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A family of stilbene-ethers as photolabile protecting groups for primary alcohols
offers controlled deprotection based on choice of wavelength
Jinn-Hsuan Ho*, Ya-Wen Lee, Ying-Zhe Chen, Pin-Sian Chen, Wei-Qi Liu, and Yi-Shun Ding
Department of Chemical Engineering, National Taiwan University of Science and Technology.
E-mail: [email protected]
Contents
1. 1H and
13C NMR of trans-1-(3-phenylpropoxy)-4-styrylbenzene (trans-1a)
2. 1H and
13C NMR of cis-1-(3-phenylpropoxy)-4-styrylbenzene (cis-1a)
3. 1H and
13C NMR of trans-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-furan (trans-1b)
4. 1H and
13C NMR of cis-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-furan (cis-1b)
5. 1H and
13C NMR of trans-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-thiophene (trans-1c)
6. 1H and
13C NMR of cis-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-thiophene (cis-1c)
7. 1H and
13C NMR of trans-4-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-benzonitrile (trans-1d)
8. 1H and
13C NMR of cis-4-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-benzonitrile (cis-1d)
9. 1H and
13C NMR of trans-1-ethoxy-4-(4-styrylphenoxy)benzene (trans-1e)
10. 1H and 13
C NMR of trans-1-propyl-4-(4-styrylphenoxy)benzene (trans-1f)
11. 1H and 13
C NMR of trans-2-(4-styrylphenoxy)naphthalene (trans-1g)
12. 1H and 13
C NMR of 1-benzyloxy-4-(trans-styryl)benzene (trans-1h)
13. 1H and 13
C NMR of 1-(cinnamyloxy)-4-(trans-styryl)benzene (trans-1i)
14. 1H NMR of trans-4-(naphthalen-2-yl)-but-3-en-2-one (trans-2a)
15. 1H NMR of trans-4-(benzo[b]furan-5-yl)-but-3-en-2-one (trans-2b)
16. 1H NMR of trans-4-(benzo[b]thiophen-5-yl)-but-3-en-2-one (trans-2c)
17. 1H NMR of trans-7-(3-oxo-but-1-enyl)-naphthalene-2-carbonitrile (trans-2d)
18. 1H and 13
C NMR of trans-4-fluorostilbene (trans-3a)
19. 1H and 13
C NMR of trans-4-fluorostyrylfuran (trans-3b)
20. 1H and 13
C NMR of trans-4-fluorostyrylthiophene (trans-3c)
21. 1H and 13
C NMR of 4-phenylbutan-2-ol (11)
22. 1H and 13
C NMR of 2-methyl-4-phenylbutan-2-ol (12)
23. 1H and 13
C NMR of 4-(3-phenylpropoxy)-benzaldehyde (A) (reactant for cis and trans-1d)
24. Test Experiment for Examining the Formation of Acid in Dichloromethane.
1H NMR of trans-1a
13
C NMR of trans-1a
O
(1a) trans
O
(1a) trans
1H NMR of cis-1a
13
C NMR of cis-1a
O
(1a) cis
O
(1a) cis
1H NMR of trans-1b
13
C NMR of trans-1b
OO
(1b) trans
OO
(1b) trans
1H NMR of cis-1b
13C NMR of cis-1b
O
(1b) cis
O
O
(1b) cis
O
1H NMR of trans-1c
13C NMR of trans-1c
SO
(1c) trans
SO
(1c) trans
1H NMR of cis-1c
13C NMR of cis-1c
O
(1c) cis
S
O
(1c) cis
S
1H NMR of trans-1d
13C NMR of trans-1d
O
(1d) trans
NC
O
(1d) trans
NC
1H NMR of cis-1d
13C NMR of cis-1d
O
(1d) cisCN
O
(1d) cisCN
1H NMR of trans-1e
13
C NMR of trans-1e
O
O
1e
O
O
1e
1H NMR of trans-1f
13
C NMR of trans-1f
O1f
O1f
1H NMR of trans-1g
13
C NMR of trans-1g
O
1g
O
1g
1H NMR of trans-1h
13C
NMR of trans-1h
O
trans-1h
O
trans-1h
1H NMR of trans-1i
13
C NMR of trans-1i
O
1i
O
1i
1H NMR of trans-2a
1H NMR of trans-2b
O
(2a) trans
(2b) trans
O
O
1H NMR of trans-2c
1H NMR of trans-2d
(2c) trans
S
O
O
(2d) trans
NC
1H NMR of trans-3a
13
C NMR of trans-3a
Ftrans-3a
Ftrans-3a
1H NMR of trans-3b
13
C NMR of trans-3b
F
O
trans-3b
F
O
trans-3b
1H NMR of trans-3c
13
C NMR of trans-3c
F
S
trans-3c
F
S
trans-3c
1H NMR of 5
13
C NMR of 5
OH
11
OH
11
1H NMR of 6
13
C NMR of 6
OH
12
OH
12
1H NMR of A
13
C NMR of A
O
H
O
A
O
H
O
A
24. Test Experiment for Examining the Formation of Acid in Dichloromethane:
We prepared 3 samples in quartz tubes as the following condition.
Tube1: Dichloromethane (20 mL) without irradiation.
Tube2: Dichloromethane (20 mL) under 300 nm-irradiation for 3 hours.
Tube3: Dichloromethane (20 mL) and compound 1a (20 mg) under 300 nm-irradiation for 3 hours.
After irradiation, we put few amount of 2-(4-(N,N-dimethylamino)styryl)quinoline (StQ) into the
quartz tubes. If the sample contains acid, protonated StQ will be obtained and the solution will
become red in color. If the sample does not contain acid, StQ will make the solution in light yellow
color.S1
The results of the test are shown in Fig S1. Unirradiated dichloromethane did not contain acid
(Tube1), but after irradiation, dichloromethane became acidic (Tube2). If irradiating
dichloromethane solution of 1a, the solution became even more acidic (Tube 3).
Fig. S1 The acidity of dichloromethane (DCM) tested by 2-(4-(N,N-dimethylamino)styryl)quinoline
(StQ). Tube1: unirradiated DCM; Tube2: irradiated DCM; Tube3: irradiated DCM solution of 1a.
Ref S1: Wang, S.-L.; Ho, T.-I. Chem. Phys. Lett. 1997, 268, 434.
N
N
N
N
HCl
HCl
light yellow in CH2Cl2 red in CH2Cl2
StQ Protonated StQ