synthetic approach towards ‘click’ modified chalcone based ... · gurjaspreet singh,* jandeep...

1

Synthetic approach towards ‘Click’ modified chalcone based organotriethoxysilanes; UV–Vis study

Gurjaspreet Singh,* Jandeep Singh, Satinderpal Singh Mangat, Aanchal Arora

Department of Chemistry and Centre of Advanced Studies, Panjab University, Chandigarh, 160014, India.

*Corresponding Author

Email: [email protected], Phone: +91-0172-2534428

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2014

mailto:[email protected]

2

1. General reaction procedure

2. NMR (1H, 13C), uv-vis spectra of silane 4a

3. NMR (1H, 13C), of silane 4b

4. NMR (1H, 13C), uv-vis spectra and MS of silane 4c

5. NMR (1H, 13C), uv-vis spectra of silane 4d

6. NMR (1H, 13C), uv-vis spectra of silane 4e

7. NMR (1H, 13C), uv-vis spectra and HRMS of silane 4f

8. NMR (1H, 13C), uv-vis spectra of silane 4g

9. NMR (1H, 13C), uv-vis spectra of silane 4h

10. NMR (1H, 13C), uv-vis spectra and HRMS of silane 4i

11. NMR (1H, 13C), uv-vis spectra of silane 6a

12. NMR (1H, 13C), uv-vis spectra of silane 6b

13. NMR (1H, 13C) and MS of silane 6c

14. NMR (1H, 13C), uv-vis spectra of silane 6d

15. NMR (1H, 13C), uv-vis spectra of silane 6e

16. NMR (1H, 13C), uv-vis spectra of silane 6f

4–5

6–8

9–10

11–14

15–17

18–20

21–24

25–27

28–30

31–34

35–37

38–40

41–43

44–46

47–49

50–52

3

17. NMR (1H, 13C), uv-vis spectra of silane 6g

18. NMR (1H, 13C), uv-vis spectra of silane 6h

19. NMR (1H, 13C), uv-vis spectra of silane 6i

53–55

56–58

59–61

4

Experimental

Caution! Azide compounds are explosive to heat and shock. Great care and protection is required for handling of these compounds.

5.1. General material and methods: All the syntheses were carried out under dry nitrogen atmosphere using vacuum glass line. The organic

solvents used were dried and purified according to the standard procedure and stored under dry nitrogen atmosphere.

bromotris(triphenylphosphine)copper(I) (Aldrich), γ-chloropropyltriethoxysilane (ClPTES) (Aldrich), propargyl bromide (80% wt. solution in

toluene) (Aldrich), sodium azide (SDFCL), potassium carbonate (THOMAS BAKER), N,N-dimethylformamide (SDFCL), were used as

supplied. Acetophenone (SDFCL), 2-hydroxyacetophenone (SDFCL), 3-hydroxyacetophenone (SDFCL), 4-hydroxyacetophenone (SDFCL),

salicylaldehyde (Aldrich), 3-hydroxybenzaldehyde (SDFCL), 4-hydroxybenzaldehyde (SDFCL), p-methoxyacetophenone (HIMEDIA), 2,4-

dimethoxyacetophenone (HIMEDIA) were used as supplied for synthesis of terminal alkynes 3a–3i and 5a–5i.

Infrared spectrum was obtained neat on a Thermo Scientific Fischer spectrometer. Multinuclear NMR (1H, 13C) spectra were recorded on a

Bruker advance II 400 spectrometer (in CDCl3) at 25 °C. HRMS data of all synthesized compounds 4a–4i and 6a–6i was recorded on Waters

QQ–TOF micro Mass Spectrometer. UV–Vis spectra were recorded on JASCO V–530 UV–Vis spectrophotometer. The elemental data were

obtained on Thermo Scientific flash 2000 organic elemental analyzer.

AzPTES was synthesized according to known procedure in literature.20

Synthesis of compounds 2a(i–iii) and 2b(i–iii)

To a uniformly stirred solution of 1a/1b (2g, 16.40 mmol, 1 equiv) in 15 ml of DMF cooled in ice bath, added K2CO3 (6.76 g, 47.2 mmol, 3

equiv) and propargyl bromide (2.15 g, 1.61 ml, 18.06 mmol, 1.1 equiv) dropwise within 5 min. After complete addition of reactants, the

temperature of reaction mixture was slowly raised to 30 ℃ and stirred for 14 h. The reaction was then quenched by addition of ice cold water

and filtered the solid product (in case of 2a(i, iii); 2b(i–iii)). In case of low melting solids 2a(ii), extraction was carried out with ethyl acetate.

5

The combined organic layers were dried over anhydrous MgSO4 and vacuum evaporation of solvent resulted into the formation of desired

compound. The solid alkynes were recrystallized by dissolving in minimum amount of ethanol.

Synthesis of compounds 3a–3i/5a–5i

To a uniformly stirred solution of 2a (1 equiv) and KOH (0.02 g, 0.36 mmol) in 15 ml of ethanol, ethanolic solution of substituted acetophenone

1c(a–c) or 2b (1 equiv) was added slowly within 10 min. The reaction was stirred for 4 h and monitored the end point using TLC (hexane:ethyl

acetate (8:2)). On completion, the reaction was quenched by ice cold water, extracted with methylene chloride and washed twice with brine

solution. The combined organic phases were dried over anhydrous MgSO4 and vacuum evaporation afforded the desired product.

Synthesis of compounds 4a–4i/6a–6i

In a 25 ml two neck round bottom flask, to stirred solution of alkyne 3a–3i/5a–5i in 1:1 solution of THF:TEA (3ml), added AzPTES (1 equiv for

3a–3i and 2 equiv for 5a–5i) followed by catalyst (0.02 mmol for 3a–3i and 0.04 mmol for 5a–5i) loading under inert atmosphere. Slowly the

temperature of reaction mixture was raised to 65 ℃ and stirred vigorously for 3 h. After completion of reaction, it was cooled to room

temperature, filtered and vacuum evaporation of solvent resulted in desired nPTES 4a–4i/6a–6i.

8

250 275 300 325 350 375 400-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

4a

Abso

rban

ce

Wavelength (nm)

11

4c

13

WATERS, Q-TOF MICROMASS (LC-MS) SAIF/CIL,PANJAB UNIVERSITY,CHANDIGARH

m/z80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560

%

0

100JANDEEP 4b 20 (0.251) Cm (10:30) TOF MS ES+

7.30e3532.37299

430.31819

301.11059102.2

900279.2611

393.3692362.2

490347.2488331.2

273

464.31171

431.3358 450.3

223

465.3332

533.32066

534.3403

14

250 300 350 400-0.8

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

4c

Abso

rban

ce

Wavelength (nm)

15

4d

17

250 275 300 325 350 375 400

0.0

0.5

1.0

1.5

2.0

2.5 4d

Abso

rban

ce

Wavelength (nm)

18

4e

20

250 275 300 325 350 375

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0 4e

Abso

rban

ce

Wavelength (nm)

21

4f

23


m/z50 75 100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775

%

0

100JANDEEP 4f 21 (0.303) AM (Top,4, Ar,5000.0,556.28,0.70,LS 10); Sm (Mn, 2x3.00); Sb (1,40.00 ); Cm (21:24) 1: TOF MS ES+

8.84e3562.22888843

494.20714839430.1759

4616

362.14944118

279.09411998

84.9628904 206.5573

701125.9861

680176.1075

467

232.5817339

289.60181547

359.2391337

363.15001065

412.1662289

431.1855872

432.1760238

495.21351327

559.23371099

496.2099340

611.32205189

563.23272557

564.2375535

612.34481684

624.2109765

625.2200243 698.2740

160763.3534

130785.3771

57

24

250 275 300 325 350 375 400

0.0

0.5

1.0

1.5

2.0

2.5

3.04f

Abso

rban

ce

Wavelength (nm)

25

4g

27

250 275 300 325 350-1.5

-1.0

-0.5

0.0

0.5

1.0 4g

Abso

rban

ce

Wavelength (nm)

28

4h

30

250 275 300 325 350 375 400 425 450-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

4h

Abso

rban

ce (n

m)

Wavelength

31

4i

33


m/z75 100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800

%

0

100JANDEEP 4i 16 (0.218) AM (Top,4, Ar,5000.0,556.28,0.70,LS 10); Sm (Mn, 2x3.00); Sb (1,40.00 ); Cm (16) 1: TOF MS ES+

4.79e3592.23654789

570.25863084

301.0778470

279.0841449102.1311

431

181.092371

103.131522

242.135160

524.2245213302.0746

62 443.645955

343.192030

422.218917

466.15975

593.25501590

594.2508272

671.396890608.2305;89 728.2656

43789.3711

24

34

250 275 300 325 350 375 400-0.8

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4 4i

Wav

elen

gth

(nm

)

Absorbance

35

6a

37

250 275 300 325 350 375 4000.0

0.5

1.0

1.5

2.0

6a

Abso

rban

ce

Wavelength (nm)

38

6b

40

250 275 300 325 350 375 400

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

6b

Abso

rban

ce

Wavelength (nm)

41

6c

43


m/z100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000

%

0

100JANDEEP 6b 23 (0.288) Cm (7:30) TOF MS ES+

6.47e3833.56470

811.62243

444.31196

301.1661102.2

444279.1423

425.3628

586.41178

564.4484445.3

261 475.4201

765.5599587.4

373632.4195 766.5

264

834.52665

835.6718

879.6486

880.6;229

44

6d

46

250 275 300 325 350 375 4000.0

0.5

1.0

1.5

2.0

2.5 6d

Abso

rban

ce

Wavelength (nm)

47

6e

49

250 275 300 325 350 375 4000.0

0.5

1.0

1.5

2.06e

Abso

rban

ce

Wavelength (nm)

50

6f

52

250 275 300 325 350 375 400-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

6f

Abso

rban

ce

Wavelength (nm)

53

6g

55

250 275 300 325 350 375 4000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.46g

Abso

rban

ce

Wavelength (nm)

56

6h

58

250 275 300 325 350 375 4000.0

0.2

0.4

0.6

0.8

1.0

1.2 6h

Abso

rban

ce

Wavelength (nm)

59

6i

61

250 275 300 325 350 375 4000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

6i

Abso

rban

ce

Wavelength (nm)

synthetic approach towards ‘click’ modified chalcone based ... · gurjaspreet singh,* jandeep...

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