1.49

1.45

1.41

1.36

1.32

1.29

1.28

1.25

0.96

0.93

0.91

0.88

0.86

0.84

2.00

2.03

3.17

6.18

6.57

5.54

27.06

2.93

2.99

2.03

19

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium octylsulfate (2c)

ppm (t1)

255075100125150

20

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(propoxycarbonylmethyl)phosphonium octylsulfate (2c)

ppm (f1)

-50-250255075

35.3

21

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium triflimide (3b)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.19

4.16

4.14

3.85

3.80

2.70

2.66

2.62

2.58

1.92

1.81

1.71

1.68

1.66

1.64

1.61

1.50

1.46

1.41

1.37

1.36

1.34

1.32

1.31

1.24

0.91

0.89

0.86

2.00

1.97

3.10

6.05

6.43

5.06

19.49

3.10

22

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium triflimide (3b)

ppm (t1)

255075100125150

23

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium triflimide (3b)

ppm (f1)

-50-250255075

35.2

24

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium octylsulfate (3c)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.18

4.16

4.14

3.85

3.81

3.69

3.67

3.65

2.71

2.67

2.63

2.59

1.92

1.80

1.71

1.68

1.66

1.63

1.61

1.50

1.48

1.46

1.41

1.37

1.36

1.33

1.32

1.31

1.29

1.25

0.91

0.88

0.86

0.84

2.00

1.95

2.10

3.04

6.09

6.42

5.28

31.66

6.26

25

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium octylsulfate (3c)

ppm (f1)

255075100125150

26

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(pentoxycarbonylmethyl)phosphonium octylsulfate (3c)

ppm (f1)

-50-250255075

35.3

27

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium triflimide (4b)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.18

4.16

4.14

3.85

3.80

2.70

2.66

2.62

2.58

1.91

1.81

1.71

1.68

1.65

1.63

1.61

1.50

1.46

1.41

1.37

1.32

1.30

1.28

1.27

0.89

0.87

0.84

2.00

2.05

3.05

6.00

6.30

5.37

23.50

3.14

28

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium triflimide (4b)

ppm (f1)

255075100125150

29

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium triflimide (4b)

ppm (f1)

-50-250255075

35.2

30

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium octylsulfate (4c)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.18

4.16

4.14

3.85

3.81

3.69

3.67

3.65

2.71

2.67

2.63

2.59

1.92

1.80

1.72

1.70

1.67

1.65

1.63

1.60

1.50

1.48

1.46

1.43

1.41

1.37

1.32

1.30

1.28

1.25

0.88

0.87

0.86

0.84

2.00

2.12

1.91

2.90

5.93

6.58

5.30

36.64

6.58

31

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium octylsulfate (4c)

ppm (f1)

255075100125150

32

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(heptoxycarbonylmethyl)phosphonium octylsulfate (4c)

ppm (f1)

-50-250255075

35.3

33

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(acetoxybutyl))phosphonium triflimide (5b)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.10

4.08

4.06

2.58

2.54

2.50

2.46

2.32

2.28

2.27

2.23

2.01

1.90

1.87

1.79

1.74

1.72

1.71

1.68

1.63

1.51

1.47

1.43

1.40

1.35

1.33

1.27

1.24

2.00

3.64

2.09

3.08

20.50

14.18

34

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(acetoxybutyl))phosphonium triflimide (5b)

ppm (f1)

255075100125150

35

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(acetoxybutyl))phosphonium triflimide (5b)

ppm (f1)

-50-250255075

34.0

36

1H NMR (DMSO-d6, 300 MHz) Tricyclohexyl(acetoxybutyl))phosphonium octylsulfate (5c)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.10

4.08

4.05

3.69

3.67

3.65

2.59

2.55

2.51

2.48

2.33

2.29

2.28

2.24

2.01

1.91

1.88

1.79

1.74

1.72

1.70

1.67

1.63

1.50

1.48

1.44

1.40

1.36

1.33

1.25

0.88

0.86

0.84

1.89

3.87

2.17

3.13

20.33

26.17

2.67

2.00

37

13C NMR (DMSO-d6, 150 MHz) Tricyclohexyl(acetoxybutyl))phosphonium octylsulfate (5c)

ppm (f1)

255075100125150

38

31P NMR (DMSO-d6, 121 MHz) Tricyclohexyl(acetoxybutyl))phosphonium octylsulfate (5c)

ppm (f1)

-50-250255075

34.0

39

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium bromide (7a)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.11

4.09

4.07

3.95

3.90

2.41

2.38

2.36

2.35

2.31

1.68

1.66

1.64

1.61

1.59

1.55

1.53

1.52

1.50

1.48

1.45

1.39

1.37

1.35

1.32

1.29

1.28

1.27

0.93

0.90

0.89

0.88

0.86

0.84

2.00

1.94

6.03

8.30

12.16

18.38

40

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium bromide (7a)

ppm (f1)

255075100125150

41

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium bromide (7a)

ppm (f1)

-50-250255075

34.1

42

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium bromide (8a)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.15

4.13

4.10

3.90

3.86

2.38

2.35

2.34

2.33

2.28

1.63

1.60

1.58

1.53

1.50

1.39

1.37

1.29

1.28

1.27

0.89

0.87

0.86

2.00

1.84

5.86

12.22

22.02

8.11

43

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium bromide (8a)

ppm (f1)

255075100125150

44

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium bromide (8a)

ppm (f1)

-50-250255075

34.2

45

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium bromide (9a)

ppm (f1)

0.000.501.001.502.002.503.003.504.004.50

4.15

4.13

4.10

3.95

3.90

2.41

2.38

2.36

2.36

2.34

2.31

1.62

1.60

1.58

1.56

1.53

1.51

1.48

1.45

1.39

1.37

1.35

1.29

1.28

1.27

1.26

0.89

0.87

0.86

0.84

5.96

1.91

2.00

8.66

26.07

12.85

46

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium bromide (9a)

ppm (f1)

255075100125150

47

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium bromide (9a)

ppm (f1)

-50-250255075

34.1

48

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium iodide (10a)

ppm (t1)

0.000.501.001.502.002.503.003.504.00

4.05

4.03

4.01

2.00

1.75

1.72

1.70

1.68

1.66

1.59

1.57

1.52

1.50

1.48

1.45

1.43

1.40

1.38

1.36

1.34

1.30

1.29

1.28

0.89

0.86

0.84

2.35

2.29

2.27

2.25

2.24

2.20

2.00

3.06

2.10

9.59

7.93

26.18

49

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium iodide (10a)

ppm (f1)

255075100125150

50

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium iodide (10a)

ppm (f1)

-50-250255075

35.0

51

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexylallylphosphonium bromide (11a)

ppm (f1)

0.000.501.001.502.002.503.003.504.004.505.005.50

5.92

5.90

5.89

5.87

5.87

5.86

5.85

5.84

5.83

5.82

5.81

5.80

5.79

5.79

5.78

5.77

5.76

5.75

5.74

5.48

5.47

5.46

5.46

5.42

5.42

5.41

5.40

5.35

5.35

5.34

5.32

5.31

5.31

3.36

3.33

3.31

3.28

2.32

2.29

2.27

2.26

2.25

2.22

1.55

1.52

1.50

1.47

1.39

1.37

1.34

1.32

1.29

1.28

1.27

0.88

0.86

0.84

1.04

1.13

1.00

6.42

6.20

18.24

9.54

52

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexylallylphosphonium bromide (11a)

ppm (f1)

255075100125150

53

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexylallylphosphonium bromide (11a)

ppm (f1)

-50-250255075

33.3

54

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(methoxymethyl)phosphonium chloride (12a)

ppm (f1)

0.000.501.001.502.002.503.003.504.004.50

4.55

4.53

3.41

2.39

2.36

2.34

2.33

2.28

1.52

1.51

1.50

1.47

1.44

1.37

1.35

1.33

1.28

1.27

1.26

0.87

0.85

0.83

3.10

6.00

2.11

9.21

5.91

18.18

55

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(methoxymethyl)phosphonium chloride (12a)

ppm (f1)

255075100125150

56

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(methoxymethyl)phosphonium chloride (12a)

ppm (f1)

-50-2502550

33.0

57

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium bromide (13a)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

3.80

3.78

3.76

3.74

3.72

3.70

3.68

3.66

3.64

3.47

3.45

3.43

2.51

2.49

2.47

2.45

2.43

2.31

2.29

2.27

2.26

2.24

2.21

1.57

1.54

1.52

1.49

1.47

1.44

1.39

1.37

1.35

1.32

1.29

1.28

1.27

1.25

0.88

0.86

0.84

6.00

9.49

6.27

18.18

3.14

2.08

58

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium bromide (13a)

ppm (f1)

255075100125150

59

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium bromide (13a)

ppm (f1)

-50-250255075

34.4

60

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium triflimide (7b)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.13

4.11

4.08

3.81

3.77

2.33

2.31

2.29

2.28

2.26

2.23

1.68

1.65

1.63

1.61

1.56

1.53

1.51

1.48

1.41

1.39

1.37

1.34

1.31

1.30

1.29

1.26

0.94

0.92

0.90

0.89

0.88

0.86

2.00

1.95

5.98

26.62

12.51

61

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium triflimide (7b)

ppm (f1)

255075100125150

62

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium triflimide (7b)

ppm (f1)

-50-2502550

34.2

63

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium octylsulfate (7c)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.12

4.10

4.08

3.84

3.80

3.70

3.68

3.66

2.36

2.33

2.31

2.31

2.26

1.67

1.65

1.62

1.60

1.55

1.53

1.51

1.48

1.40

1.38

1.36

1.30

1.28

1.25

0.94

0.91

0.88

0.86

0.84

2.00

1.92

2.19

5.94

15.62

10.85

28.67

64

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium octylsulfate (7c)

ppm (f1)

255075100125150

65

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(propoxycarbonylmethyl)phosphonium octylsulfate (7c)

ppm (t1)

-50-250255075

34.2

66

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium triflimide (8b)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.16

4.14

4.12

3.81

3.76

2.33

2.31

2.29

2.28

2.23

1.62

1.60

1.56

1.53

1.51

1.48

1.41

1.39

1.37

1.33

1.31

1.30

1.29

0.90

0.88

0.86

2.00

1.88

5.91

30.28

12.54

67

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium triflimide (8b)

ppm (f1)

255075100125150

68

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium triflimide (8b)

ppm (f1)

-50-250255075

34.2

69

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium octylsulfate (8c)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.15

4.13

4.11

3.84

3.79

3.70

3.68

3.66

2.36

2.33

2.31

2.30

2.29

2.26

1.64

1.62

1.59

1.58

1.55

1.53

1.51

1.48

1.46

1.40

1.38

1.36

1.33

1.30

1.29

1.28

1.25

0.90

0.88

0.88

0.86

0.85

2.00

1.92

1.99

5.97

10.59

32.67

15.32

70

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium octylsulfate (8c)

ppm (f1)

255075100125150

71

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(pentoxycarbonylmethyl)phosphonium octylsulfate (8c)

ppm (f1)

-50-250255075

34.2

72

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium triflimide (9b)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.16

4.14

4.12

3.81

3.76

2.33

2.30

2.28

2.28

2.26

2.23

1.64

1.61

1.59

1.56

1.53

1.51

1.48

1.41

1.39

1.36

1.31

1.30

1.29

1.28

0.90

0.88

0.87

0.86

2.00

1.85

5.95

8.31

26.08

12.20

73

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium triflimide (9b)

ppm (f1)

255075100125150

74

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium triflimide (9b)

ppm (f1)

-50-250255075

34.2

75

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium octylsulfate (9c)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.15

4.13

4.11

3.83

3.78

3.70

3.68

3.66

2.36

2.33

2.31

2.30

2.29

2.26

1.63

1.61

1.59

1.56

1.53

1.51

1.48

1.40

1.38

1.36

1.30

1.29

1.28

1.25

0.90

0.88

0.87

0.86

0.85

0.84

1.87

2.00

2.08

5.84

10.03

36.25

15.33

76

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium octylsulfate (9c)

ppm (f1)

255075100125150

77

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(heptoxycarbonylmethyl)phosphonium octylsulfate (9c)

ppm (f1)

-50-250255075

34.2

78

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium triflimide (10b)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.07

4.05

4.02

2.28

2.23

2.23

2.21

2.19

2.18

2.13

2.00

1.76

1.73

1.71

1.69

1.67

1.61

1.59

1.56

1.55

1.53

1.50

1.48

1.45

1.44

1.42

1.40

1.37

1.35

1.31

1.30

1.29

0.90

0.88

0.86

2.00

8.21

3.04

2.15

26.10

9.31

79

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium triflimide (10b)

ppm (f1)

255075100125150

80

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium triflimide (10b)

ppm (f1)

-50-250255075

35.0

81

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium octylsulfate (10c)

ppm (f1)

0.000.501.001.502.002.503.003.504.004.50

4.06

4.04

4.02

3.70

3.68

3.66

2.31

2.26

2.23

2.21

2.20

2.16

2.00

1.75

1.73

1.70

1.68

1.66

1.59

1.56

1.52

1.50

1.48

1.45

1.41

1.39

1.36

1.34

1.31

1.30

1.29

1.25

0.90

0.88

0.86

0.84

1.82

2.00

8.58

3.11

2.30

38.61

12.38

82

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium octylsulfate (10c)

ppm (f1)

255075100125150

83

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(acetoxybutyl))phosphonium octylsulfate (10c)

ppm (f1)

-50-250255075

35.0

84

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexylallylphosphonium triflimide (11b)

ppm (f1)

0.501.001.502.002.503.003.504.004.505.005.50

5.87

5.85

5.85

5.84

5.83

5.82

5.81

5.80

5.80

5.79

5.78

5.77

5.76

5.76

5.75

5.74

5.73

5.72

5.46

5.45

5.44

5.44

5.40

5.40

5.39

5.37

5.35

5.34

3.22

3.20

3.17

3.14

2.23

2.21

2.19

2.18

2.16

2.13

1.56

1.53

1.50

1.48

1.42

1.39

1.37

1.35

1.32

1.31

1.29

1.27

0.91

0.88

0.86

1.00

2.00

2.01

5.90

5.92

18.15

9.00

85

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexylallylphosphonium triflimide (11b)

ppm (f1)

255075100125150

86

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexylallylphosphonium triflimide (11b)

ppm (f1)

-50-250255075

33.4

87

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexylallylphosphonium octylsulfate (11c)

ppm (f1)

0.501.001.502.002.503.003.504.004.505.005.506.00

5.88

5.86

5.85

5.85

5.84

5.83

5.82

5.81

5.80

5.80

5.79

5.78

5.77

5.76

5.76

5.75

5.74

5.72

5.46

5.46

5.45

5.44

5.41

5.40

5.39

5.39

5.37

5.36

5.35

5.33

5.33

5.32

3.71

3.68

3.66

3.26

3.23

3.20

3.18

2.26

2.23

2.21

2.20

2.19

2.16

1.55

1.52

1.50

1.47

1.45

1.40

1.38

1.36

1.36

1.33

1.31

1.29

1.28

1.27

1.25

0.90

0.88

0.86

0.85

0.84

1.00

2.00

1.84

2.00

5.91

8.19

27.91

11.77

88

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexylallylphosphonium octylsulfate (11c)

ppm (f1)

255075100125150

89

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexylallylphosphonium octylsulfate (11c)

ppm (f1)

-50-250255075

33.3

90

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(methoxymethyl)phosphonium triflimide (12b)

ppm (f1)

0.501.001.502.002.503.003.504.00

4.38

4.36

3.44

2.28

2.25

2.23

2.22

2.21

2.20

2.17

1.59

1.57

1.54

1.51

1.50

1.49

1.46

1.44

1.41

1.39

1.37

1.35

1.31

1.30

1.29

1.27

0.91

0.88

0.86

2.00

3.02

6.00

6.39

18.65

9.32

91

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(methoxymethyl)phosphonium triflimide (12b)

ppm (f1)

255075100125150

92

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(methoxymethyl)phosphonium triflimide (12b)

ppm (f1)

-50-250255075

33.1

93

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(methoxymethyl)phosphonium octylsulfate (12c)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

4.42

4.40

3.71

3.69

3.67

3.43

2.30

2.28

2.26

2.25

2.23

2.20

1.58

1.56

1.53

1.51

1.49

1.40

1.38

1.36

1.30

1.29

1.28

1.25

0.90

0.88

0.86

0.84

2.00

2.07

3.03

6.15

8.00

28.20

12.31

94

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(methoxymethyl)phosphonium octylsulfate (12c)

ppm (f1)

255075100125150

95

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(methoxymethyl)phosphonium octylsulfate (12c)

ppm (f1)

-50-250255075

33.0

96

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium triflimide (13b)

ppm (f1)

0.000.501.001.502.002.503.003.504.004.50

3.82

3.80

3.78

3.76

3.74

3.72

2.45

2.43

2.41

2.38

2.36

2.25

2.22

2.20

2.19

2.15

1.53

1.51

1.48

1.45

1.41

1.39

1.31

1.30

1.29

0.90

0.88

0.86

2.00

2.04

6.18

6.12

18.68

9.39

97

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium triflimide (13b)

ppm (f1)

255075100125150

98

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium triflimide (13b)

ppm (f1)

-50-250255075

34.5

99

1H NMR (DMSO-d6, 300 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium octylsulfate (13c)

ppm (f1)

0.000.501.001.502.002.503.003.504.00

3.82

3.80

3.78

3.76

3.73

3.71

3.69

3.66

2.47

2.45

2.43

2.41

2.39

2.27

2.24

2.22

2.21

2.19

2.17

1.57

1.55

1.52

1.50

1.49

1.47

1.45

1.40

1.38

1.36

1.31

1.29

1.28

1.25

0.90

0.87

0.86

0.84

1.92

4.00

6.03

8.28

28.51

12.36

100

13C NMR (DMSO-d6, 150 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium octylsulfate (13c)

ppm (f1)

255075100125150

101

31P NMR (DMSO-d6, 121 MHz) Tri-n-hexyl(2-hydroxyethyl)phosphonium octylsulfate (13c)

ppm (f1)

-50-250255075

34.4