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Supplementary Information for publication

Synthesis of piperitone-derived halogenated lactones and their effect on aphid probing,

feeding, and settling behavior

Aleksandra Grudniewska,a Katarzyna Dancewicz,b Agata Białońska,c Zbigniew Ciunik,c

Beata Gabryśb* and Czesław Wawrzeńczyka*

aWrocław University of Environmental and Life Sciences, Department of Chemistry, Norwida 25,

50-375 Wrocław, Poland, czeslaw.wawrzenczyk@up.wroc.pl

bUniversity of Zielona Góra, Department of Biology and Ecology, Szafrana 1, 65-516 Zielona Góra,

Poland

cUniversity of Wrocław, Faculty of Chemistry, 14 F. Joliot-Curie, 50-383 Wrocław, Poland

List of contents

NMR spectra (1H NMR, COSY, 13C NMR, HSQC) NMR spectra of 2c (Figs 1-4)……………………………………………………...….…..2

NMR spectra of 3c (Figs 5-8)…………………………………………………………......4

NMR spectra of 4c (Figs 9-12)…………………………………………………………....6

NMR spectra of 5c (Figs 13-16)………………………………………………………......8

NMR spectra of 7c (Figs 17-20)………………………………………………………....10

NMR spectra of 8c (Figs 21-24)………………………………………………………....12

NMR spectra of 9c (Figs 25-28)………………………………………………………....14

NMR spectra of 10c (Figs 29-32)………………………………………………………..16

NMR spectra of 11c (Figs 33-36)………………………………………………………..18

Chiral Gas Chromatography chromatograms CGC chromatograms of 4a-c (Figs 37-39)………………………………………...….…20

CGC chromatograms of 5a-c (Figs 40-42)…………………………………………........21

CGC chromatograms of 9a-c (Figs 43-45)………………………………………...….....22

CGC chromatograms of 10a-c (Figs 46-48)…………………………………………......23

CGC chromatograms of 11a-c (Figs 49-51)………………………………………...…...24

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0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.0

3.023.13

3.06

3.32

2.17

2.65

1.001.04

2.05

2.04

2.00

0.860.870.890.90

1.081.231.251.261.341.341.361.361.361.371.371.391.571.581.591.59

2.25

4.094.104.114.12

5.495.495.505.515.515.515.525.535.535.545.54

Fig. 1. 1H NMR (CDCl3, 600 MHz) spectrum of 2c.

Fig. 2. COSY spectrum of 2c.

O

O

21'

2'

3'

4'

5'

6'

1

2c

O

O

21'

2'

3'

4'

5'

6'

1

2c

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Fig. 3. 13C NMR (CDCl3, 151 MHz) spectrum of 2c.

Fig. 4. HSQC spectrum of 2c.

O

O

21'

2'

3'

4'

5'

6'

1

2c

O

O

21'

2'

3'

4'

5'

6'

1

2c

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Fig. 5. 1H NMR (CDCl3, 600 MHz) spectrum of 3c.

0.51.01.52.02.53.03.54.04.55.05.5

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

Fig. 6. COSY spectra of 3c.

OH

O

21'

2'

3'4'

5'

6'

1

3c

OH

O

21'

2'

3'4'

5'

6'

1

3c

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Fig. 7. 13C NMR (CDCl3, 151 MHz) spectrum of 3c.

Fig. 8. HSQC spectrum of 3c.

OH

O

21'

2'

3'4'

5'

6'

1

3c

OH

O

21'

2'

3'4'

5'

6'

1

3c

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Fig. 9. 1H NMR (CDCl3, 600 MHz) spectrum of 4c.

Fig. 10. COSY spectrum of 4c.

O

O

I

123

456

789

4c

O

O

I

123

456

789

4c

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Fig. 11. 13C NMR (CDCl3, 151 MHz) spectrum of 4c.

Fig. 12. HSQC spectrum of 4c.

O

O

I

123

456

789

4c

O

O

I

123

456

789

4c

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Fig. 13. 1H NMR (CDCl3, 600 MHz) spectrum of 5c.

Fig. 14. COSY spectrum of 5c.

O

O

Br

123

456

789

5c

O

O

Br

123

456

789

5c

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Fig. 15. 13C NMR (CDCl3, 151 MHz) spectrum of 5c.

Fig. 16. HSQC spectrum of 5c.

O

O

Br

123

456

789

5c

O

O

Br

123

456

789

5c

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3.103.26

3.07

3.32

1.19

4.49

0.21

1.06

2.06

2.08

2.00

0.850.870.880.891.061.231.241.251.571.581.591.601.611.62

1.871.871.881.881.891.89

2.24

4.094.094.104.104.114.124.13

5.505.505.525.535.545.545.545.555.555.56

Fig. 17. 1H NMR (CDCl3, 600 MHz) spectrum of 7c.

Fig. 18. COSY spectrum of 7c.

O

O

21'

2'

3'

4'5'

6'

1

7c

O

O

21'

2'

3'

4'5'

6'

1

7c

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14.31

19.21

19.58

21.89

26.68

31.90

34.54

34.66

41.60

47.59

59.92

76.78

77.00

77.21

129.64

135.09

171.88

Fig. 19. 13C NMR (CDCl3, 151 MHz) spectrum of 7c.

Fig. 20. HSQC spectrum of 7c.

O

O

21'

2'

3'

4'5'

6'

1

7c

O

O

21'

2'

3'

4'5'

6'

1

7c

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3.012.94

3.04

1.20

4.02

1.02

2.06

2.00

0.860.870.890.90

1.101.431.581.591.601.611.621.631.64

1.891.891.901.901.911.91

2.29

5.535.545.565.565.575.58

Fig. 21. 1H NMR (CDCl3, 600 MHz) spectrum of 8c.

0.51.01.52.02.53.03.54.04.55.05.56.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

Fig. 22. COSY spectrum of 8c.

OH

O

21'

2'

3'

4'5'

6'

1

8c

OH

O

21'

2'

3'

4'5'

6'

1

8c

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-100102030405060708090100110120130140150160170180190200210

Fig. 23. 13C NMR (CDCl3, 151 MHz) spectrum of 8c.

Fig. 24. HSQC spectrum of 8c.

OH

O

21'

2'

3'

4'5'

6'

1

8c

OH

O

21'

2'

3'

4'5'

6'

1

8c

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0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.4

Fig. 25. 1H NMR (CDCl3, 600 MHz) spectrum of 9c.

Fig. 26. COSY spectrum of 9c.

O

O

I

123

456

789

9c

O

O

I

123

456

789

9c

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Fig. 27. 13C NMR (CDCl3, 151 MHz) spectrum of 9c.

Fig. 28. HSQC spectrum of 9c.

O

O

I

123

456

789

9c

O

O

I

123

456

789

9c

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0.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.8

Fig. 29. 1H NMR (CDCl3, 600 MHz) spectrum of 10c.

Fig. 30. COSY spectrum of 10c.

O

O

Br

123

456

789

10c

O

O

Br

123

456

789

10c

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Fig. 31. 13C NMR (CDCl3, 151 MHz) spectrum of 10c.

Fig. 32. HSQC spectrum of 10c.

O

O

Br

123

456

789

10c

O

O

Br

123

456

789

10c

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0.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.0

Fig. 33. 1H NMR (CDCl3, 600 MHz) spectrum of 11c.

0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

Fig. 34. COSY spectrum of 11c.

O

O

Cl

123

456

789

11c

O

O

Cl

123

456

789

11c

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Fig. 35. 13C NMR (CDCl3, 151 MHz) spectrum of 11c.

Fig. 36. HSQC spectrum of 11c.

O

O

Cl

123

456

789

11c

O

O

Cl

123

456

789

11c

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Fig. 37. CGC chromatogram of (+)-4a (ee = 97%).

Fig. 38. CGC chromatogram of (–)-4b (ee = 96%).

Fig. 39. CGC chromatogram of (±)-4c.

O

O

I

123

456

789

(+)-(1S,4R,5R,6R)-4a

O

O

I

123

456

789

(−)-(1R,4S,5S,6S)-4b

O

O

I

123

456

789

(−)-(1R,4S,5S,6S)-4b

O

O

I

123

456

789

(+)-(1S,4R,5R,6R)-4a

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Fig. 40. CGC chromatogram of (+)-5a (ee = 97%).

Fig. 41. CGC chromatogram of (–)-5b (ee = 91%).

Fig. 42. CGC chromatogram of (±)-5c.

O

O

Br

123

456

789

(+)-(1S,4R,5R,6R)-5a

O

O

Br

123

456

789

(−)-(1R,4S,5S,6S)-5b

O

O

Br

123

456

789

(+)-(1S,4R,5R,6R)-5a

O

O

Br

123

456

789

(−)-(1R,4S,5S,6S)-5b

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Fig. 43. CGC chromatogram of (+)-9a (ee = 98%).

Fig. 44. CGC chromatogram of (–)-9b (ee = 94%).

Fig. 45. CGC chromatogram of (±)-9c.

O

O

I

123

456

789

(+)-(1S,4S,5R,6R)-9a

O

O

I

123

456

789

(−)-(1R,4R,5S,6S)-9b

O

O

I

123

456

789

(+)-(1S,4S,5R,6R)-9a

O

O

I

123

456

789

(−)-(1R,4R,5S,6S)-9b

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Fig. 46. CGC chromatogram of (+)-10a (ee = 94%).

Fig. 47. CGC chromatogram of (–)-10b (ee = 96%).

Fig. 48. CGC chromatogram of (±)-10c.

O

O

Br

123

456

789

(+)-(1S,4S,5R,6R)-10a

O

O

Br

123

456

789

(−)-(1R,4R,5S,6S)-10b

O

O

Br

123

456

789

(−)-(1R,4R,5S,6S)-10b

O

O

Br

123

456

789

(+)-(1S,4S,5R,6R)-10a

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Fig. 49. CGC chromatogram of (–)-11a (ee = 91%).

Fig. 50. CGC chromatogram of (+)-11b (ee = 96%).

Fig. 51. CGC chromatogram of (±)-11c.

O

O

Cl

123

456

789

(−)-(1S,4S,5R,6R)-11a

O

O

Cl

123

456

789

(+)-(1R,4R,5S,6S)-11b

O

O

Cl

123

456

789

(−)-(1S,4S,5R,6R)-11a

O

O

Cl

123

456

789

(+)-(1R,4R,5S,6S)-11b

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